Polymers

2022

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20 pages, 3662 KiB

Open AccessArticle

Study of the Dilution-Induced Deposition of Concentrated Mixtures of Polyelectrolytes and Surfactants

by Laura Fernández-Peña, Eduardo Guzmán, Coral Fernández-Pérez, Irene Barba-Nieto, Francisco Ortega, Fabien Leonforte, Ramón G. Rubio and Gustavo S. Luengo

Polymers 2022, 14(7), 1335; https://doi.org/10.3390/polym14071335 - 25 Mar 2022

Cited by 12 | Viewed by 3002

Abstract

Mixtures of polyelectrolytes and surfactants are commonly used in many technological applications where the challenge is to provide well-defined modifications of the surface properties, as is the case of washing formulations in cosmetics. However, if contemporary experimental and theoretical methods can provide insights [...] Read more.

Mixtures of polyelectrolytes and surfactants are commonly used in many technological applications where the challenge is to provide well-defined modifications of the surface properties, as is the case of washing formulations in cosmetics. However, if contemporary experimental and theoretical methods can provide insights on their behavior in concentrated formulations, less is known on their behavior under practical use conditions, e.g., under dilution and vectorization of deposits. This makes it difficult to make predictions for specific performance, as, for example, good hair manageability after a shampoo or a comfortable sensorial appreciation after a skin cleanser. This is especially important when considering the formulation of new, more eco-friendly formulations. In this work, a detailed study of the phase separation process induced by dilution is described, as well as the impact on the deposition of conditioning material on negatively charged surfaces. In order to gain a more detailed physical insight, several polyelectrolyte–surfactant pairs, formed by two different polymers and five surfactants that, although non-natural or eco-friendly, can be considered as models of classical formulations, have been studied. The results evidenced that upon dilution the behavior, and hence its deposition onto the surface, cannot be predicted in terms of the behavior of simpler pseudo-binary (mixtures of a polymer and a surfactant) or pseudo-ternary mixtures (two polymers and a surfactant). In many cases, phase separation was observed for concentrations similar to those corresponding to the components in some technological formulations, whereas the latter appeared as monophasic systems. Therefore, it may be assumed that the behavior in multicomponent formulations is the result of a complex interplay of synergistic interactions between the different components that will require revisiting when new, more eco-sustainable ingredients are considered. Full article

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2020

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23 pages, 4908 KiB

Open AccessReview

Strategies to Functionalize the Anionic Biopolymer Na-Alginate without Restricting Its Polyelectrolyte Properties

by Luca Szabó, Sandrine Gerber-Lemaire and Christine Wandrey

Polymers 2020, 12(4), 919; https://doi.org/10.3390/polym12040919 - 15 Apr 2020

Cited by 49 | Viewed by 8732

Abstract

The natural anionic polyelectrolyte alginate and its derivatives are of particular interest for pharmaceutical and biomedical applications. Most interesting for such applications are alginate hydrogels, which can be processed into various shapes, self-standing or at surfaces. Increasing efforts are underway to functionalize the [...] Read more.

The natural anionic polyelectrolyte alginate and its derivatives are of particular interest for pharmaceutical and biomedical applications. Most interesting for such applications are alginate hydrogels, which can be processed into various shapes, self-standing or at surfaces. Increasing efforts are underway to functionalize the alginate macromolecules prior to hydrogel formation in order to overcome the shortcomings of purely ionically cross-linked alginate hydrogels that are hindering the progress of several sophisticated biomedical applications. Particularly promising are derivatives of alginate, which allow simultaneous ionic and covalent cross-linking to improve the physical properties and add biological activity to the hydrogel. This review will report recent progress in alginate modification and functionalization with special focus on synthesis procedures, which completely conserve the ionic functionality of the carboxyl groups along the backbone. Recent advances in analytical techniques and instrumentation supported the goal-directed modification and functionalization. Full article

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14 pages, 7288 KiB

Open AccessArticle

Electrical Field-Assisted Gene Delivery from Polyelectrolyte Multilayers

by Yu-Che Cheng, Shu-Lin Guo, Kun-Da Chung and Wei-Wen Hu

Polymers 2020, 12(1), 133; https://doi.org/10.3390/polym12010133 - 6 Jan 2020

Cited by 3 | Viewed by 2944

Abstract

To sustain gene delivery and elongate transgene expression, plasmid DNA and cationic nonviral vectors can be deposited through layer-by-layer (LbL) assembly to form polyelectrolyte multilayers (PEMs). Although these macromolecules can be released for transfection purposes, their entanglement only allows partial delivery. Therefore, how [...] Read more.

To sustain gene delivery and elongate transgene expression, plasmid DNA and cationic nonviral vectors can be deposited through layer-by-layer (LbL) assembly to form polyelectrolyte multilayers (PEMs). Although these macromolecules can be released for transfection purposes, their entanglement only allows partial delivery. Therefore, how to efficiently deliver immobilized genes from PEMs remains a challenge. In this study, we attempt to facilitate their delivery through the pretreatment of the external electrical field. Multilayers of polyethylenimine (PEI) and DNA were deposited onto conductive polypyrrole (PPy), which were placed in an aqueous environment to examine their release after electric field pretreatment. Only the electric field perpendicular to the substrate with constant voltage efficiently promoted the release of PEI and DNA from PEMs, and the higher potential resulted in the more releases which were enhanced with treatment time. The roughness of PEMs also increased after electric field treatment because the electrical field not only caused electrophoresis of polyelectrolytes and but also allowed electrochemical reaction on the PPy electrode. Finally, the released DNA and PEI were used for transfection. Polyplexes were successfully formed after electric field treatment, and the transfection efficiency was also improved, suggesting that this electric field pretreatment effectively assists gene delivery from PEMs and should be beneficial to regenerative medicine application. Full article

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2019

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22 pages, 9484 KiB

Open AccessArticle

Enhanced Pervaporation Properties of PVA-Based Membranes Modified with Polyelectrolytes. Application to IPA Dehydration

by Mariia Dmitrenko, Anna Kuzminova, Andrey Zolotarev, Sergey Ermakov, Denis Roizard and Anastasia Penkova

Polymers 2020, 12(1), 14; https://doi.org/10.3390/polym12010014 - 19 Dec 2019

Cited by 22 | Viewed by 4764

Abstract

In this work, dense and supported pervaporation polyvinyl alcohol (PVA)-based membranes modified with poly(allylamine hydrochloride) (PAH) and poly(sodium 4-styrenesulfonate)(PSS)/PAH top nanolayers were synthesized. Two main points were investigated: the role of the polyelectrolyte PAH on water selectivity of the selective polymer matrix and [...] Read more.

In this work, dense and supported pervaporation polyvinyl alcohol (PVA)-based membranes modified with poly(allylamine hydrochloride) (PAH) and poly(sodium 4-styrenesulfonate)(PSS)/PAH top nanolayers were synthesized. Two main points were investigated: the role of the polyelectrolyte PAH on water selectivity of the selective polymer matrix and the impact of the porous substrate based on polyacrylonitrile (PAN) and aromatic polysulfone amide (UPM-20^®), used to get supported high-performance membranes. Various methods of analysis (fourier-transform infrared spectroscopy (FTIR), scanning electron microscopy (SEM), atomic force microscopy (AFM), small-angle X-ray scattering (SAXS), porosity, contact angles, ultrafiltration) were applied to study the developed membranes. Transport characteristics of the developed membranes were studied in isopropanol dehydration by pervaporation. Obtained results are discussed in the light of the structure and physicochemical characteristics of these PVA/PAH membranes and the types of porous substrate. It was shown that the PAN-supported membrane with the selective layer based on PVA/PAH modified by 10 polyelectrolyte PSS/PAH bilayers possessed ~4.5 times higher permeation flux with the same high selectivity level (99.9 wt % water in the permeate) for the dehydration of the isopropanol (20 wt % water) at 60 °C compared to the commercial analog PERVAP^TM 1201. Full article

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15 pages, 1512 KiB

Open AccessArticle

Revealing Adsorption Behaviors of Amphoteric Polyacrylamide on Cellulose Fibers and Impact on Dry Strength of Fiber Networks

by Xinyu Zhang, Yangyang Zhu, Xiaoyan Wang, Peipei Wang, Jing Tian, Wenyuan Zhu, Junlong Song and Huining Xiao

Polymers 2019, 11(11), 1886; https://doi.org/10.3390/polym11111886 - 15 Nov 2019

Cited by 16 | Viewed by 2981

Abstract

Amphoteric polyacrylamide (AmPAM) has been widely used in a variety of industrial areas and the adsorption behavior of AmPAM plays a crucial role in its applications. In this study, a series of AmPAMs with various molecular weights (MW) were synthesized; and their impact [...] Read more.

Amphoteric polyacrylamide (AmPAM) has been widely used in a variety of industrial areas and the adsorption behavior of AmPAM plays a crucial role in its applications. In this study, a series of AmPAMs with various molecular weights (MW) were synthesized; and their impact on dry strength of fiber networks or paper was assessed. The results showed that the optimal MW of AmPAM for strength enhancement ranged between 300 and 500 k. More importantly, the adsorption behaviors of three typical AmPAM samples on silica (model substrate) and cellulose surfaces were revealed using a quartz crystal microbalance with dissipation monitoring (QCM-D) in situ and in real time. The adsorption dynamics of AmPAM and the conformation of the adlayers were further derived. The results indicated that a relatively high adsorption amount was achieved under the conditions of a high polymer concentration, a medium pH close to its isoelectric point (IEP), a mild ionic strength, and a high charged surface; whereas the MW of AmPAM had little effect on the equilibrium adsorption mass of AmPAM, but significantly affected the conformation of adsorbed layer on substrates. Based on the adsorption behaviors of AmPAM, the explanation of the best dry strength achieved in a narrow range of MW of AmPAM is proposed. It was concluded that the appropriate balance between bridging and flocculation, penetration into fiber pores, and conformation were only achieved in the optimal MW range of AmPAM. The findings obtained from in this work enable us to better understand the adsorption behaviors of polyampholyte, and provide a guideline on molecular design of AmPAM and its applications from both fundamental and practical points of view. Full article

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16 pages, 1936 KiB

Open AccessArticle

Synthesis, Characterisation and Biological Evaluation of Ampicillin–Chitosan–Polyanion Nanoparticles Produced by Ionic Gelation and Polyelectrolyte Complexation Assisted by High-Intensity Sonication

by Yhors Ciro, John Rojas, Jose Oñate-Garzon and Constain H. Salamanca

Polymers 2019, 11(11), 1758; https://doi.org/10.3390/polym11111758 - 25 Oct 2019

Cited by 28 | Viewed by 4038

Abstract

Recently, one of the promising strategies to fight sensitive and resistant bacteria, and decrease the morbidity and mortality rates due to non-nosocomial infections, is to use antibiotic-loaded nanoparticles. In this study, ampicillin-loaded chitosan–polyanion nanoparticles were produced through the techniques of ionic gelation and [...] Read more.

Recently, one of the promising strategies to fight sensitive and resistant bacteria, and decrease the morbidity and mortality rates due to non-nosocomial infections, is to use antibiotic-loaded nanoparticles. In this study, ampicillin-loaded chitosan–polyanion nanoparticles were produced through the techniques of ionic gelation and polyelectrolyte complexation assisted by high-intensity sonication, using several crosslinking agents, including phytic acid (non-polymeric polyanion), sodium and potassium salts of poly(maleic acid-alt-ethylene) and poly(maleic acid-alt-octadecene) (polymeric polyanions). These nanoparticles were analysed and characterised in terms of particle size, polydispersity index, zeta potential and encapsulation efficiency. The stability of these nanosystems was carried out at temperatures of 4 and 40 °C, and the antimicrobial effect was determined by the broth microdilution method using sensitive and resistant Staphylococcus aureus strains. The results reveal that most of the nanosystems have sizes <220 nm, positive zeta potential values and a monodisperse population, except for the nanoparticles crosslinked with PAM-18 polyanions. The nanometric systems exhibited adequate stability preventing aggregation and revealed a two-fold increase in antimicrobial activity when compared with free ampicillin. This study demonstrates the potential application of synthesised nanoparticles in the field of medicine, especially for treating infections caused by pathogenic S. aureus strains. Full article

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24 pages, 4966 KiB

Open AccessEditor’s ChoiceArticle

Employing of Trukhan Model to Estimate Ion Transport Parameters in PVA Based Solid Polymer Electrolyte

by Shujahadeen B. Aziz, Rawezh B. Marif, M. A. Brza, M. H. Hamsan and M. F. Z. Kadir

Polymers 2019, 11(10), 1694; https://doi.org/10.3390/polym11101694 - 16 Oct 2019

Cited by 66 | Viewed by 4840

Abstract

In the current paper, ion transport parameters in poly (vinyl alcohol) (PVA) based solid polymer electrolyte were examined using Trukhan model successfully. The desired amount of lithium trifluoromethanesulfonate (LiCF₃SO₃) was dissolved in PVA host polymer to synthesis of solid [...] Read more.

In the current paper, ion transport parameters in poly (vinyl alcohol) (PVA) based solid polymer electrolyte were examined using Trukhan model successfully. The desired amount of lithium trifluoromethanesulfonate (LiCF₃SO₃) was dissolved in PVA host polymer to synthesis of solid polymer electrolytes (SPEs). Ion transport parameters such as mobility (μ), diffusion coefficient (D), and charge carrier number density (n) are investigated in detail using impedance spectroscopy. The data results from impedance plots illustrated a decrement of bulk resistance with an increase in temperature. Using electrical equivalent circuits (EEC), electrical impedance plots (ZivsZr) are fitted at various temperatures. The results of impedance study demonstrated that the resistivity of the sample decreases with increasing temperature. The decrease of resistance or impedance with increasing temperature distinguished from Bode plots. The dielectric constant and dielectric loss values increased with an increase in temperature. The loss tangent peaks shifted to higher frequency region and the intensity increased with an increase in temperature. In this contribution, ion transport as a complicated subject in polymer physics is studied. The conductivity versus reciprocal of temperature was found to obey Arrhenius behavior type. The ion transport mechanism is discussed from the tanδ spectra. The ion transport parameters at ambient temperature are found to be 9 × 10⁻⁸ cm²/s, 0.8 × 10¹⁷ cm⁻³, and 3 × 10⁻⁶ cm²/Vs for D, n, andμ respectively. All these parameters have shown increasing as temperature increased. The electric modulus parameters are studied in an attempt to understand the relaxation dynamics and to clarify the relaxation process and ion dynamics relationship. Full article

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8 pages, 3396 KiB

Open AccessArticle

Novel Ruthenium-Silver PTA-Based Polymers and Their Behavior in Water

by Benjamin Sierra-Martin, Manuel Serrano-Ruiz, Franco Scalambra, Antonio Fernandez-Barbero and Antonio Romerosa

Polymers 2019, 11(8), 1249; https://doi.org/10.3390/polym11081249 - 28 Jul 2019

Cited by 7 | Viewed by 2897

Abstract

New coordination polymers based on two metal-containing moieties Ru–Ag are synthesized: Na[RuCpX(PTA)-μ-(PTA)-1κP:2κ²N-AgX₂]_∞ (X = Cl (1), Br (2), I (3)). Characterization is performed by NMR, UV-visible and FT-IR spectroscopy, [...] Read more.

New coordination polymers based on two metal-containing moieties Ru–Ag are synthesized: Na[RuCpX(PTA)-μ-(PTA)-1κP:2κ²N-AgX₂]_∞ (X = Cl (1), Br (2), I (3)). Characterization is performed by NMR, UV-visible and FT-IR spectroscopy, optical-electron microscopy, and elemental analyses (C, H, N, S). Light scattering is employed to characterize the colloidal particles growth by polymer self-assembling. These structures are stable over a broad range of pH and exhibit thermally-driven swelling, thus resembling a typical thermosensitive hydrogel. Full article

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19 pages, 2095 KiB

Open AccessArticle

Effects of Chain Length of Chitosan Oligosaccharides on Solution Properties and Complexation with siRNA

by Tim Delas, Maxime Mock-Joubert, Jimmy Faivre, Mirjam Hofmaier, Olivier Sandre, François Dole, Jean Paul Chapel, Agnès Crépet, Stéphane Trombotto, Thierry Delair and Christophe Schatz

Polymers 2019, 11(8), 1236; https://doi.org/10.3390/polym11081236 - 25 Jul 2019

Cited by 20 | Viewed by 4597

Abstract

In the context of gene delivery, chitosan has been widely used as a safe and effective polycation to complex DNA, RNA and more recently, siRNA. However, much less attention has been paid to chitosan oligosaccharides (COS) despite their biological properties. This study proposed [...] Read more.

In the context of gene delivery, chitosan has been widely used as a safe and effective polycation to complex DNA, RNA and more recently, siRNA. However, much less attention has been paid to chitosan oligosaccharides (COS) despite their biological properties. This study proposed to carry out a physicochemical study of COS varying in degree of polymerization (DP) from 5 to 50, both from the point of view of the solution properties and the complexing behavior with siRNA. The main parameters studied as a function of DP were the apparent pK_a, the solubility versus pH, the binding affinity with siRNA and the colloidal properties of complexes. Some parameters, like the pK_a or the binding enthalpy with siRNA, showed a marked transition from DP 5 to DP 13, suggesting that electrostatic properties of COS vary considerably in this range of DP. The colloidal properties of siRNA/COS complexes were affected in a different way by the COS chain length. In particular, COS of relatively high DP (≥50) were required to form small complex particles with good stability. Full article

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18 pages, 1440 KiB

Open AccessArticle

Role of Protein Self-Association on DNA Condensation and Nucleoid Stability in a Bacterial Cell Model

by Rita S. Dias

Polymers 2019, 11(7), 1102; https://doi.org/10.3390/polym11071102 - 29 Jun 2019

Cited by 6 | Viewed by 3474

Abstract

Bacterial cells do not have a nuclear membrane that encompasses and isolates the genetic material. In addition, they do not possess histone proteins, which are responsible for the first levels of genome condensation in eukaryotes. Instead, there is a number of more or [...] Read more.

Bacterial cells do not have a nuclear membrane that encompasses and isolates the genetic material. In addition, they do not possess histone proteins, which are responsible for the first levels of genome condensation in eukaryotes. Instead, there is a number of more or less specific nucleoid-associated proteins that induce DNA bridging, wrapping and bending. Many of these proteins self-assemble into oligomers. The crowded environment of cells is also believed to contribute to DNA condensation due to excluded volume effects. Ribosomes are protein-RNA complexes found in large concentrations in the cytosol of cells. They are overall negatively charged and some DNA-binding proteins have been reported to also bind to ribosomes. Here the effect of protein self-association on DNA condensation and stability of DNA-protein complexes is explored using Monte Carlo simulations and a simple coarse-grained model. The DNA-binding proteins are described as positively charged dimers with the same linear charge density as the DNA, described using a bead and spring model. The crowding molecules are simply described as hard-spheres with varying charge density. It was found that applying a weak attractive potential between protein dimers leads to their association in the vicinity of the DNA (but not in its absence), which greatly enhances the condensation of the model DNA. The presence of neutral crowding agents does not affect the DNA conformation in the presence or absence of protein dimers. For weakly self-associating proteins, the presence of negatively charged crowding particles induces the dissociation of the DNA-protein complex due to the partition of the proteins between the DNA and the crowders. Protein dimers with stronger association potentials, on the other hand, stabilize the nucleoid, even in the presence of highly charged crowders. The interactions between protein dimers and crowding agents are not completely prevented and a few crowding molecules typically bind to the nucleoid. Full article

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34 pages, 7461 KiB

Open AccessReview

Protein–Polyelectrolyte Complexes and Micellar Assemblies

by Shang Gao, Advait Holkar and Samanvaya Srivastava

Polymers 2019, 11(7), 1097; https://doi.org/10.3390/polym11071097 - 28 Jun 2019

Cited by 73 | Viewed by 11277

Abstract

In this review, we highlight the recent progress in our understanding of the structure, properties and applications of protein–polyelectrolyte complexes in both bulk and micellar assemblies. Protein–polyelectrolyte complexes form the basis of the genetic code, enable facile protein purification, and have emerged as [...] Read more.

In this review, we highlight the recent progress in our understanding of the structure, properties and applications of protein–polyelectrolyte complexes in both bulk and micellar assemblies. Protein–polyelectrolyte complexes form the basis of the genetic code, enable facile protein purification, and have emerged as enterprising candidates for simulating protocellular environments and as efficient enzymatic bioreactors. Such complexes undergo self-assembly in bulk due to a combined influence of electrostatic interactions and entropy gains from counterion release. Diversifying the self-assembly by incorporation of block polyelectrolytes has further enabled fabrication of protein–polyelectrolyte complex micelles that are multifunctional carriers for therapeutic targeted delivery of proteins such as enzymes and antibodies. We discuss research efforts focused on the structure, properties and applications of protein–polyelectrolyte complexes in both bulk and micellar assemblies, along with the influences of amphoteric nature of proteins accompanying patchy distribution of charges leading to unique phenomena including multiple complexation windows and complexation on the wrong side of the isoelectric point. Full article

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8 pages, 2770 KiB

Open AccessArticle

Structure and Rheology of Polyelectrolyte Complexes in the Presence of a Hydrogen-Bonded Co-Solvent

by Mor Boas, Gleb Vasilyev, Rita Vilensky, Yachin Cohen and Eyal Zussman

Polymers 2019, 11(6), 1053; https://doi.org/10.3390/polym11061053 - 17 Jun 2019

Cited by 11 | Viewed by 4127

Abstract

Intermolecular interactions as well as macromolecular conformation affect the rheological and microstructural properties of polyelectrolyte complexes (PECs) solutions. The properties of semi-dilute solutions of weakly charged PECs can be controlled by the degree of ionization and solvent composition. In this work, we examined [...] Read more.

Intermolecular interactions as well as macromolecular conformation affect the rheological and microstructural properties of polyelectrolyte complexes (PECs) solutions. The properties of semi-dilute solutions of weakly charged PECs can be controlled by the degree of ionization and solvent composition. In this work, we examined the effect of ethanol as a co-solvent on PECs composed of poly(allylamine hydrochloride) (PAH) and poly(acrylic acid) (PAA) at low pH. The aqueous PECs solution was turbid, indicating formation of large aggregates, whereas PECs solution in water/ethanol (60:40 w/w) was transparent, implying no aggregation, and demonstrated higher relative viscosity than the aqueous solution, implying pronounced network formation. Imaging PECs solution by transmission electron microscopy (TEM) demonstrated aggregation, whereas the solution prepared with the mixed solvent revealed almost no phase contrast. Small-angle X-ray scattering (SAXS) of PECs in the aqueous solution indicated the presence of aggregates, while PECs in mixed solvent demonstrated a swelled macromolecular conformation with diminished aggregation. PECs with no ionic interactions in the mixed solvent assumes a homogenous network structure, which enables PECs solution processing by electrospinning. Full article

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23 pages, 1223 KiB

Open AccessEditor’s ChoiceReview

Intrinsic Disorder-Based Emergence in Cellular Biology: Physiological and Pathological Liquid-Liquid Phase Transitions in Cells

by April L. Darling, Boris Y. Zaslavsky and Vladimir N. Uversky

Polymers 2019, 11(6), 990; https://doi.org/10.3390/polym11060990 - 4 Jun 2019

Cited by 57 | Viewed by 5591

Abstract

The visible outcome of liquid-liquid phase transitions (LLPTs) in cells is the formation and disintegration of various proteinaceous membrane-less organelles (PMLOs). Although LLPTs and related PMLOs have been observed in living cells for over 200 years, the physiological functions of these transitions (also [...] Read more.

The visible outcome of liquid-liquid phase transitions (LLPTs) in cells is the formation and disintegration of various proteinaceous membrane-less organelles (PMLOs). Although LLPTs and related PMLOs have been observed in living cells for over 200 years, the physiological functions of these transitions (also known as liquid-liquid phase separation, LLPS) are just starting to be understood. While unveiling the functionality of these transitions is important, they have come into light more recently due to the association of abnormal LLPTs with various pathological conditions. In fact, several maladies, such as various cancers, different neurodegenerative diseases, and cardiovascular diseases, are known to be associated with either aberrant LLPTs or some pathological transformations within the resultant PMLOs. Here, we will highlight both the physiological functions of cellular liquid-liquid phase transitions as well as the pathological consequences produced through both dysregulated biogenesis of PMLOs and the loss of their dynamics. We will also discuss the potential downstream toxic effects of proteins that are involved in pathological formations. Full article

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18 pages, 3923 KiB

Open AccessArticle

Interactions of Casein and Polypeptides in Multilayer Films Studied by FTIR and Molecular Dynamics

by Lilianna Szyk-Warszyńska, Katarzyna Raszka and Piotr Warszyński

Polymers 2019, 11(5), 920; https://doi.org/10.3390/polym11050920 - 25 May 2019

Cited by 28 | Viewed by 4935

Abstract

Multilayer films containing α- and β-casein and polypeptides, poly-L-lysine (PLL), and poly-L-arginine (PLArg) were formed by the layer-by-layer technique and Fourier Transform InfraRed spectroscopy with Attenuated Total Reflection (FTIR-ATR) and FTIR/Grazing Angle analyzed their infrared spectra. We investigated the changes of conformations of [...] Read more.

Multilayer films containing α- and β-casein and polypeptides, poly-L-lysine (PLL), and poly-L-arginine (PLArg) were formed by the layer-by-layer technique and Fourier Transform InfraRed spectroscopy with Attenuated Total Reflection (FTIR-ATR) and FTIR/Grazing Angle analyzed their infrared spectra. We investigated the changes of conformations of casein and polypeptides in the complexes formed during the build-up of the films. To elucidate the differences in the mechanism of complex formation leading to various growths of (PLL/casein)_n and (PLArg/casein)_n films, we performed the molecular dynamics simulations of the systems consisting of short PLL and PLArg chains and the representative peptide chains—casein fragments, which consists of several aminoacid sequences. The results of the simulation indicated the preferential formation of hydrogen bonds of poly-L-arginine with phosphoserine and glutamic acid residues of caseins. FTIR spectra confirmed those, which revealed greater conformational changes during the formation of casein complex with poly-L-arginine than with poly-L-lysine resulting from stronger interactions, which was also reflected in the bigger growth of (PLArg/casein)_n films with the number of deposited layers. Full article

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11 pages, 3731 KiB

Open AccessArticle

Simultaneous Measurements of Structure and Water Permeability in an Isolated Human Skin Stratum Corneum Sheet

by Hiromitsu Nakazawa, Tomohiro Imai, Mika Suzuki, Natsuki Akakabe, Ichiro Hatta and Satoru Kato

Polymers 2019, 11(5), 829; https://doi.org/10.3390/polym11050829 - 8 May 2019

Cited by 7 | Viewed by 3270

Abstract

Stratum corneum (SC), the outermost layer of human skin, acts as an intelligent physicochemical interface between the inside and the outside of our body. To make clear the relationship between structure and physical barrier properties of SC, we developed a method that enables [...] Read more.

Stratum corneum (SC), the outermost layer of human skin, acts as an intelligent physicochemical interface between the inside and the outside of our body. To make clear the relationship between structure and physical barrier properties of SC, we developed a method that enables us to simultaneously acquire X-ray diffraction (XD) patterns and transepidermal water loss (TEWL) values using a spread SC sheet isolated from human skin. The synchrotron X-ray was incident on the SC sheet surface at an angle of 45° to avoid interference between the two kinds of measurements. Detailed comparison between XD and TEWL data suggested that the thermal behavior of water permeability is closely related to the thermal expansion of the lattice spacings of the hexagonal phases above 40 °C and to the existence ratio of the orthorhombic phase below 40 °C. Thus, the new method we developed can give useful information on the mechanism of water permeation in SC without ambiguity caused by separate measurements of structure and water permeability with different samples. Full article

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20 pages, 4947 KiB

Open AccessEditor’s ChoiceArticle

Effect of Solution Composition Variables on Electrospun Alginate Nanofibers: Response Surface Analysis

by Janja Mirtič, Helena Balažic, Špela Zupančič and Julijana Kristl

Polymers 2019, 11(4), 692; https://doi.org/10.3390/polym11040692 - 16 Apr 2019

Cited by 56 | Viewed by 5550

Abstract

Alginate is a promising biocompatible and biodegradable polymer for production of nanofibers for drug delivery and tissue engineering. However, alginate is difficult to electrospin due to its polyelectrolyte nature. The aim was to improve the ‘electrospinability’ of alginate with addition of exceptionally high [...] Read more.

Alginate is a promising biocompatible and biodegradable polymer for production of nanofibers for drug delivery and tissue engineering. However, alginate is difficult to electrospin due to its polyelectrolyte nature. The aim was to improve the ‘electrospinability’ of alginate with addition of exceptionally high molecular weight poly(ethylene oxide) (PEO) as a co-polymer. The compositions of the polymer-blend solutions for electrospinning were varied for PEO molecular weight, total (alginate plus PEO) polymer concentration, and PEO proportion in the dry alginate–PEO polymer mix used. These were tested for rheology (viscosity, complex viscosity, storage and loss moduli) and conductivity, and the electrospun nanofibers were characterized by scanning electron microscopy. One-parameter-at-a-time approach and response surface methodology (RSM) were used to optimize the polymer-blend solution composition to obtain defined nanofibers. Both approaches revealed that the major influence on nanofiber formation and diameter were total polymer concentration and PEO proportion. These polymer-blend solutions of appropriate conductivity and viscosity enabled fine-tuning of nanofiber diameter. PEO molecular weight of 2–4 million Da greatly improved the electrospinnability of alginate, producing nanofibers with >85% alginate. This study shows that RSM can be used to design nanofibers with optimal alginate and co-polymer contents to provide efficient scaffold material for regenerative medicine. Full article

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11 pages, 2391 KiB

Open AccessArticle

Upper Critical Solution Temperature (UCST) Behavior of Coacervate of Cationic Protamine and Multivalent Anions

by Hyungbin Kim, Byoung-jin Jeon, Sangsik Kim, YongSeok Jho and Dong Soo Hwang

Polymers 2019, 11(4), 691; https://doi.org/10.3390/polym11040691 - 16 Apr 2019

Cited by 31 | Viewed by 7953

Abstract

Complex coacervation is an emerging liquid/liquid phase separation (LLPS) phenomenon that behaves as a membrane-less organelle in living cells. Yet while one of the critical factors for complex coacervation is temperature, little analysis and research has been devoted to the temperature effect on [...] Read more.

Complex coacervation is an emerging liquid/liquid phase separation (LLPS) phenomenon that behaves as a membrane-less organelle in living cells. Yet while one of the critical factors for complex coacervation is temperature, little analysis and research has been devoted to the temperature effect on complex coacervation. Here, we performed a complex coacervation of cationic protamine and multivalent anions (citrate and tripolyphosphate (TPP)). Both mixtures (i.e., protamine/citrate and protamine/TPP) underwent coacervation in an aqueous solution, while a mixture of protamine and sodium chloride did not. Interestingly, the complex coacervation of protamine and multivalent anions showed upper critical solution temperature (UCST) behavior, and the coacervation of protamine and multivalent anions was reversible with solution temperature changes. The large asymmetry in molecular weight between positively charged protamine (~4 kDa) and the multivalent anions (<0.4 kDa) and strong electrostatic interactions between positively charged guanidine residues in protamine and multivalent anions were likely to contribute to UCST behavior in this coacervation system. Full article

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12 pages, 1996 KiB

Open AccessEditor’s ChoiceReview

Polyelectrolyte Complexes of Natural Polymers and Their Biomedical Applications

by Masayuki Ishihara, Satoko Kishimoto, Shingo Nakamura, Yoko Sato and Hidemi Hattori

Polymers 2019, 11(4), 672; https://doi.org/10.3390/polym11040672 - 12 Apr 2019

Cited by 89 | Viewed by 9677

Abstract

Polyelectrolyte complexes (PECs), composed of natural and biodegradable polymers, (such as positively charged chitosan or protamine and negatively charged glycosaminoglycans (GAGs)) have attracted attention as hydrogels, films, hydrocolloids, and nano-/micro-particles (N/MPs) for biomedical applications. This is due to their biocompatibility and biological activities. [...] Read more.

Polyelectrolyte complexes (PECs), composed of natural and biodegradable polymers, (such as positively charged chitosan or protamine and negatively charged glycosaminoglycans (GAGs)) have attracted attention as hydrogels, films, hydrocolloids, and nano-/micro-particles (N/MPs) for biomedical applications. This is due to their biocompatibility and biological activities. These PECs have been used as drug and cell delivery carriers, hemostats, wound dressings, tissue adhesives, and scaffolds for tissue engineering. In addition to their comprehensive review, this review describes our original studies and provides an overview of the characteristics of chitosan-based hydrogel, including photo-cross-linkable chitosan hydrogel and hydrocolloidal PECs, as well as molecular-weight heparin (LH)/positively charged protamine (P) N/MPs. These are generated by electrostatic interactions between negatively charged LH and positively charged P together with their potential biomedical applications. Full article

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15 pages, 1879 KiB

Open AccessArticle

Aqueous Liquid-Liquid Phase Separation of Natural and Synthetic Polyguanidiniums

by Leland J. Prather, G. Mahika Weerasekare, Monika Sima, Colette Quinn and Russell J. Stewart

Polymers 2019, 11(4), 649; https://doi.org/10.3390/polym11040649 - 9 Apr 2019

Cited by 19 | Viewed by 5333

Abstract

Protamines are natural polyguanidiniums, arginine(R)-rich proteins involved in the compaction of chromatin during vertebrate spermatogenesis. Salmine, a protamine isolated from salmon sperm, contains 65 mol% R residues, with positively charged guanidino (Gdm⁺) sidechains, and no other amino acids with ionizable or [...] Read more.

Protamines are natural polyguanidiniums, arginine(R)-rich proteins involved in the compaction of chromatin during vertebrate spermatogenesis. Salmine, a protamine isolated from salmon sperm, contains 65 mol% R residues, with positively charged guanidino (Gdm⁺) sidechains, and no other amino acids with ionizable or aromatic sidechains. Salmine sulfate solutions undergo liquid-liquid phase separation (LLPS) with a concentration-dependent upper critical solution temperature (UCST). The condensed liquid phase comprises 50 wt % water and >600 mg·mL⁻¹ salmine with a constant 1:2 ratio of sulfate (SO₄²⁻) to Gdm⁺. Isothermal titration calorimetry, titrating Na₂SO₄ into salmine chloride above and below the UCST, allowed isolation of exothermic sulfate binding to salmine chloride from subsequent endothermic condensation and exothermic phase separation events. Synthetic random polyacrylate analogs of salmine, with 3-guanidinopropyl sidechains, displayed similar counterion dependent phase behavior, demonstrating that the LLPS of polyguanidiniums does not depend upon subunit sequence or polymer backbone chirality, and was due entirely to Gdm⁺ sidechain interactions. The results provide experimental evidence for like-charge pairing of Gdm⁺ sidechains, and an experimental approach for further characterizing these interactions. Full article

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18 pages, 2013 KiB

Open AccessArticle

Effect of Multivalent Cations on Intermolecular Association of Isotactic and Atactic Poly(Methacrylic Acid) Chains in Aqueous Solutions

by Patricija Hriberšek and Ksenija Kogej

Polymers 2019, 11(4), 605; https://doi.org/10.3390/polym11040605 - 2 Apr 2019

Cited by 8 | Viewed by 3170

Abstract

The formation of nanoparticles of two poly(methacrylic acid) (PMA) isomers, atactic (aPMA) and isotactic (iPMA), was investigated in aqueous solutions in the presence of mono- (Na⁺) and multivalent cations (Mg²⁺ and La³⁺). Using dynamic (DLS) and static light [...] Read more.

The formation of nanoparticles of two poly(methacrylic acid) (PMA) isomers, atactic (aPMA) and isotactic (iPMA), was investigated in aqueous solutions in the presence of mono- (Na⁺) and multivalent cations (Mg²⁺ and La³⁺). Using dynamic (DLS) and static light scattering (SLS), we show that PMA nanoparticles have characteristics of microgel-like particles with a denser core and a swollen corona. iPMA aggregates are stable at a much higher degree of neutralization (α_N) than the aPMA ones, indicating a much stronger association between iPMA chains. This is explained by proposing segregation of ionized and unionized carboxyl groups within the iPMA aggregates and subsequent cooperative hydrogen-bonding between COOH groups. The calculated shape parameter (ρ) suggests different behavior of both isomers in the presence of Mg²⁺ ions on one hand and Na⁺ and La³⁺ on the other. The microgel-like particles formed in the presence of Mg²⁺ ions have a more even mass distribution (possibly a no core-shell structure) in comparison with those in the presence of Na⁺ and La³⁺ ions. Differences between the aggregate structures in the presence of different ions are reflected also in calorimetric experiments and supported by pH and fluorimetric measurements. Reasons for different behavior in the presence of Mg²⁺ ions lie in specific properties of this cation, in particular in its strong hydration and preference towards monodentate binding to carboxylate groups. Full article

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13 pages, 3918 KiB

Open AccessArticle

Effect of Material Composition on Tunable Surface Roughness of Magnetoactive Elastomers

by Gašper Glavan, Wolfgang Kettl, Alexander Brunhuber, Mikhail Shamonin and Irena Drevenšek-Olenik

Polymers 2019, 11(4), 594; https://doi.org/10.3390/polym11040594 - 1 Apr 2019

Cited by 23 | Viewed by 4576

Abstract

We investigated magnetic-field-induced modifications of the surface roughness of magnetoactive elastomers (MAEs) with four material compositions incorporating two concentrations of ferromagnetic microparticles (70 wt% and 80 wt%) and exhibiting two shear storage moduli of the resulting composite material (about 10 kPa and 30 [...] Read more.

We investigated magnetic-field-induced modifications of the surface roughness of magnetoactive elastomers (MAEs) with four material compositions incorporating two concentrations of ferromagnetic microparticles (70 wt% and 80 wt%) and exhibiting two shear storage moduli of the resulting composite material (about 10 kPa and 30 kPa). The analysis was primarily based on spread optical reflection measurements. The surfaces of all four materials were found to be very smooth in the absence of magnetic field (RMS roughness below 50 nm). A maximal field-induced roughness modification (approximately 1 μm/T) was observed for the softer material with the lower filler concentration, and a minimal modification (less than 50 nm/T) was observed for the harder material with the higher filler concentration. All four materials showed a significant decrease in the total optical reflectivity with an increasing magnetic field as well. This effect is attributed to the existence of a distinct surface layer that is depleted of microparticles in the absence of a magnetic field but becomes filled with particles in the presence of the field. We analyzed the temporal response of the reflective properties to the switching on and off of the magnetic field and found switching-on response times of around 0.1 s and switching-off response times in the range of 0.3–0.6 s. These observations provide new insight into the magnetic-field-induced surface restructuring of MAEs and may be useful for the development of magnetically reconfigurable elastomeric optical surfaces. Full article

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26 pages, 4269 KiB

Open AccessEditor’s ChoiceReview

Macro- and Microphase Separated Protein-Polyelectrolyte Complexes: Design Parameters and Current Progress

by Justin M. Horn, Rachel A. Kapelner and Allie C. Obermeyer

Polymers 2019, 11(4), 578; https://doi.org/10.3390/polym11040578 - 29 Mar 2019

Cited by 61 | Viewed by 11069

Abstract

Protein-containing polyelectrolyte complexes (PECs) are a diverse class of materials, composed of two or more oppositely charged polyelectrolytes that condense and phase separate near overall charge neutrality. Such phase-separation can take on a variety of morphologies from macrophase separated liquid condensates, to solid [...] Read more.

Protein-containing polyelectrolyte complexes (PECs) are a diverse class of materials, composed of two or more oppositely charged polyelectrolytes that condense and phase separate near overall charge neutrality. Such phase-separation can take on a variety of morphologies from macrophase separated liquid condensates, to solid precipitates, to monodispersed spherical micelles. In this review, we present an overview of recent advances in protein-containing PECs, with an overall goal of defining relevant design parameters for macro- and microphase separated PECs. For both classes of PECs, the influence of protein characteristics, such as surface charge and patchiness, co-polyelectrolyte characteristics, such as charge density and structure, and overall solution characteristics, such as salt concentration and pH, are considered. After overall design features are established, potential applications in food processing, biosensing, drug delivery, and protein purification are discussed and recent characterization techniques for protein-containing PECs are highlighted. Full article

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10 pages, 1712 KiB

Open AccessArticle

Ferrocene-Modified Polyelectrolyte Film-Coated Electrode and Its Application in Glucose Detection

by Zhiping Jiang, Yonggang Shangguan and Qiang Zheng

Polymers 2019, 11(3), 551; https://doi.org/10.3390/polym11030551 - 22 Mar 2019

Cited by 20 | Viewed by 5596

Abstract

A polyelectrolyte film-coated electrode for the quantitative detection of glucose was reported. Carbon nanotubes, graphene oxide and polyelectrolyte with a ferrocenyl group were used to modify an enzyme electrode to facilitate the electron transfer between glucose oxidase and the electrode. Cyclic voltammetry and [...] Read more.

A polyelectrolyte film-coated electrode for the quantitative detection of glucose was reported. Carbon nanotubes, graphene oxide and polyelectrolyte with a ferrocenyl group were used to modify an enzyme electrode to facilitate the electron transfer between glucose oxidase and the electrode. Cyclic voltammetry and amperometric methods were adopted to investigate the effects of different polyelectrolytes and carbon nanomaterials on the electrochemical properties of enzyme electrodes. The results indicate that the ferrocenyl groups on a polyelectrolyte skeleton act as a mediator between the redox center of glucose oxidase and the electrode, which efficiently enhances the electron transfer between a glassy carbon electrode and glucose oxidase. The calibration curve of the sensor shows a linear range from 0.2 to 5 mM for glucose response. The sensor can achieve 95% of the steady-state current within 10 s. The electrodes also present high operational stability and long-term storage stability. Full article

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15 pages, 3099 KiB

Open AccessArticle

Gelatin Films Modified with Acidic and Polyelectrolyte Polymers—Material Selection for Soft Gastroresistant Capsules

by Bartosz Maciejewski and Małgorzata Sznitowska

Polymers 2019, 11(2), 338; https://doi.org/10.3390/polym11020338 - 15 Feb 2019

Cited by 6 | Viewed by 5418

Abstract

The following investigation comprised the formation of acid-resistant gelatin-based films, intended for future use in soft-capsule technology. Such film compositions were obtained by including nonionized forms of acid-insoluble polymers in a gelatin-based film-forming mixture. The selected films were additionally modified with small amounts [...] Read more.

The following investigation comprised the formation of acid-resistant gelatin-based films, intended for future use in soft-capsule technology. Such film compositions were obtained by including nonionized forms of acid-insoluble polymers in a gelatin-based film-forming mixture. The selected films were additionally modified with small amounts of anionic polysaccharides that have potential to interact with gelatin, forming polyelectrolyte complexes. The obtained film compositions were subjected to, e.g., disintegration tests, adhesiveness tests, differential scanning calorimetry (DSC), and a transparency study. As a result of the performed study, some commercial enteric polymers (acrylates), as well as cellulose acetate phthalate, were selected as components that have the ability to coalesce and form a continuous phase within a gelatin film. The use of a small amount (1.5%) of additional gelling polymers improved the rheological characteristics and adhesive properties of the obtained films, with ί-carrageenan and gellan gum appearing to be the most beneficial. Full article

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13 pages, 2389 KiB

Open AccessArticle

Upper Critical Solution Temperature (UCST) Behavior of Polystyrene-Based Polyampholytes in Aqueous Solution

by Komol Kanta Sharker, Yuki Ohara, Yusuke Shigeta, Shinji Ozoe and Shin-ichi Yusa

Polymers 2019, 11(2), 265; https://doi.org/10.3390/polym11020265 - 4 Feb 2019

Cited by 20 | Viewed by 8816

Abstract

Strong polyampholytes comprising cationic vinylbenzyl trimethylammonium chloride (VBTAC) bearing a pendant quaternary ammonium group and anionic sodium p-styrenesulfonate (NaSS) bearing a pendant sulfonate group were prepared via reversible addition-fragmentation chain-transfer polymerization. The resultant polymers are labelled P(VBTAC/NaSS)_n, where n indicates [...] Read more.

Strong polyampholytes comprising cationic vinylbenzyl trimethylammonium chloride (VBTAC) bearing a pendant quaternary ammonium group and anionic sodium p-styrenesulfonate (NaSS) bearing a pendant sulfonate group were prepared via reversible addition-fragmentation chain-transfer polymerization. The resultant polymers are labelled P(VBTAC/NaSS)_n, where n indicates the degree of polymerization (n = 20 or 97). The percentage VBTAC content in P(VBTAC/NaSS)_n is always about 50 mol%, as revealed by ¹H NMR measurements, meaning that P(VBTAC/NaSS)_n is a close to stoichiometrically charge-neutralized polymer. Although P(VBTAC/NaSS)_n cannot dissolve in pure water at room temperature, the addition of NaCl or heating solubilizes the polymers. Furthermore, P(VBTAC/NaSS)_n exhibits upper critical solution temperature (UCST) behavior in aqueous NaCl solutions. The UCST is shifted to higher temperatures by increasing the polymer concentration and molecular weight, and by decreasing the NaCl concentration. The UCST behavior was measured ranging the polymer concentrations from 0.5 to 5.0 g/L. Full article

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14 pages, 3575 KiB

Open AccessArticle

Layer-by-Layer Assembly and Electrochemical Study of Alizarin Red S-Based Thin Films

by Wei Ma, Yanpu Zhang, Fei Li, Donghui Kou and Jodie L. Lutkenhaus

Polymers 2019, 11(1), 165; https://doi.org/10.3390/polym11010165 - 18 Jan 2019

Cited by 8 | Viewed by 6463

Abstract

Electroactive organic dyes incorporated in layer-by-layer (LbL) assemblies are of great interest for a variety of applications. In this paper, Alizarin Red S (ARS), an electroactive anthraquinone dye, is employed to construct LbL (BPEI/ARS)_n films with branched poly(ethylene imine) (BPEI) as the [...] Read more.

Electroactive organic dyes incorporated in layer-by-layer (LbL) assemblies are of great interest for a variety of applications. In this paper, Alizarin Red S (ARS), an electroactive anthraquinone dye, is employed to construct LbL (BPEI/ARS)_n films with branched poly(ethylene imine) (BPEI) as the complementary polymer. Unconventional LbL methods, including co-adsorption of ARS and poly(4-styrene sulfonate) (PSS) with BPEI to assemble (BPEI/(ARS+PSS))_n, as well as pre-complexation of ARS with BPEI and further assembly with PSS to fabricate ((BPEI+ARS)/PSS)_n, are designed for investigation and comparison. Film growth patterns, UV–Vis spectra and surface morphology of the three types of LbL assemblies are measured and compared to reveal the formation mechanism of the LbL films. Electrochemical properties including cyclic voltammetry and spectroelectrochemistry of (BPEI/ARS)₁₂₀, (BPEI/(ARS+PSS))₁₂₀ and ((BPEI+ARS)/PSS)₁₂₀ films are studied, and the results show a slight color change due to the redox reaction of ARS. ((BPEI+ARS)/PSS)₁₂₀ shows the best stability among the three samples. It is concluded that the manner of dye- incorporation has a great effect on the electrochemical properties of the resultant films. Full article

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15 pages, 5846 KiB

Open AccessEditor’s ChoiceArticle

Polyelectrolyte Complexation of Oligonucleotides by Charged Hydrophobic—Neutral Hydrophilic Block Copolymers

by Alexander E. Marras, Jeffrey R. Vieregg, Jeffrey M. Ting, Jack D. Rubien and Matthew V. Tirrell

Polymers 2019, 11(1), 83; https://doi.org/10.3390/polym11010083 - 7 Jan 2019

Cited by 40 | Viewed by 9188

Abstract

Polyelectrolyte complex micelles (PCMs, core-shell nanoparticles formed by complexation of a polyelectrolyte with a polyelectrolyte-hydrophilic neutral block copolymer) offer a solution to the critical problem of delivering therapeutic nucleic acids, Despite this, few systematic studies have been conducted on how parameters such as [...] Read more.

Polyelectrolyte complex micelles (PCMs, core-shell nanoparticles formed by complexation of a polyelectrolyte with a polyelectrolyte-hydrophilic neutral block copolymer) offer a solution to the critical problem of delivering therapeutic nucleic acids, Despite this, few systematic studies have been conducted on how parameters such as polycation charge density, hydrophobicity, and choice of charged group influence PCM properties, despite evidence that these strongly influence the complexation behavior of polyelectrolyte homopolymers. In this article, we report a comparison of oligonucleotide PCMs and polyelectrolyte complexes formed by poly(lysine) and poly((vinylbenzyl) trimethylammonium) (PVBTMA), a styrenic polycation with comparatively higher charge density, increased hydrophobicity, and a permanent positive charge. All of these differences have been individually suggested to provide increased complex stability, but we find that PVBTMA in fact complexes oligonucleotides more weakly than does poly(lysine), as measured by stability versus added salt. Using small angle X-ray scattering and electron microscopy, we find that PCMs formed from both cationic blocks exhibit very similar structure-property relationships, with PCM radius determined by the cationic block size and shape controlled by the hybridization state of the oligonucleotides. These observations narrow the design space for optimizing therapeutic PCMs and provide new insights into the rich polymer physics of polyelectrolyte self-assembly. Full article

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18 pages, 5093 KiB

Open AccessEditor’s ChoiceReview

Protein–Polyelectrolyte Interaction: Thermodynamic Analysis Based on the Titration Method ^†

by Xiaohan Wang, Kai Zheng, Yi Si, Xuhong Guo and Yisheng Xu

Polymers 2019, 11(1), 82; https://doi.org/10.3390/polym11010082 - 7 Jan 2019

Cited by 30 | Viewed by 6754

Abstract

This review discussed the mechanisms including theories and binding stages concerning the protein–polyelectrolyte (PE) interaction, as well as the applications for both complexation and coacervation states of protein–PE pairs. In particular, this review focused on the applications of titration techniques, that is, turbidimetric [...] Read more.

This review discussed the mechanisms including theories and binding stages concerning the protein–polyelectrolyte (PE) interaction, as well as the applications for both complexation and coacervation states of protein–PE pairs. In particular, this review focused on the applications of titration techniques, that is, turbidimetric titration and isothermal titration calorimetry (ITC), in understanding the protein–PE binding process. To be specific, by providing thermodynamic information such as pH_c, pH_φ, binding constant, entropy, and enthalpy change, titration techniques could shed light on the binding affinity, binding stoichiometry, and driving force of the protein–PE interaction, which significantly guide the applications by utilization of these interactions. Recent reports concerning interactions between proteins and different types of polyelectrolytes, that is, linear polyelectrolytes and polyelectrolyte modified nanoparticles, are summarized with their binding differences systematically discussed and compared based on the two major titration techniques. We believe this short review could provide valuable insight in the understanding of the structure–property relationship and the design of applied biomedical PE-based systems with optimal performance. Full article

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2018

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28 pages, 4484 KiB

Open AccessReview

Intermolecular Interactions in Polyelectrolyte and Surfactant Complexes in Solution

by Nasreen Khan and Blair Brettmann

Polymers 2019, 11(1), 51; https://doi.org/10.3390/polym11010051 - 31 Dec 2018

Cited by 140 | Viewed by 17969

Abstract

Polyelectrolytes are an important class of polymeric materials and are increasingly used in complex industrial formulations. A core use of these materials is in mixtures with surfactants, where a combination of hydrophobic and electrostatic interactions drives unique solution behavior and structure formation. In [...] Read more.

Polyelectrolytes are an important class of polymeric materials and are increasingly used in complex industrial formulations. A core use of these materials is in mixtures with surfactants, where a combination of hydrophobic and electrostatic interactions drives unique solution behavior and structure formation. In this review, we apply a molecular level perspective to the broad literature on polyelectrolyte-surfactant complexes, discussing explicitly the hydrophobic and electrostatic interaction contributions to polyelectrolyte surfactant complexes (PESCs), as well as the interplay between the two molecular interaction types. These interactions are sensitive to a variety of solution conditions, such as pH, ionic strength, mixing procedure, charge density, etc. and these parameters can readily be used to control the concentration at which structures form as well as the type of structure in the bulk solution. Full article

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10 pages, 1593 KiB

Open AccessReview

Exploring Structure–Property Relationships of GAGs to Tailor ECM-Mimicking Hydrogels

by Ralf Zimmermann, Carsten Werner and James Sterling

Polymers 2018, 10(12), 1376; https://doi.org/10.3390/polym10121376 - 11 Dec 2018

Cited by 7 | Viewed by 3409

Abstract

Glycosaminoglycans (GAGs) are a class of linear polysaccharides that are ubiquitous in the extracellular matrix (ECM) and on cell surfaces. Due to their key role in development, homeostasis, pathogenesis, and regeneration, GAGs are increasingly used in the design of ECM-mimicking hydrogels to stimulate [...] Read more.

Glycosaminoglycans (GAGs) are a class of linear polysaccharides that are ubiquitous in the extracellular matrix (ECM) and on cell surfaces. Due to their key role in development, homeostasis, pathogenesis, and regeneration, GAGs are increasingly used in the design of ECM-mimicking hydrogels to stimulate tissue formation and regenerative processes via specifically orchestrated cell-instructive signals. These applications first and foremost build on the ability of GAGs to effectively bind, protect, and release morphogens. The specificity and strength of morphogen-GAG interactions are largely governed by the number and spatial distribution of negatively charged sulfate groups carried by GAGs. Herein, we summarize a mean-field approach to quantify the density of ionizable groups, GAG concentration, and cross-linking degree of GAG-containing hydrogels on the basis of microslit electrokinetic experiments. We further present and discuss a continuum model of mucosa that accounts for charge regulation by glycan-ion pairing in biological contexts and under conditions of macromolecular crowding. Finally, we discuss the modulation of the morphogen binding and transport in GAG hydrogels by selective desulfation of the GAG component. Full article

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13 pages, 2038 KiB

Open AccessArticle

Separation and Characterization of Highly Charged Polyelectrolytes Using Free-Solution Capillary Electrophoresis

by Isabelle Desvignes, Joseph Chamieh and Hervé Cottet

Polymers 2018, 10(12), 1331; https://doi.org/10.3390/polym10121331 - 2 Dec 2018

Cited by 3 | Viewed by 3720

Abstract

The characterization of statistical copolymers of various charge densities remains an important and challenging analytical issue. Indeed, the polyelectrolyte (PE) effective electrophoretic mobility tends to level off above a certain charge density, due to the occurrence of Manning counterion condensation. Surprisingly, we demonstrate [...] Read more.

The characterization of statistical copolymers of various charge densities remains an important and challenging analytical issue. Indeed, the polyelectrolyte (PE) effective electrophoretic mobility tends to level off above a certain charge density, due to the occurrence of Manning counterion condensation. Surprisingly, we demonstrate in this work that it is possible to get highly resolutive separations of charged PE using free-solution capillary electrophoresis, even above the critical value predicted by the Manning counterion condensation theory. Full separation of nine statistical poly(acrylamide-co-2-acrylamido-2-methylpropanesulfonate) polymers of different charge densities varying between 3% and 100% was obtained by adjusting the ionic strength of the background electrolyte (BGE) in counter electroosmotic mode. Distributions of the chemical charge density could be obtained for the nine PE samples, showing a strong asymmetry of the distribution for the highest-charged PE. This asymmetry can be explained by the different reactivity ratios during the copolymerization. To shed more light on the separation mechanism, effective and apparent selectivities were determined by a systematic study and modeling of the electrophoretic mobility dependence according to the ionic strength. It is demonstrated that the increase in resolution with increasing BGE ionic strength is not only due to a closer matching of the electroosmotic flow magnitude with the PE electrophoretic effective mobility, but also to an increase of the dependence of the PE effective mobility according to the charge density. Full article

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19 pages, 3638 KiB

Open AccessArticle

Switchable Release of Bone Morphogenetic Protein from Thermoresponsive Poly(NIPAM-co-DMAEMA)/Cellulose Sulfate Particle Coatings

by Martin Müller, Birgit Urban, Berthold Reis, Xiaoqian Yu, Anna Luise Grab, Elisabetta Ada Cavalcanti-Adam and Dirk Kuckling

Polymers 2018, 10(12), 1314; https://doi.org/10.3390/polym10121314 - 27 Nov 2018

Cited by 14 | Viewed by 4727

Abstract

Thermoresponsive coatings of poly(N-isopropylacrylamide-co-DMAEMA)/cellulose sulfate (PNIPAM-DMAEMA/CS) complexes are reported eluting bone-morphogenetic-protein-2 (BMP-2) on demand relevant for implant assisted local bone healing. PNIPAM-DMAEMA/CS dispersions contained colloid particles with hydrodynamic radii R_H = 170–288 nm at T = 25 °C [...] Read more.

Thermoresponsive coatings of poly(N-isopropylacrylamide-co-DMAEMA)/cellulose sulfate (PNIPAM-DMAEMA/CS) complexes are reported eluting bone-morphogenetic-protein-2 (BMP-2) on demand relevant for implant assisted local bone healing. PNIPAM-DMAEMA/CS dispersions contained colloid particles with hydrodynamic radii R_H = 170–288 nm at T = 25 °C shrinking to R_H = 74–103 nm at T = 60 °C. Obviously, PNIPAM-DMAEMA/CS undergoes volume phase transition (VPT) analogously to pure PNIPAM, when critical VPT temperature (VPTT) is exceeded. Temperature dependent turbidity measurements revealed broad VPT and VPTT 47 °C for PNIPAM-DMAEMA/CS colloid dispersions at pH = 7.0. FTIR spectroscopy on thermoresponsive PNIPAM-DMAEMA/CS particle coatings at germanium model substrates under HEPES buffer indicated both wet-adhesiveness and VPT behavior based on diagnostic band intensity increases with temperature. From respective temperature courses empirical VPTT ≈ 42 °C for PNIPAM-DMAEMA/CS coatings at pH = 7.0 were found, which were comparable to VPTT found for respective dispersions. Finally, the PNIPAM-DMAEMA/CS coatings were loaded with BMP-2 and model protein papain (PAP). Time dependent FTIR spectroscopic measurements showed, that for T = 37 °C there was a relative protein release of ≈30% for PAP and ≈10% for BMP-2 after 24 h, which did not increase further. Heating to T = 42 °C for PAP and to 47 °C for BMP-2 further secondary protein release of ≈20% after 24 h was found, respectively, interesting for clinical applications. BMP-2 eluted even at 47 °C was found to be still biologically active. Full article

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14 pages, 5081 KiB

Open AccessArticle

Effect of the Surface Hydrophobicity Degree on the In Vitro Release of Polar and Non-Polar Drugs from Polyelectrolyte Matrix Tablets

by Cristhian J. Yarce, Juan D. Echeverri and Constain H. Salamanca

Polymers 2018, 10(12), 1313; https://doi.org/10.3390/polym10121313 - 27 Nov 2018

Cited by 2 | Viewed by 5326

Abstract

This work is the continuation of a series of studies focused on establishing the relationship between the surface thermodynamic properties of polyelectrolyte matrix tablets and drug release mechanisms. In this case, two model drugs with different polarity features, such as carbamazepine (non-polar) and [...] Read more.

This work is the continuation of a series of studies focused on establishing the relationship between the surface thermodynamic properties of polyelectrolyte matrix tablets and drug release mechanisms. In this case, two model drugs with different polarity features, such as carbamazepine (non-polar) and metoprolol succinate (polar) were used in combination with polymeric material hydroxypropyl-methyl cellulose (HPMC) and two polyelectrolytes derived from maleic anhydride corresponding to the sodium salts of poly(maleic acid-alt-ethylene) and poly(maleic acid-alt-octadecene) named PAM-0Na and PAM-18Na, respectively. The polymers were obtained and characterized as reported previously. Surface studies were performed by the sessile drop method, whilst the surface free energy was determined through Owens, Wendt, Rable and Kaeble (OWRK) semi-empirical model. By contrast, the drug release studies were performed by in vitro dissolution tests, where data were analyzed through dissolution efficiency. The results showed that, depending on the drug polarity, type and polymer proportion, surface properties and drug release processes are significantly affected. Full article

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18 pages, 7748 KiB

Open AccessArticle

Design of Oligonucleotide Carriers: Importance of Polyamine Chain Length

by Vadim V. Annenkov, Uma Maheswari Krishnan, Viktor A. Pal’shin, Stanislav N. Zelinskiy, Gayathri Kandasamy and Elena N. Danilovtseva

Polymers 2018, 10(12), 1297; https://doi.org/10.3390/polym10121297 - 23 Nov 2018

Cited by 5 | Viewed by 4411

Abstract

Amine containing polymers are extensively studied as special carriers for short-chain RNA (13–25 nucleotides), which are applied as gene silencing agents in gene therapy of various diseases including cancer. Elaboration of the oligonucleotide carriers requires knowledge about peculiarities of the oligonucleotide–polymeric amine interaction. [...] Read more.

Amine containing polymers are extensively studied as special carriers for short-chain RNA (13–25 nucleotides), which are applied as gene silencing agents in gene therapy of various diseases including cancer. Elaboration of the oligonucleotide carriers requires knowledge about peculiarities of the oligonucleotide–polymeric amine interaction. The critical length of the interacting chains is an important parameter which allows us to design sophisticated constructions containing oligonucleotide binding segments, solubilizing, protective and aiming parts. We studied interactions of (TCAG)n, n = 1–6 DNA oligonucleotides with polyethylenimine and poly(N-(3-((3-(dimethylamino)propyl)(methyl)amino)propyl)-N-methylacrylamide). The critical length for oligonucleotides in interaction with polymeric amines is 8–12 units and complexation at these length can be accompanied by “all-or-nothing” effects. New dimethylacrylamide based polymers with grafted polyamine chains were obtained and studied in complexation with DNA and RNA oligonucleotides. The most effective interaction and transfection activity into A549 cancer cells and silencing efficiency against vascular endothelial growth factor (VEGF) was found for a sample with average number of nitrogens in polyamine chain equal to 27, i.e., for a sample in which all grafted chains are longer than the critical length for polymeric amine–oligonucleotide complexation. Full article

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15 pages, 3022 KiB

Open AccessArticle

Conformation Study of Dual Stimuli-Responsive Core-Shell Diblock Polymer Brushes

by Kaimin Chen, Lan Cao, Ying Zhang, Kai Li, Xue Qin and Xuhong Guo

Polymers 2018, 10(10), 1084; https://doi.org/10.3390/polym10101084 - 30 Sep 2018

Cited by 9 | Viewed by 4461

Abstract

Stimuli-responsive nanoparticles are among the most popular research topics. In this study, two types of core-shell (polystyrene with a photoiniferter (PSV) as the core and diblock as the shell) polymer brushes (PSV@PNIPA-b-PAA and PSV@PAA-b-PNIPA) were designed and prepared using [...] Read more.

Stimuli-responsive nanoparticles are among the most popular research topics. In this study, two types of core-shell (polystyrene with a photoiniferter (PSV) as the core and diblock as the shell) polymer brushes (PSV@PNIPA-b-PAA and PSV@PAA-b-PNIPA) were designed and prepared using surface-initiated photoiniferter-mediated polymerization (SI-PIMP). Moreover, their pH- and temperature-stimuli responses were explored by dynamic light scattering (DLS) and turbidimeter under various conditions. The results showed that the conformational change was determined on the basis of the competition among electrostatic repulsion, hydrophobic interaction, hydrogen bonding, and steric hindrance, which was also confirmed by protein adsorption experiments. These results are not only helpful for the design and synthesis of stimuli-responsive polymer brushes but also shed light on controlled protein immobilization under mild conditions. Full article

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14 pages, 2273 KiB

Open AccessArticle

Sulfonated Poly(Arylene Ether Sulfone) and Perfluorosulfonic Acid Composite Membranes Containing Perfluoropolyether Grafted Graphene Oxide for Polymer Electrolyte Membrane Fuel Cell Applications

by Min-Young Lim and Kihyun Kim

Polymers 2018, 10(6), 569; https://doi.org/10.3390/polym10060569 - 23 May 2018

Cited by 18 | Viewed by 7277

Abstract

Sulfonated poly(arylene ether sulfone) (SPAES) and perfluorosulfonic acid (PFSA) composite membranes were prepared using perfluoropolyether grafted graphene oxide (PFPE-GO) as a reinforcing filler for polymer electrolyte membrane fuel cell (PEMFC) applications. PFPE-GO was obtained by grafting poly(hexafluoropropylene oxide) having a carboxylic acid end [...] Read more.

Sulfonated poly(arylene ether sulfone) (SPAES) and perfluorosulfonic acid (PFSA) composite membranes were prepared using perfluoropolyether grafted graphene oxide (PFPE-GO) as a reinforcing filler for polymer electrolyte membrane fuel cell (PEMFC) applications. PFPE-GO was obtained by grafting poly(hexafluoropropylene oxide) having a carboxylic acid end group onto the surface of GO via ring opening reaction between the carboxylic acid group in poly(hexafluoropropylene oxide) and the epoxide groups in GO, using 4-dimethylaminopyridine as a base catalyst. Both SPAES and PFSA composite membranes containing PFPE-GO showed much improved mechanical strength and dimensional stability, compared to each linear SPAES and PFSA membrane, respectively. The enhanced mechanical strength and dimensional stability of composite membranes can be ascribed to the homogeneous dispersion of rigid conjugated carbon units in GO through the increased interfacial interactions between PFPE-GO and SPAES/PFSA matrices. Full article

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11 pages, 17800 KiB

Open AccessArticle

Effect of Counterion Valence on Conformational Behavior of Spherical Polyelectrolyte Brushes Confined between Two Parallel Walls

by Lujuan Li, Qianqian Cao and Chuncheng Zuo

Polymers 2018, 10(4), 363; https://doi.org/10.3390/polym10040363 - 24 Mar 2018

Cited by 3 | Viewed by 3514

Abstract

We study the conformational behavior of spherical polyelectrolyte brushes in the presence of monovalent and trivalent counterions in a confined environment. The confinement is exerted by two parallel walls on the brushes. The enhancement of the confinement induces the extension of grafted chains. [...] Read more.

We study the conformational behavior of spherical polyelectrolyte brushes in the presence of monovalent and trivalent counterions in a confined environment. The confinement is exerted by two parallel walls on the brushes. The enhancement of the confinement induces the extension of grafted chains. For the monovalent case, the increase of the charge fraction leads to extended brush conformation for different slit width (distance between two walls) but collapsed brush in the presence of trivalent counterions is observed. The confinement does not affect electrostatic correlation between trivalent counterions and charged monomers. However, it was found that narrow slit width contributes to stronger electrostatic correlation for the monovalent case. This is because more monovalent counterions are inside the brush at strong confinement, but almost all trivalent counterions are trapped into the brush independently of the slit width. The diffusion of counterions under the confinement is related to the electrostatic correlation. Our simulations also reveal that the brush thickness depends on the slit width nonlinearly. Full article

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2017

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2766 KiB

Open AccessArticle

Preparation and Characterization of Water-Soluble Xylan Ethers

by Kay Hettrich, Ulrich Drechsler, Fritz Loth and Bert Volkert

Polymers 2017, 9(4), 129; https://doi.org/10.3390/polym9040129 - 31 Mar 2017

Cited by 18 | Viewed by 7913

Abstract

Xylan is a predominant hemicellulose component that is found in plants and in some algae. This polysaccharide is made from units of xylose (a pentose sugar). One promising source of xylan is oat spelt. This feedstock was used for the synthesis of two [...] Read more.

Xylan is a predominant hemicellulose component that is found in plants and in some algae. This polysaccharide is made from units of xylose (a pentose sugar). One promising source of xylan is oat spelt. This feedstock was used for the synthesis of two xylan ethers. To achieve water soluble products, we prepared dihydroxypropyl xylan as a non-ionic ether on the one hand, and carboxymethyl xylan as an ionic derivative on the other hand. Different preparation methods like heterogeneous, pseudo-homogeneous, and homogeneous syntheses were compared. In the case of dihydroxypropyl xylan, the synthesis method did not significantly affect the degree of substitution (DS). In contrast, in the case of carboxymethyl xylan, clear differences of the DS values were found in dependence on the synthesis method. Xylan ethers with DS values of >1 could be obtained, which mostly show good water solubility. The synthesized ionic, as well as non-ionic, xylan ethers were soluble in water, even though the aqueous solutions showed slight turbidity. Nevertheless, stable, transparent, and stainable films could be prepared from aqueous solutions from carboxymethyl xylans. Full article

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1955 KiB

Open AccessArticle

Hydrophilic Polyelectrolyte Multilayers Improve the ELISA System: Antibody Enrichment and Blocking Free

by Xing Lai, Gan Gao, Junji Watanabe, Huiyu Liu and Heyun Shen

Polymers 2017, 9(2), 51; https://doi.org/10.3390/polym9020051 - 12 Feb 2017

Cited by 14 | Viewed by 7566

Abstract

In this study, polyelectrolyte multilayers were fabricated on a polystyrene (PS) plate using a Layer-by-Layer (LbL) self-assembly technique. The resulting functional platform showed improved performance compared with conventional enzyme-linked immunosorbent assay (ELISA) systems. Poly(diallyldimethylammonium chloride) (PDDA) and poly(acrylic acid) (PAA) were used as [...] Read more.

In this study, polyelectrolyte multilayers were fabricated on a polystyrene (PS) plate using a Layer-by-Layer (LbL) self-assembly technique. The resulting functional platform showed improved performance compared with conventional enzyme-linked immunosorbent assay (ELISA) systems. Poly(diallyldimethylammonium chloride) (PDDA) and poly(acrylic acid) (PAA) were used as cationic and anionic polyelectrolytes. On the negatively-charged (PDDA/PAA)₃ polyelectrolyte multilayers the hydrophilic PAA surface could efficiently decrease the magnitude of the noise signal, by inhibiting nonspecific adsorption even without blocking reagent adsorption. Moreover, the (PDDA/PAA)₃ substrate covalently immobilized the primary antibody, greatly increasing the amount of primary antibody adsorption and enhancing the specific detection signal compared with a conventional PS plate. The calibration curve of the (PDDA/PAA)₃ substrate showed a wide linear range, for concentrations from 0.033 to 33 nM, a large specific signal change, and a detection limit of 33 pM, even though the conventional blocking reagent adsorption step was omitted. The (PDDA/PAA)₃ substrate provided a high-performance ELISA system with a simple fabrication process and high sensitivity; the system presented here shows potential for a variety of immunosensor applications. Full article

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2024 KiB

Open AccessArticle

The Effect of Molar Mass and Charge Density on the Formation of Complexes between Oppositely Charged Polyelectrolytes

by Feriel Meriem Lounis, Joseph Chamieh, Laurent Leclercq, Philippe Gonzalez and Hervé Cottet

Polymers 2017, 9(2), 50; https://doi.org/10.3390/polym9020050 - 4 Feb 2017

Cited by 14 | Viewed by 6544

Abstract

The interactions between model polyanions and polycations have been studied using frontal continuous capillary electrophoresis (FACCE) which allows the determination of binding stoichiometry and binding constant of the formed polyelectrolyte complex (PEC). In this work, the effect of the poly(l-lysine) (PLL) [...] Read more.

The interactions between model polyanions and polycations have been studied using frontal continuous capillary electrophoresis (FACCE) which allows the determination of binding stoichiometry and binding constant of the formed polyelectrolyte complex (PEC). In this work, the effect of the poly(l-lysine) (PLL) molar mass on the interaction with statistical copolymers of acrylamide and 2-acrylamido-2-methyl-1-propanesulfonate (PAMAMPS) has been systematically investigated for different PAMAMPS chemical charge densities (15% and 100%) and different ionic strengths. The study of the ionic strength dependence of the binding constant allowed the determination of the total number of released counter-ions during the formation of the PEC, which can be compared to the total number of counter-ions initially condensed on the individual polyelectrolyte partners before the association. Interestingly, this fraction of released counter-ions, which was strongly dependent on the PLL molar mass, was almost independent of the PAMAMPS charge density. These findings are useful to predict the binding constant according to the molar mass and charge density of the polyelectrolyte partners. Full article

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3860 KiB

Open AccessArticle

Polyion Complex Vesicles with Solvated Phosphobetaine Shells Formed from Oppositely Charged Diblock Copolymers

by Keita Nakai, Kazuhiko Ishihara, Michael Kappl, Syuji Fujii, Yoshinobu Nakamura and Shin-ichi Yusa

Polymers 2017, 9(2), 49; https://doi.org/10.3390/polym9020049 - 4 Feb 2017

Cited by 23 | Viewed by 7243

Abstract

Diblock copolymers consisting of a hydrophilic poly(2-(methacryloyloxy)ethyl phosphorylcholine) (PMPC) block and either a cationic or anionic block were prepared from (3-(methacrylamido)propyl)trimethylammonium chloride (MAPTAC) or sodium 2-(acrylamido)-2-methylpropanesulfonate (AMPS). Polymers were synthesized via reversible addition-fragmentation chain transfer (RAFT) radical polymerization using a PMPC macro-chain transfer [...] Read more.

Diblock copolymers consisting of a hydrophilic poly(2-(methacryloyloxy)ethyl phosphorylcholine) (PMPC) block and either a cationic or anionic block were prepared from (3-(methacrylamido)propyl)trimethylammonium chloride (MAPTAC) or sodium 2-(acrylamido)-2-methylpropanesulfonate (AMPS). Polymers were synthesized via reversible addition-fragmentation chain transfer (RAFT) radical polymerization using a PMPC macro-chain transfer agent. The degree of polymerization for PMPC, cationic PMAPTAC, and anionic PAMPS blocks was 20, 190, and 196, respectively. Combining two solutions of oppositely charged diblock copolymers, PMPC-b-PMAPTAC and PMPC-b-PAMPS, led to the spontaneous formation of polyion complex vesicles (PICsomes). The PICsomes were characterized using ¹H NMR, static abd dynamic light scattering, transmittance electron microscopy (TEM), and atomic force microscopy. Maximum hydrodynamic radius (R_h) for the PICsome was observed at a neutral charge balance of the cationic and anionic diblock copolymers. The R_h value and aggregation number (N_agg) of PICsomes in 0.1 M NaCl was 78.0 nm and 7770, respectively. A spherical hollow vesicle structure was observed in TEM images. The hydrodynamic size of the PICsomes increased with concentration of the diblock copolymer solutions before mixing. Thus, the size of the PICsomes can be controlled by selecting an appropriate preparation method. Full article

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4330 KiB

Open AccessReview

Engineering Cell Surfaces with Polyelectrolyte Materials for Translational Applications

by Peipei Zhang, Michelle L. Bookstaver and Christopher M. Jewell

Polymers 2017, 9(2), 40; https://doi.org/10.3390/polym9020040 - 28 Jan 2017

Cited by 13 | Viewed by 9223

Abstract

Engineering cell surfaces with natural or synthetic materials is a unique and powerful strategy for biomedical applications. Cells exhibit more sophisticated migration, control, and functional capabilities compared to nanoparticles, scaffolds, viruses, and other engineered materials or agents commonly used in the biomedical field. [...] Read more.

Engineering cell surfaces with natural or synthetic materials is a unique and powerful strategy for biomedical applications. Cells exhibit more sophisticated migration, control, and functional capabilities compared to nanoparticles, scaffolds, viruses, and other engineered materials or agents commonly used in the biomedical field. Over the past decade, modification of cell surfaces with natural or synthetic materials has been studied to exploit this complexity for both fundamental and translational goals. In this review we present the existing biomedical technologies for engineering cell surfaces with one important class of materials, polyelectrolytes. We begin by introducing the challenges facing the cell surface engineering field. We then discuss the features of polyelectrolytes and how these properties can be harnessed to solve challenges in cell therapy, tissue engineering, cell-based drug delivery, sensing and tracking, and immune modulation. Throughout the review, we highlight opportunities to drive the field forward by bridging new knowledge of polyelectrolytes with existing translational challenges. Full article

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1109 KiB

Open AccessArticle

Polymer Conformations in Ionic Microgels in the Presence of Salt: Theoretical and Mesoscale Simulation Results

by Hideki Kobayashi, Rene Halver, Godehard Sutmann and Roland G. Winkler

Polymers 2017, 9(1), 15; https://doi.org/10.3390/polym9010015 - 5 Jan 2017

Cited by 43 | Viewed by 6669

Abstract

We investigate the conformational properties of polymers in ionic microgels in the presence of salt ions by molecular dynamics simulations and analytical theory. A microgel particle consists of coarse-grained linear polymers, which are tetra-functionally crosslinked. Counterions and salt ions are taken into account [...] Read more.

We investigate the conformational properties of polymers in ionic microgels in the presence of salt ions by molecular dynamics simulations and analytical theory. A microgel particle consists of coarse-grained linear polymers, which are tetra-functionally crosslinked. Counterions and salt ions are taken into account explicitly, and charge-charge interactions are described by the Coulomb potential. By varying the charge interaction strength and salt concentration, we characterize the swelling of the polyelectrolytes and the charge distribution. In particular, we determine the amount of trapped mobile charges inside the microgel and the Debye screening length. Moreover, we analyze the polymer extension theoretically in terms of the tension blob model taking into account counterions and salt ions implicitly by the Debye–Hückel model. Our studies reveal a strong dependence of the amount of ions absorbed in the interior of the microgel on the electrostatic interaction strength, which is related to the degree of the gel swelling. This implies a dependence of the inverse Debye screening length κ on the ion concentration; we find a power-law increase of κ with the Coulomb interaction strength with the exponent

3 / 5

for a salt-free microgel and an exponent

1 / 2

for moderate salt concentrations. Additionally, the radial dependence of polymer conformations and ion distributions is addressed. Full article

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2016

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8966 KiB

Open AccessArticle

Influence of Polyelectrolyte Multilayer Properties on Bacterial Adhesion Capacity

by Davor Kovačević, Rok Pratnekar, Karmen Godič Torkar, Jasmina Salopek, Goran Dražić, Anže Abram and Klemen Bohinc

Polymers 2016, 8(10), 345; https://doi.org/10.3390/polym8100345 - 26 Sep 2016

Cited by 48 | Viewed by 7696

Abstract

Bacterial adhesion can be controlled by different material surface properties, such as surface charge, on which we concentrate in our study. We use a silica surface on which poly(allylamine hydrochloride)/sodium poly(4-styrenesulfonate) (PAH/PSS) polyelectrolyte multilayers were formed. The corresponding surface roughness and hydrophobicity were [...] Read more.

Bacterial adhesion can be controlled by different material surface properties, such as surface charge, on which we concentrate in our study. We use a silica surface on which poly(allylamine hydrochloride)/sodium poly(4-styrenesulfonate) (PAH/PSS) polyelectrolyte multilayers were formed. The corresponding surface roughness and hydrophobicity were determined by atomic force microscopy and tensiometry. The surface charge was examined by the zeta potential measurements of silica particles covered with polyelectrolyte multilayers, whereby ionic strength and polyelectrolyte concentrations significantly influenced the build-up process. For adhesion experiments, we used the bacterium Pseudomonas aeruginosa. The extent of adhered bacteria on the surface was determined by scanning electron microscopy. The results showed that the extent of adhered bacteria mostly depends on the type of terminating polyelectrolyte layer, since relatively low differences in surface roughness and hydrophobicity were obtained. In the case of polyelectrolyte multilayers terminating with a positively charged layer, bacterial adhesion was more pronounced than in the case when the polyelectrolyte layer was negatively charged. Full article

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434 KiB

Open AccessCommunication

Rheological Properties of DNA Molecules in Solution: Molecular Weight and Entanglement Influences

by Lourdes Mónica Bravo-Anaya, Frédéric Pignon, Félix Armando Soltero Martínez and Marguerite Rinaudo

Polymers 2016, 8(8), 279; https://doi.org/10.3390/polym8080279 - 3 Aug 2016

Cited by 11 | Viewed by 6776

Abstract

Molecular weight, stiffness, temperature, and polymer and ionic concentrations are known to widely influence the viscosity of polymer solutions. Additionally, polymer molecular weight—which is related to its dimensions in solution—is one of its most important characteristics. In this communication, low molecular weight DNA [...] Read more.

Molecular weight, stiffness, temperature, and polymer and ionic concentrations are known to widely influence the viscosity of polymer solutions. Additionally, polymer molecular weight—which is related to its dimensions in solution—is one of its most important characteristics. In this communication, low molecular weight DNA from salmon sperm was purified and then studied in solutions in a wide concentration range (between 0.5 and 1600 mg/mL). The intrinsic viscosity of this low molecular weight DNA sample was firstly determined and the evidence of the overlap concentration was detected around the concentration of 125 mg/mL. The chain characteristics of these short molecules were studied in terms of the influence of their molecular weight on the solution viscosities and on the overlap parameter C_DNA[η]. Furthermore, to complete previously reported experimental data, solutions of a large molecular weight DNA from calf-thymus were studied in a high concentration range (up to 40 mg/mL). The rheological behavior is discussed in terms of the generalized master curve obtained from the variation of the specific viscosity at zero shear rate (η_sp,0) as a function of C_DNA[η]. Full article

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1622 KiB

Open AccessCommunication

Rapid Mercury(II) Removal by Electrospun Sulfur Copolymers

by Michael W. Thielke, Lindsey A. Bultema, Daniel D. Brauer, Bernadette Richter, Markus Fischer and Patrick Theato

Polymers 2016, 8(7), 266; https://doi.org/10.3390/polym8070266 - 20 Jul 2016

Cited by 86 | Viewed by 9850

Abstract

Electrospinning was performed with a blend of commercially available poly(methyl methacrylate) (PMMA) and a sulfur-rich copolymer based on poly(sulfur-statistical-diisopropenylbenzene), which was synthesized via inverse vulcanization. The polysulfide backbone of sulfur-containing polymers is known to bind mercury from aqueous solutions and can [...] Read more.

Electrospinning was performed with a blend of commercially available poly(methyl methacrylate) (PMMA) and a sulfur-rich copolymer based on poly(sulfur-statistical-diisopropenylbenzene), which was synthesized via inverse vulcanization. The polysulfide backbone of sulfur-containing polymers is known to bind mercury from aqueous solutions and can be utilized for recycling water. Increasing the surface area by electrospinning can maximize the effect of binding mercury regarding the rate and maximum uptake. These fibers showed a mercury decrease of more than 98% after a few seconds and a maximum uptake of 440 mg of mercury per gram of electrospun fibers. These polymeric fibers represent a new class of efficient water filtering systems that show one of the highest and fastest mercury uptakes for electrospun fibers reported. Full article

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2414 KiB

Open AccessArticle

Physicochemical Properties of Biopolymer Hydrogels Treated by Direct Electric Current

by Żaneta Król, Magdalena Malik, Krzysztof Marycz and Andrzej Jarmoluk

Polymers 2016, 8(7), 248; https://doi.org/10.3390/polym8070248 - 12 Jul 2016

Cited by 22 | Viewed by 7608

Abstract

The objective of this study was to evaluate the changes within the physicochemical properties of gelatine (2%; 4%; 8%), carrageenan (1.5%; 2%; 2.5%) and sodium alginate (0.75%; 1%; 1.25%) hydrogels with different sodium chloride concentrations that were triggered by applying direct current (DC) [...] Read more.

The objective of this study was to evaluate the changes within the physicochemical properties of gelatine (2%; 4%; 8%), carrageenan (1.5%; 2%; 2.5%) and sodium alginate (0.75%; 1%; 1.25%) hydrogels with different sodium chloride concentrations that were triggered by applying direct current (DC) of 400 mA for a duration of five minutes. There were three types of gels prepared for the purpose of the study: C, control; H, gels on the basis of hydrosols that were treated with DC; and G, gels treated with DC. In the course of the study, the authors carried out the following analyses: Texture Profile Analysis (TPA), Fourier Transform Infrared spectroscopy (FTIR), Scanning Electron Microscopy (SEM) and Swelling Ratio (SR). Furthermore, the color and pH of hydrogels were measured. The FTIR spectra showed that the structures of gelatine, carrageenan and sodium alginate do not significantly change upon applying DC. The results of TPA, SR, color and pH measurement indicate that hydrogels’ properties are significantly dependent on the type of polymer, its concentration and the type of the gel. By changing those parameters, the characteristics of such gels can be additionally tuned, which extends their applicability, e.g., in the food industry. Moreover, the analysis revealed that SR of H gel gelatine after 72 h of storage was 1.84-times higher than SR of the control sample, which indicated that this gel may be considered as a possible component for wound dressing materials. Full article

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3599 KiB

Open AccessArticle

Effect of Very High Charge Density and Monomer Constitution on the Synthesis and Properties of Cationic Polyelectrolytes

by Hamideh Ahmadloo, Ricardo Losada and Christine Wandrey

Polymers 2016, 8(6), 234; https://doi.org/10.3390/polym8060234 - 16 Jun 2016

Cited by 7 | Viewed by 8661

Abstract

The free-radical homopolymerization of 1,3-bis(N,N,N-trimethylammonium)-2-propylmethacrylate dichloride (di-M) and 1,3-bis(N,N,N-trimethylammonium)-2-propylacrylate dichloride (di-A) in aqueous solution yields cationic polyelectrolytes (PEL) with theoretical/structural charge spacing of only ≈0.12 nm. The high charge density causes condensation of ≈82% of the chloride counterions. The [...] Read more.

The free-radical homopolymerization of 1,3-bis(N,N,N-trimethylammonium)-2-propylmethacrylate dichloride (di-M) and 1,3-bis(N,N,N-trimethylammonium)-2-propylacrylate dichloride (di-A) in aqueous solution yields cationic polyelectrolytes (PEL) with theoretical/structural charge spacing of only ≈0.12 nm. The high charge density causes condensation of ≈82% of the chloride counterions. The high level of counterion condensation reduces the ionic strength in the polymerizing batch when the monomer molecules connect to PEL chains. This has the consequence that the hydrodynamic and excluded volume of the PEL molecules will change. Studies of the free radical polymerization revealed non-ideal polymerization kinetics already at low conversion and additionally autoacceleration above a certain monomer concentration and conversion. Similar autoacceleration was not observed for monomers yielding PEL with charge spacing of 0.25 or 0.5 nm. Coulomb interactions, monomer association, steric effects, and specific features of the monomer constitution have been evaluated concerning their contributions to the concentration dependence and conversion dependence of kinetic parameters. The different backbone constitutions of di-M and di-A not only influence the polymerization kinetics but also equip poly(di-M) with higher hydrolytic stability. The experimental results confirm the impact of electrochemical parameters and the necessity to reconsider their inclusion in kinetic models. Full article

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Open AccessArticle

pH- and Metal Ion- Sensitive Hydrogels based on N-[2-(dimethylaminoethyl)acrylamide]

by Leena Nebhani, Veena Choudhary, Hans-Jürgen P. Adler and Dirk Kuckling

Polymers 2016, 8(6), 233; https://doi.org/10.3390/polym8060233 - 15 Jun 2016

Cited by 24 | Viewed by 7837

Abstract

Smart hydrogels are promising materials for actuators and sensors, as they can respond to small changes in their environment with a large property change. Hydrogels can respond to a variety of stimuli, for example temperature, pH, metal ions, etc. In this article, [...] Read more.

Smart hydrogels are promising materials for actuators and sensors, as they can respond to small changes in their environment with a large property change. Hydrogels can respond to a variety of stimuli, for example temperature, pH, metal ions, etc. In this article, the synthesis and characterization of polyampholyte hydrogels based on open chain ligands showing pH and metal ion sensitivity are described. Copolymer and terpolymer gels using different mixtures of monomers i.e., N-[2-(dimethylaminoethyl)acrylamide] (DMAEAAm), N,N-dimethylacrylamide (DMAAm), acrylic acid (AA) and 2-acrylamido-2-methyl-1-propanesulphonic acid (AMPS), have been synthesized. The effect of copolymer composition, i.e., the ratio and amount of ionic monomers and the degree of crosslinking on the swelling characteristics, was evaluated as a function of pH. On this basis, metal ion sensitivity measurements were performed at selected pH values. The metal ion sensitivity was measured by varying the concentration of Cu²⁺, Zn²⁺ and Ag⁺ ions under acidic pH conditions. Full article

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1593 KiB

Open AccessArticle

SANS from Salt-Free Aqueous Solutions of Hydrophilic and Highly Charged Star-Branched Polyelectrolytes

by François Boué, Jérôme Combet, Bruno Demé, Martine Heinrich, Jean-Georges Zilliox and Michel Rawiso

Polymers 2016, 8(6), 228; https://doi.org/10.3390/polym8060228 - 8 Jun 2016

Cited by 10 | Viewed by 6219

Abstract

Scattering functions of sodium sulfonated polystyrene (NaPSS) star-branched polyelectrolytes with high sulfonation degrees were measured from their salt-free aqueous solutions, using the Small Angle Neutron Scattering (SANS) technique. Whatever the concentration c, they display two maxima. The first, of abscissa q₁ [...] Read more.

Scattering functions of sodium sulfonated polystyrene (NaPSS) star-branched polyelectrolytes with high sulfonation degrees were measured from their salt-free aqueous solutions, using the Small Angle Neutron Scattering (SANS) technique. Whatever the concentration c, they display two maxima. The first, of abscissa q₁*, is related to a position order between star cores and scales as q₁* ∝ c^1/3. The second, of abscissa q₂*, is also observed in the scattering function of a semi-dilute solution of NaPSS linear polyelectrolytes. In the dilute regime (c < c*, non-overlapping stars), peak abscissa does not depend on concentration c and is just an intramolecular characteristic associated with the electrostatic repulsion between arms of the same star. In the semi-dilute regime, due to the star interpenetration, the scattering function – through the peak position, reflects repulsion between arms of the same star or of different stars. The c threshold between these distinct c-dependencies of q₂* in the dilute and semi-dilute regimes is estimated as c*. Just as simple is the measurement of the geometrical radius R of the star obtained from the q₁* value at c* through the relation 2R = 2π/q₁*. By considering NaPSS stars of the same functionality with different degrees of polymerization per arm N_a, we find R scaling linearly with N_a, suggesting an elongated average conformation of the arms. This is in agreement with theoretical predictions and simulations. Meanwhile the value of q₂* measured in the dilute regime does not allow any inhomogeneous counterion distribution inside the stars to be revealed. Full article

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2023 KiB

Open AccessArticle

Influence of Polyplex Formation on the Performance of Star-Shaped Polycationic Transfection Agents for Mammalian Cells

by Alexander Raup, Ullrich Stahlschmidt, Valérie Jérôme, Christopher V. Synatschke, Axel H. E. Müller and Ruth Freitag

Polymers 2016, 8(6), 224; https://doi.org/10.3390/polym8060224 - 6 Jun 2016

Cited by 27 | Viewed by 7454

Abstract

Genetic modification (“transfection”) of mammalian cells using non-viral, synthetic agents such as polycations, is still a challenge. Polyplex formation between the DNA and the polycation is a decisive step in such experiments. Star-shaped polycations have been proposed as superior transfection agents, yet have [...] Read more.

Genetic modification (“transfection”) of mammalian cells using non-viral, synthetic agents such as polycations, is still a challenge. Polyplex formation between the DNA and the polycation is a decisive step in such experiments. Star-shaped polycations have been proposed as superior transfection agents, yet have never before been compared side-by-side, e.g., in view of structural effects. Herein four star-shaped polycationic structures, all based on (2-dimethylamino) ethyl methacrylate (DMAEMA) building blocks, were investigated for their potential to deliver DNA to adherent (CHO, L929, HEK-293) and non-adherent (Jurkat, primary human T lymphocytes) mammalian cells. The investigated vectors included three structures where the PDMAEMA arms (different arm length and grafting densities) had been grown from a center silsesquioxane or silica-coated γ-Fe₂O₃-core and one micellar structure self-assembled from poly(1,2-butadiene)-block PDMAEMA polymers. All nano-stars combined high transfection potential with excellent biocompatibility. The micelles slightly outperformed the covalently linked agents. For method development and optimization, the absolute amount of polycation added to the cells was more important than the N/P-ratio (ratio between polycation nitrogen and DNA phosphate), provided a lower limit was passed and enough polycation was present to overcompensate the negative charge of the plasmid DNA. Finally, the matrix (NaCl vs. HEPES-buffered glucose solution), but also the concentrations adjusted during polyplex formation, affected the results. Full article

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4349 KiB

Open AccessArticle

Polypeptide-Nanoparticle Interactions and Corona Formation Investigated by Monte Carlo Simulations

by Fabrice Carnal, Arnaud Clavier and Serge Stoll

Polymers 2016, 8(6), 203; https://doi.org/10.3390/polym8060203 - 25 May 2016

Cited by 17 | Viewed by 6132

Abstract

Biomacromolecule activity is usually related to its ability to keep a specific structure. However, in solution, many parameters (pH, ionic strength) and external compounds (polyelectrolytes, nanoparticles) can modify biomacromolecule structure as well as acid/base properties, thus resulting in a loss of activity and [...] Read more.

Biomacromolecule activity is usually related to its ability to keep a specific structure. However, in solution, many parameters (pH, ionic strength) and external compounds (polyelectrolytes, nanoparticles) can modify biomacromolecule structure as well as acid/base properties, thus resulting in a loss of activity and denaturation. In this paper, the impact of neutral and charged nanoparticles (NPs) is investigated by Monte Carlo simulations on polypeptide (PP) chains with primary structure based on bovine serum albumin. The influence of pH, salt valency, and NP surface charge density is systematically studied. It is found that the PP is extended at extreme pH, when no complex formation is observed, and folded at physiological pH. PP adsorption around oppositely-charged NPs strongly limits chain structural changes and modifies its acid/base properties. At physiological pH, the complex formation occurs only with positively-charged NPs. The presence of salts, in particular those with trivalent cations, introduces additional electrostatic interactions, resulting in a mitigation of the impact of negative NPs. Thus, the corona structure is less dense with locally-desorbed segments. On the contrary, very limited impact of salt cation valency is observed when NPs are positive, due to the absence of competitive effects between multivalent cations and NP. Full article

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Open AccessArticle

Polyester-Based, Biodegradable Core-Multishell Nanocarriers for the Transport of Hydrophobic Drugs

by Karolina A. Walker, Jean-François Stumbé and Rainer Haag

Polymers 2016, 8(5), 192; https://doi.org/10.3390/polym8050192 - 14 May 2016

Cited by 6 | Viewed by 8426

Abstract

A water-soluble, core-multishell (CMS) nanocarrier based on a new hyperbranched polyester core building block was synthesized and characterized towards drug transport and degradation of the nanocarrier. The hydrophobic drug dexamethasone was encapsulated and the enzyme-mediated biodegradability was investigated by NMR spectroscopy. The new [...] Read more.

A water-soluble, core-multishell (CMS) nanocarrier based on a new hyperbranched polyester core building block was synthesized and characterized towards drug transport and degradation of the nanocarrier. The hydrophobic drug dexamethasone was encapsulated and the enzyme-mediated biodegradability was investigated by NMR spectroscopy. The new CMS nanocarrier can transport one molecule of dexamethasone and degrades within five days at a skin temperature of 32 °C to biocompatible fragments. Full article

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Open AccessFeature PaperArticle

Porphyrin Diacid-Polyelectrolyte Assemblies: Effective Photocatalysts in Solution

by Sabine Frühbeißer, Giacomo Mariani and Franziska Gröhn

Polymers 2016, 8(5), 180; https://doi.org/10.3390/polym8050180 - 4 May 2016

Cited by 20 | Viewed by 7633

Abstract

Developing effective and versatile photocatalytic systems is of great potential in solar energy conversion. Here we investigate the formation of supramolecular catalysts by electrostatic self-assembly in aqueous solution: Combining positively charged porphyrins with negatively charged polyelectrolytes leads to nanoscale assemblies where, next to [...] Read more.

Developing effective and versatile photocatalytic systems is of great potential in solar energy conversion. Here we investigate the formation of supramolecular catalysts by electrostatic self-assembly in aqueous solution: Combining positively charged porphyrins with negatively charged polyelectrolytes leads to nanoscale assemblies where, next to electrostatic interactions, π–π interactions also play an important role. Porphyrin diacid-polyelectrolyte assemblies exhibit a substantially enhanced catalytic activity for the light-driven oxidation of iodide. Aggregates with the hexavalent cationic porphyrin diacids show up to 22 times higher catalytic activity than the corresponding aggregates under neutral conditions. The catalytic activity can be increased by increasing the valency of the porphyrin and by choice of the loading ratio. The structural investigation of the supramolecular catalysts took place via atomic force microscopy and small angle neutron scattering. Hence, a new facile concept for the design of efficient and tunable self-assembled photocatalysts is presented. Full article

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Open AccessArticle

Amyloid Beta Aggregation in the Presence of Temperature-Sensitive Polymers

by Sebastian Funtan, Zhanna Evgrafova, Juliane Adler, Daniel Huster and Wolfgang H. Binder

Polymers 2016, 8(5), 178; https://doi.org/10.3390/polym8050178 - 2 May 2016

Cited by 17 | Viewed by 9749

Abstract

The formation of amyloid fibrils is considered to be one of the main causes for many neurodegenerative diseases, such as Alzheimer’s, Parkinson’s or Huntington’s disease. Current knowledge suggests that amyloid-aggregation represents a nucleation-dependent aggregation process in vitro, where a sigmoidal growth phase [...] Read more.

The formation of amyloid fibrils is considered to be one of the main causes for many neurodegenerative diseases, such as Alzheimer’s, Parkinson’s or Huntington’s disease. Current knowledge suggests that amyloid-aggregation represents a nucleation-dependent aggregation process in vitro, where a sigmoidal growth phase follows an induction period. Here, we studied the fibrillation of amyloid β 1-40 (Aβ₄₀) in the presence of thermoresponsive polymers, expected to alter the Aβ₄₀ fibrillation kinetics due to their lower critical solution behavior. To probe the influence of molecular weight and the end groups of the polymer on its lower critical solution temperature (LCST), also considering its concentration dependence in the presence of buffer-salts needed for the aggregation studies of the amyloids, poly(oxazolines) (POx) with LCSTs ranging from 14.2–49.8 °C and poly(methoxy di(ethylene glycol)acrylates) with LCSTs ranging from 34.4–52.7 °C were synthesized. The two different polymers allowed the comparison of the influence of different molecular structures onto the fibrillation process. Mixtures of Aβ₄₀ with these polymers in varying concentrations were studied via time-dependent measurements of the thioflavin T (ThT) fluorescence. The studies revealed that amyloid fibrillation was accelerated in, accompanied by an extension of the lag phase of Aβ₄₀ fibrillation from 18.3 h in the absence to 19.3 h in the presence of the poly(methoxy di(ethylene glycol)acrylate) (3600 g/mol). Full article

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Open AccessArticle

Evaluation of the Performance of Dual Polyelectrolyte Systems on the Re-Flocculation Ability of Calcium Carbonate Aggregates in Turbulent Environment

by Maria G. Rasteiro, Fernando A. Garcia, David Hunkeler and Ineide Pinheiro

Polymers 2016, 8(5), 174; https://doi.org/10.3390/polym8050174 - 29 Apr 2016

Cited by 7 | Viewed by 5252

Abstract

Flocculation can be used in turbulent environments resulting in floc breakage due to shearing. The degree of re-flocculation relates directly to product quality and process efficiency. This study aimed at looking for alternatives to improve the re-flocculation ability of aggregates when polyelectrolytes (PEL) [...] Read more.

Flocculation can be used in turbulent environments resulting in floc breakage due to shearing. The degree of re-flocculation relates directly to product quality and process efficiency. This study aimed at looking for alternatives to improve the re-flocculation ability of aggregates when polyelectrolytes (PEL) are used as flocculation agents. Moreover, because branched PEL have proved previously to lead to high flocculation efficiencies, the work presented focus on the improvement of the re-flocculation ability of branched PEL. Thus, a selection of branched polymers were used primarily as flocculation aid and after flocs break up a linear polymer was added to the system in order to improve re-flocculation. Different mixtures were tested with the objective to try to induce, during re-flocculation, complementary flocculation mechanisms, favoring the patching mechanism. Re-flocculation improved significantly with this strategy. Laser Diffraction Spectroscopy was used to monitor the flocculation and re-flocculation processes supplying information about the floc size and structure. Since inorganic materials, namely bentonite, have been widely used to improve the re-flocculation capacity of polyelectrolytes, the results of using dual polyelectrolyte systems were compared with the effect of adding bentonite to the system. Full article

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Open AccessArticle

Thermodynamic Analysis of the Conformational Transition in Aqueous Solutions of Isotactic and Atactic Poly(Methacrylic Acid) and the Hydrophobic Effect

by Ksenija Kogej

Polymers 2016, 8(5), 168; https://doi.org/10.3390/polym8050168 - 28 Apr 2016

Cited by 21 | Viewed by 6435

Abstract

The affinity of amphiphilic compounds for water is important in various processes, e.g., in conformational transitions of biopolymers, protein folding/unfolding, partitioning of drugs in the living systems, and many others. Herein, we study the conformational transition of two isomer forms of poly(methacrylic acid) [...] Read more.

The affinity of amphiphilic compounds for water is important in various processes, e.g., in conformational transitions of biopolymers, protein folding/unfolding, partitioning of drugs in the living systems, and many others. Herein, we study the conformational transition of two isomer forms of poly(methacrylic acid) (PMA), isotactic (iPMA) and atactic (aPMA), in water. These isomers are chemically equivalent and differ only in the arrangement of functional groups along the chain. A complete thermodynamic analysis of the transition of the PMA chains from the compact to the extended form (comprising the conformational transition) in water in the presence of three alkali chlorides is conducted by determining the free energy, enthalpy, and entropy changes of the process as a function of temperature, and therefrom also the heat capacity change. The heat capacity change of the transition is positive (+20 J/K mol) for aPMA and negative (−50 J/K mol) for iPMA. This result suggests a different affinity of PMA isomers for water. The conformational transition of iPMA is parallel to the transfer of polar solutes into water, whereas that of aPMA agrees with the transfer of nonpolar solutes into water. Full article

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Open AccessArticle

Mesogenic Polyelectrolyte Gels Absorb Organic Solvents and Liquid Crystalline Molecules

by Yusuke Nishikori, Kazuya Iseda, Kenta Kokado and Kazuki Sada

Polymers 2016, 8(4), 148; https://doi.org/10.3390/polym8040148 - 19 Apr 2016

Cited by 9 | Viewed by 6120

Abstract

In this paper, mesogenic polyelectrolyte gels (MPEgels) tethering mesogenic groups on the side chains were synthesized from a mesogenic monomer and ionic monomer via a conventional radical polymerization process. The obtained MPEgels absorbed various organic solvents in a wide range of dielectric constants [...] Read more.

In this paper, mesogenic polyelectrolyte gels (MPEgels) tethering mesogenic groups on the side chains were synthesized from a mesogenic monomer and ionic monomer via a conventional radical polymerization process. The obtained MPEgels absorbed various organic solvents in a wide range of dielectric constants from chloroform (ε = 7.6) to DMSO (ε = 46.5). The electrostatic repulsion among the polymer chains and the osmotic pressure between the interior and exterior of the MPEgel is responsible for the high swelling ability, revealed by the common ion effect using tetra(n-hexyl)ammonium tetra(3,5-bis(trifluoromethyl)phenylborate (THATFPB). The obtained MPEgels could also absorb liquid crystalline molecules such as 4-cyano-4’-pentylbiphenyl (5CB), analogously caused by the above-mentioned polyelectrolyte characteristic. The MPEgels exhibited liquid crystal transition temperature (T_NI) on differential scanning calorimetry (DSC) measurement, and the increase of the ionic group content lowered T_NI. The MPEgels absorbing liquid crystalline molecules exhibited differing T_NI, dependent on the compatibility of the mesogenic group on the side chain to the liquid crystalline molecule. Full article

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Open AccessArticle

Modification of Spherical Polyelectrolyte Brushes by Layer-by-Layer Self-Assembly as Observed by Small Angle X-ray Scattering

by Yuchuan Tian, Li Li, Haoya Han, Weihua Wang, Yunwei Wang, Zhishuang Ye and Xuhong Guo

Polymers 2016, 8(4), 145; https://doi.org/10.3390/polym8040145 - 15 Apr 2016

Cited by 16 | Viewed by 6978

Abstract

Multilayer modified spherical polyelectrolyte brushes were prepared through alternate deposition of positively charged poly(allylamine hydrochloride) (PAH) and negatively charged poly-l-aspartic acid (PAsp) onto negatively charged spherical poly(acrylic acid) (PAA) brushes (SPBs) on a poly(styrene) core. The charge reversal determined by the [...] Read more.

Multilayer modified spherical polyelectrolyte brushes were prepared through alternate deposition of positively charged poly(allylamine hydrochloride) (PAH) and negatively charged poly-l-aspartic acid (PAsp) onto negatively charged spherical poly(acrylic acid) (PAA) brushes (SPBs) on a poly(styrene) core. The charge reversal determined by the zeta potential indicated the success of layer-by-layer (LBL) deposition. The change of the structure during the construction of multilayer modified SPBs was observed by small-angle X-ray scattering (SAXS). SAXS results indicated that some PAH chains were able to penetrate into the PAA brush for the PAA-PAH double-layer modified SPBs whereas part of the PAH moved towards the outer layer when the PAsp layer was loaded to form a PAA-PAH-PAsp triple-layer system. The multilayer modified SPBs were stable upon changing the pH (5 to 9) and ionic strength (1 to 100 mM). The triple-layer modified SPBs were more tolerated to high pH (even at 11) compared to the double-layer ones. SAXS is proved to be a powerful tool for studying the inner structure of multilayer modified SPBs, which can establish guidelines for the a range of potential applications of multilayer modified SPBs. Full article

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Open AccessFeature PaperArticle

Uptake of pH-Sensitive Gold Nanoparticles in Strong Polyelectrolyte Brushes

by Dikran Kesal, Stephanie Christau, Patrick Krause, Tim Möller and Regine Von Klitzing

Polymers 2016, 8(4), 134; https://doi.org/10.3390/polym8040134 - 8 Apr 2016

Cited by 24 | Viewed by 8748

Abstract

The impact of electrostatic attraction on the uptake of gold nanoparticles (AuNPs) into positively charged strong poly-[2-(Methacryloyloxy) ethyl] trimethylammonium chloride (PMETAC) polyelectrolyte brushes was investigated. In this work, PMETAC brushes were synthesized via surface-initiated atom transfer radical polymerization (Si-ATRP). PMETAC/AuNP composite materials were [...] Read more.

The impact of electrostatic attraction on the uptake of gold nanoparticles (AuNPs) into positively charged strong poly-[2-(Methacryloyloxy) ethyl] trimethylammonium chloride (PMETAC) polyelectrolyte brushes was investigated. In this work, PMETAC brushes were synthesized via surface-initiated atom transfer radical polymerization (Si-ATRP). PMETAC/AuNP composite materials were prepared by incubation of the polymer brush coated samples into 3-mercaptopropionic acid-capped AuNP (5 nm in diameter) suspension. The electrostatic interactions were tuned by changing the surface charge of the AuNPs through variations in pH value, while the charge of the PMETAC brush was not affected. Atomic-force microscopy (AFM), ellipsometry, UV/Vis spectroscopy, gravimetric analysis and transmission electron microscopy (TEM) were employed to study the loading and penetration into the polymer brush. The results show that the number density of attached AuNPs depends on the pH value and increases with increasing pH value. There is also strong evidence that the particle assembly is dependent on the pH value of the AuNP suspension. Incubation of PMETAC brushes in AuNP suspension at pH 4 led to the formation of a surface layer on top of the brush (2D assembly) due to sterical hindrance of the clustered AuNPs, while incubation in AuNP suspension at pH 8 led to deeper particle penetration into the brush (3D assembly). The straightforward control of particle uptake and assembly by tuning the charge density of the nanoparticle surface is a valuable tool for the development of materials for colorimetric sensor applications. Full article

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Open AccessReview

Activated Charge-Reversal Polymeric Nano-System: The Promising Strategy in Drug Delivery for Cancer Therapy

by Yichen Hu, Xiao Gong, Jinming Zhang, Fengqian Chen, Chaomei Fu, Peng Li, Liang Zou and Gang Zhao

Polymers 2016, 8(4), 99; https://doi.org/10.3390/polym8040099 - 5 Apr 2016

Cited by 39 | Viewed by 10489

Abstract

Various polymeric nanoparticles (NPs) with optimal size, tumor-targeting functionalization, or microenvironment sensitive characteristics have been designed to solve several limitations of conventional chemotherapy. Nano-sized polymeric drug carrier systems have remarkably great advantages in drug delivery and cancer therapy, which are still plagued with [...] Read more.

Various polymeric nanoparticles (NPs) with optimal size, tumor-targeting functionalization, or microenvironment sensitive characteristics have been designed to solve several limitations of conventional chemotherapy. Nano-sized polymeric drug carrier systems have remarkably great advantages in drug delivery and cancer therapy, which are still plagued with severe deficiencies, especially insufficient cellular uptake. Recently, surface charge of medical NPs has been demonstrated to play an important role in cellular uptake. NPs with positive charge show higher affinity to anionic cell membranes such that with more efficient cellular internalization, but otherwise cause severe aggregation and fast clearance in circulation. Thus, surface charge-reversal NPs, specifically activated at the tumor site, have shown to elegantly resolve the enhanced cellular uptake in cancer cells vs. non-specific protein adsorption dilemma. Herein, this review mainly focuses on the effect of tumor-site activated surface charge reversal NPs on tumor treatment, including the activated mechanisms and various applications in suppressing cancer cells, killing cancer stem cell and overcoming multidrug resistance, with the emphasis on recent research in these fields. With the comprehensive and in-depth understanding of the activated surface charge reversal NPs, this approach might arouse great interest of scientific research on enhanced efficient polymeric nano-carriers in cancer therapy. Full article

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Open AccessArticle

The Effect of Temperature Treatment on the Structure of Polyelectrolyte Multilayers

by Maximilian Zerball, André Laschewsky, Ralf Köhler and Regine Von Klitzing

Polymers 2016, 8(4), 120; https://doi.org/10.3390/polym8040120 - 2 Apr 2016

Cited by 15 | Viewed by 6458

Abstract

The study addresses the effect of thermal treatment on the internal structure of polyelectrolyte multilayers (PEMs). In order to get insight into the internal structure of PEMs, Neutron Reflectometry (NR) was used. PEMs with a deuterated inner block towards the substrate and a [...] Read more.

The study addresses the effect of thermal treatment on the internal structure of polyelectrolyte multilayers (PEMs). In order to get insight into the internal structure of PEMs, Neutron Reflectometry (NR) was used. PEMs with a deuterated inner block towards the substrate and a non-deuterated outer block were prepared and measured in 1% RH and in D₂O before and after a thermal treatment. Complementarily, PEMs with the same number of layers but completely non-deuterated were investigated by ellipsometry. The analysis for the overall thickness (d), the average scattering length density (SLD) and the refractive index (n) indicate a degradation of the PEM. The loss in material is independent of the number of layers, i.e., only a constant part of the PEM is affected by degradation. The analysis of the internal structure revealed a more complex influence of thermal treatment on PEM structure. Only the outermost part of the PEM degenerates, while the inner part becomes denser during the thermal treatment. In addition, the swelling behavior of PEMs is influenced by the thermal treatment. The untreated PEM shows a well pronounced odd—even effect, i.e., PDADMAC-terminated PEMs take up more water than PSS-terminated PEMs. After the thermal treatment, the odd-even effect becomes much weaker. Full article

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Open AccessArticle

Influence of the Near Molecular Vicinity on the Temperature Regulated Fluorescence Response of Poly(N-vinylcaprolactam)

by Anne Enzenberg, André Laschewsky, Christine Boeffel and Erik Wischerhoff

Polymers 2016, 8(4), 109; https://doi.org/10.3390/polym8040109 - 25 Mar 2016

Cited by 12 | Viewed by 5850

Abstract

A series of new fluorescent dye bearing monomers, including glycomonomers, based on maleamide and maleic esteramide was synthesized. The dye monomers were incorporated by radical copolymerization into thermo-responsive poly(N‑vinyl-caprolactam) that displays a lower critical solution temperature (LCST) in aqueous solution. The [...] Read more.

A series of new fluorescent dye bearing monomers, including glycomonomers, based on maleamide and maleic esteramide was synthesized. The dye monomers were incorporated by radical copolymerization into thermo-responsive poly(N‑vinyl-caprolactam) that displays a lower critical solution temperature (LCST) in aqueous solution. The effects of the local molecular environment on the polymers’ luminescence, in particular on the fluorescence intensity and the extent of solvatochromism, were investigated below as well as above the phase transition. By attaching substituents of varying size and polarity in the close vicinity of the fluorophore, and by varying the spacer groups connecting the dyes to the polymer backbone, we explored the underlying structure–property relationships, in order to establish rules for successful sensor designs, e.g., for molecular thermometers. Most importantly, spacer groups of sufficient length separating the fluorophore from the polymer backbone proved to be crucial for obtaining pronounced temperature regulated fluorescence responses. Full article

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Open AccessFeature PaperArticle

Water-Dispersible Silica-Polyelectrolyte Nanocomposites Prepared via Acid-Triggered Polycondensation of Silicic Acid and Directed by Polycations

by Philip Overton, Elena Danilovtseva, Erno Karjalainen, Mikko Karesoja, Vadim Annenkov, Heikki Tenhu and Vladimir Aseyev

Polymers 2016, 8(3), 96; https://doi.org/10.3390/polym8030096 - 22 Mar 2016

Cited by 7 | Viewed by 11641

Abstract

The present work describes the acid-triggered condensation of silicic acid, Si(OH)₄, as directed by selected polycations in aqueous solution in the pH range of 6.5–8.0 at room temperature, without the use of additional solvents or surfactants. This process results in the [...] Read more.

The present work describes the acid-triggered condensation of silicic acid, Si(OH)₄, as directed by selected polycations in aqueous solution in the pH range of 6.5–8.0 at room temperature, without the use of additional solvents or surfactants. This process results in the formation of silica-polyelectrolyte (S-PE) nanocomposites in the form of precipitate or water-dispersible particles. The mean hydrodynamic diameter (d_h) of size distributions of the prepared water-dispersible S-PE composites is presented as a function of the solution pH at which the composite formation was achieved. Poly(2-(dimethylamino)ethyl methacrylate) (PDMAEMA) and block copolymers of DMAEMA and oligo(ethylene glycol) methyl ether methacrylate (OEGMA) were used as weak polyelectrolytes in S-PE composite formation. The activity of the strong polyelectrolytes poly(methacryloxyethyl trimethylammonium iodide) (PMOTAI) and PMOTAI-b-POEGMA in S-PE formation is also examined. The effect of polyelectrolyte strength and the OEGMA block on the formation of the S-PE composites is assessed with respect to the S-PE composites prepared using the PDMAEMA homopolymer. In the presence of the PDMAEMA₆₀ homopolymer (M_w = 9400 g/mol), the size of the dispersible S-PE composites increases with solution pH in the range pH 6.6–8.1, from d_h = 30 nm to d_h = 800 nm. S-PDMAEMA₆₀ prepared at pH 7.8 contained 66% silica by mass (TGA). The increase in dispersible S-PE particle size is diminished when directed by PDMAEMA₃₀₀ (M_w = 47,000 g/mol), reaching a maximum of d_h = 75 nm. S-PE composites formed using PDMAEMA-b-POEGMA remain in the range d_h = 20–30 nm across this same pH regime. Precipitated S-PE composites were obtained as spheres of up to 200 nm in diameter (SEM) and up to 65% mass content of silica (TGA). The conditions of pH for the preparation of dispersible and precipitate S-PE nanocomposites, as directed by the five selected polyelectrolytes PDMAEMA₆₀, PDMAEMA₃₀₀, PMOTAI₆₀, PDMAEMA₆₀-b-POEGMA₃₈ and PMOTAI₆₀-b-POEGMA₃₈ is summarized. Full article

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Open AccessArticle

Systematic Limitations in Concentration Analysis via Anomalous Small-Angle X-ray Scattering in the Small Structure Limit

by Guenter Goerigk, Sebastian Lages and Klaus Huber

Polymers 2016, 8(3), 85; https://doi.org/10.3390/polym8030085 - 16 Mar 2016

Cited by 2 | Viewed by 10835

Abstract

Anomalous small angle scattering measurements have been applied to diluted solutions of anionic polyacrylates decorated by specifically-interacting Pb²⁺ cations, revealing partial collapse of the polyacrylate into pearl-like subdomains with a size on the order of a few nanometers. From the pure-resonant scattering [...] Read more.

Anomalous small angle scattering measurements have been applied to diluted solutions of anionic polyacrylates decorated by specifically-interacting Pb²⁺ cations, revealing partial collapse of the polyacrylate into pearl-like subdomains with a size on the order of a few nanometers. From the pure-resonant scattering contribution of the Pb²⁺ cations, and from subsequent analysis of the resonant-invariant, the amount of Pb²⁺ cations condensed onto the polyanions with respect to the total amount of Pb²⁺ cations in the solvent was estimated. In order to scrutinize systematic limitations in the determination of the chemical concentrations of resonant scattering counterions in the collapsed phase, Monte Carlo simulations have been performed. The simulations are based on structural confinements at variable size in the range of few nanometers, which represent the collapsed subdomains in the polyanions. These confinements were gradually filled to a high degree of the volume fraction with resonant scattering counterions giving access to a resonant-invariant at a variable degree of filling. The simulations revealed in the limit of small structures a significant underestimation of the true degree of filling of the collapsed subdomains when determining chemical concentrations of Pb²⁺ cations from the resonant invariant. Full article

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Open AccessFeature PaperArticle

Enzymatic Synthesis and Characterization of Hydrophilic Sugar Based Polyesters and Their Modification with Stearic Acid

by Muhammad Humayun Bilal, Marko Prehm, Andrew Efraim Njau, Muhammad Haris Samiullah, Annette Meister and Jörg Kressler

Polymers 2016, 8(3), 80; https://doi.org/10.3390/polym8030080 - 16 Mar 2016

Cited by 22 | Viewed by 9567

Abstract

Biodegradable and hydrophilic functional polyesters were synthesized enzymatically using xylitol or d-sorbitol together with divinyl adipate and lipase B from Candida antartica (CAL-B). The resulting polyesters had pendant OH-groups from their sugar units which were esterified to different degrees with stearic acid [...] Read more.

Biodegradable and hydrophilic functional polyesters were synthesized enzymatically using xylitol or d-sorbitol together with divinyl adipate and lipase B from Candida antartica (CAL-B). The resulting polyesters had pendant OH-groups from their sugar units which were esterified to different degrees with stearic acid chloride. The structure and the degrees of polymerization of the resulting graft copolymers based on poly(xylitol adipate) and poly(d-sorbitol adipate) were characterized by ¹H NMR spectroscopy and SEC. DSC, WAXS and SAXS measurements indicated that a phase separation between polymer backbone and stearoyl side chains occurred in the graft copolymers, and, additionally, the side chains were able to crystallize which resulted in the formation of a lamellar morphology. Additionally, nanoparticles of the graft copolymers in an aqueous environment were studied by DLS and negative stain TEM. Full article

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Open AccessFeature PaperArticle

Hybrid Polymer-Network Hydrogels with Tunable Mechanical Response

by Sebastian Czarnecki, Torsten Rossow and Sebastian Seiffert

Polymers 2016, 8(3), 82; https://doi.org/10.3390/polym8030082 - 15 Mar 2016

Cited by 34 | Viewed by 9949

Abstract

Hybrid polymer-network gels built by both physical and covalent polymer crosslinking combine the advantages of both these crosslinking types: they exhibit high mechanical strength along with excellent fracture toughness and extensibility. If these materials are extensively deformed, their physical crosslinks can break such [...] Read more.

Hybrid polymer-network gels built by both physical and covalent polymer crosslinking combine the advantages of both these crosslinking types: they exhibit high mechanical strength along with excellent fracture toughness and extensibility. If these materials are extensively deformed, their physical crosslinks can break such that strain energy is dissipated and irreversible fracturing is restricted to high strain only. This mechanism of energy dissipation is determined by the kinetics and thermodynamics of the physical crosslinking contribution. In this paper, we present a poly(ethylene glycol) (PEG) based material toolkit to control these contributions in a rational and custom fashion. We form well-defined covalent polymer-network gels with regularly distributed additional supramolecular mechanical fuse links, whose strength of connectivity can be tuned without affecting the primary polymer-network composition. This is possible because the supramolecular fuse links are based on terpyridine–metal complexation, such that the mere choice of the fuse-linking metal ion adjusts their kinetics and thermodynamics of complexation–decomplexation, which directly affects the mechanical properties of the hybrid gels. We use oscillatory shear rheology to demonstrate this rational control and enhancement of the mechanical properties of the hybrid gels. In addition, static light scattering reveals their highly regular and well-defined polymer-network structures. As a result of both, the present approach provides an easy and reliable concept for preparing hybrid polymer-network gels with rationally designed properties. Full article

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Open AccessArticle

Polyelectrolyte Threading through a Nanopore

by Pai-Yi Hsiao

Polymers 2016, 8(3), 73; https://doi.org/10.3390/polym8030073 - 3 Mar 2016

Cited by 12 | Viewed by 6645

Abstract

Threading charged polymers through a nanopore, driven by electric fields E, is investigated by means of Langevin dynamics simulations. The mean translocation time ⟨ τ ⟩ is shown to follow a scaling law N^α, and the exponent α increases monotonically from [...] Read more.

Threading charged polymers through a nanopore, driven by electric fields E, is investigated by means of Langevin dynamics simulations. The mean translocation time 〈 τ 〉 is shown to follow a scaling law N^α, and the exponent α increases monotonically from 1.16 (4) to 1.40 (3) with E. The result is double-checked by the calculation of mean square displacement of translocation coordinate, which asserts a scaling behavior t^β (for t near τ) with β complying with the relation αβ = 2. At a fixed chain length N, 〈τ〉 displayed a reciprocal scaling behavior E⁻¹ in the weak and also in the strong fields, connected by a transition E^−1.64(5) in the intermediate fields. The variations of the radius of gyration of chain and the positions of chain end are monitored during a translocation process; far-from-equilibrium behaviors are observed when the driving field is strong. A strong field can strip off the condensed ions on the chain when it passes the pore. The total charges of condensed ions are hence decreased. The studies for the probability and density distributions reveal that the monomers in the trans-region are gathered near the wall and form a pancake-like density profile with a hump cloud over it in the strong fields, due to fast translocation. Full article

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Open AccessFeature PaperArticle

pH-Responsive Intra- and Inter-Molecularly Micelle Formation of Anionic Diblock Copolymer in Water

by Masanobu Mizusaki, Yoshihiko Shimada, Yotaro Morishima and Shin-ichi Yusa

Polymers 2016, 8(2), 56; https://doi.org/10.3390/polym8020056 - 19 Feb 2016

Cited by 6 | Viewed by 7074

Abstract

Poly(sodium2-(acrylamido)-2-methylpropanesulfonate)-block-poly(sodium11-(acrylamido)undecanoate) (PAMPS–PAaU) was synthesized via reversible addition-fragmentation chain transfer (RAFT)-controlled radical polymerization. The “living” polymerization of PAaU was evidenced by the fact that the molecular weight distribution was narrow (M_w/M_n = 1.23). The pH-induced association behavior [...] Read more.

Poly(sodium2-(acrylamido)-2-methylpropanesulfonate)-block-poly(sodium11-(acrylamido)undecanoate) (PAMPS–PAaU) was synthesized via reversible addition-fragmentation chain transfer (RAFT)-controlled radical polymerization. The “living” polymerization of PAaU was evidenced by the fact that the molecular weight distribution was narrow (M_w/M_n = 1.23). The pH-induced association behavior of PAMPS–PAaU in 0.1 M NaCl aqueous solutions as a function of solution pH was investigated by ¹H NMR spin-spin relaxation time, dynamic light scattering (DLS), static light scattering (SLS), and fluorescence probe techniques. These results indicated that PAMPS–PAaU formed polymer micelles in 0.1 M NaCl aqueous solutions at pH < 9. At pH = 8–9, the polymer formed the micelles intramolecularly due to hydrophobic self-association of the PAaU block within the single polymer chain. On the other hand, at pH < 8, micellization occurred intermolecularly to form polymer micelles comprising hydrophobic PAaU cores and hydrophilic PAMPS shells. Full article

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6880 KiB

Open AccessArticle

Conformation and Rheological Properties of Calf-Thymus DNA in Solution

by Lourdes Mónica Bravo-Anaya, Marguerite Rinaudo and Félix Armando Soltero Martínez

Polymers 2016, 8(2), 51; https://doi.org/10.3390/polym8020051 - 11 Feb 2016

Cited by 31 | Viewed by 9347

Abstract

Studies of DNA molecule behavior in aqueous solutions performed through different approaches allow assessment of the solute-solvent interactions and examination of the strong influence of conformation on its physicochemical properties, in the presence of different ionic species and ionic concentrations. Firstly, the conformational [...] Read more.

Studies of DNA molecule behavior in aqueous solutions performed through different approaches allow assessment of the solute-solvent interactions and examination of the strong influence of conformation on its physicochemical properties, in the presence of different ionic species and ionic concentrations. Firstly, the conformational behavior of calf-thymus DNA molecules in TE buffer solution is presented as a function of temperature. Secondly, their rheological behavior is discussed, as well as the evidence of the critical concentrations, i.e., the overlap and the entanglement concentrations (C* and C_e, respectively) from steady state flow and oscillatory dynamic shear experiments. The determination of the viscosity in the Newtonian plateau obtained from flow curves η ( ) allows estimation of the intrinsic viscosity and the specific viscosities at zero shear when C[η] < 40. At end, a generalized master curve is obtained from the variation of the specific viscosity as a function of the overlap parameter C[η]. The variation of the exponent s obtained from the power law η~ ^−s for both flow and dynamic results is discussed in terms of Graessley’s analysis. In the semi-dilute regime with entanglements, a dynamic master curve is obtained as a function of DNA concentration (C_DNA > 2.0 mg/mL) and temperature (10 °C < T < 40 °C). Full article

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2015

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1637 KiB

Open AccessReview

Recent Progress and Perspectives in the Electrokinetic Characterization of Polyelectrolyte Films

by Ralf Zimmermann, Carsten Werner and Jérôme F. L. Duval

Polymers 2016, 8(1), 7; https://doi.org/10.3390/polym8010007 - 31 Dec 2015

Cited by 15 | Viewed by 6057

Abstract

The analysis of the charge, structure and molecular interactions of/within polymeric substrates defines an important analytical challenge in materials science. Accordingly, advanced electrokinetic methods and theories have been developed to investigate the charging mechanisms and structure of soft material coatings. In particular, there [...] Read more.

The analysis of the charge, structure and molecular interactions of/within polymeric substrates defines an important analytical challenge in materials science. Accordingly, advanced electrokinetic methods and theories have been developed to investigate the charging mechanisms and structure of soft material coatings. In particular, there has been significant progress in the quantitative interpretation of streaming current and surface conductivity data of polymeric films from the application of recent theories developed for the electrohydrodynamics of diffuse soft planar interfaces. Here, we review the theory and experimental strategies to analyze the interrelations of the charge and structure of polyelectrolyte layers supported by planar carriers under electrokinetic conditions. To illustrate the options arising from these developments, we discuss experimental and simulation data for plasma-immobilized poly(acrylic acid) films and for a polyelectrolyte bilayer consisting of poly(ethylene imine) and poly(acrylic acid). Finally, we briefly outline potential future developments in the field of the electrokinetics of polyelectrolyte layers. Full article

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2014

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646 KiB

Open AccessArticle

Charge Inversion Effects in Electrophoresis of Polyelectrolytes in the Presence of Multivalent Counterions and Transversal Electric Fields

by Sorin Nedelcu and Jens-Uwe Sommer

Polymers 2014, 6(12), 2942-2960; https://doi.org/10.3390/polym6122942 - 4 Dec 2014

Cited by 1 | Viewed by 6055

Abstract

By molecular dynamics simulations we investigate the transport of charged polymers in confinement, under externally applied electric fields, in straight cylinders of uniform diameter and in the presence of monovalent or multivalent counterions. The applied electric field has two components; a longitudinal component [...] Read more.

By molecular dynamics simulations we investigate the transport of charged polymers in confinement, under externally applied electric fields, in straight cylinders of uniform diameter and in the presence of monovalent or multivalent counterions. The applied electric field has two components; a longitudinal component along the axis of the cylinder and a transversal component perpendicular to the cylinder axis. The direction of electrophoretic velocity depends on the polyelectrolyte length, valency of the counterions present in solution and transversal electric field value. A statistical model is put forward in order to explain these observations. Full article

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1351 KiB

Open AccessReview

Polyelectrolyte Multilayers in Microfluidic Systems for Biological Applications

by Saugandhika Minnikanti, Aveek Gangopadhyay and Darwin R. Reyes

Polymers 2014, 6(8), 2100-2115; https://doi.org/10.3390/polym6082100 - 31 Jul 2014

Cited by 10 | Viewed by 8383

Abstract

The formation of polyelectrolyte multilayers (PEMs) for the first time, two decades ago, demonstrating the assembly on charged substrates in a very simple and efficient way, has proven to be a reliable method to obtain structures tunable at the nanometer scale. Much effort [...] Read more.

The formation of polyelectrolyte multilayers (PEMs) for the first time, two decades ago, demonstrating the assembly on charged substrates in a very simple and efficient way, has proven to be a reliable method to obtain structures tunable at the nanometer scale. Much effort has been put into the assembly of these structures for their use in biological applications. A number of these efforts have been in combination with microfluidic systems, which add to the nanoassembly that is already possible with polyelectrolytes, a new dimension in the construction of valuable structures, some of them not possible with conventional systems. This review focuses on the advancements demonstrated by the combination of PEMs and microfluidic systems, and their use in biological applications. Full article

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801 KiB

Open AccessArticle

Lipid Monolayers with Adsorbed Oppositely Charged Polyelectrolytes: Influence of Reduced Charge Densities

by Thomas Ortmann, Heiko Ahrens, Sven Milewski, Frank Lawrenz, Andreas Gröning, André Laschewsky, Sebastien Garnier and Christiane A. Helm

Polymers 2014, 6(7), 1999-2017; https://doi.org/10.3390/polym6071999 - 10 Jul 2014

Cited by 4 | Viewed by 7776

Abstract

Polyelectrolytes in dilute solutions (0.01 mmol/L) adsorb in a two-dimensional lamellar phase to oppositely charged lipid monolayers at the air/water interface. The interchain separation is monitored by Grazing Incidence X-ray Diffraction. On monolayer compression, the interchain separation decreases to a factor of two. [...] Read more.

Polyelectrolytes in dilute solutions (0.01 mmol/L) adsorb in a two-dimensional lamellar phase to oppositely charged lipid monolayers at the air/water interface. The interchain separation is monitored by Grazing Incidence X-ray Diffraction. On monolayer compression, the interchain separation decreases to a factor of two. To investigate the influence of the electrostatic interaction, either the line charge density of the polymer is reduced (a statistic copolymer with 90% and 50% charged monomers) or mixtures between charged and uncharged lipids are used (dipalmitoylphosphatidylcholine (DPPC)/ dioctadecyldimethylammonium bromide (DODAB)) On decrease of the surface charge density, the interchain separation increases, while on decrease of the linear charge density, the interchain separation decreases. The ratio between charged monomers and charged lipid molecules is fairly constant; it decreases up to 30% when the lipids are in the fluid phase. With decreasing surface charge or linear charge density, the correlation length of the lamellar order decreases. Full article

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Open AccessArticle

Salt Effect on Osmotic Pressure of Polyelectrolyte Solutions: Simulation Study

by Jan-Michael Y. Carrillo and Andrey V. Dobrynin

Polymers 2014, 6(7), 1897-1913; https://doi.org/10.3390/polym6071897 - 4 Jul 2014

Cited by 30 | Viewed by 10267

Abstract

Abstract: We present results of the hybrid Monte Carlo/molecular dynamics simulations of the osmotic pressure of salt solutions of polyelectrolytes. In our simulations, we used a coarse-grained representation of polyelectrolyte chains, counterions and salt ions. During simulation runs, we alternate Monte Carlo [...] Read more.

Abstract: We present results of the hybrid Monte Carlo/molecular dynamics simulations of the osmotic pressure of salt solutions of polyelectrolytes. In our simulations, we used a coarse-grained representation of polyelectrolyte chains, counterions and salt ions. During simulation runs, we alternate Monte Carlo and molecular dynamics simulation steps. Monte Carlo steps were used to perform small ion exchange between simulation box containing salt ions (salt reservoir) and simulation box with polyelectrolyte chains, counterions and salt ions (polyelectrolyte solution). This allowed us to model Donnan equilibrium and partitioning of salt and counterions across membrane impermeable to polyelectrolyte chains. Our simulations have shown that the main contribution to the system osmotic pressure is due to salt ions and osmotically active counterions. The fraction of the condensed (osmotically inactive) counterions first increases with decreases in the solution ionic strength then it saturates. The reduced value of the system osmotic coefficient is a universal function of the ratio of the concentration of osmotically active counterions and salt concentration in salt reservoir. Simulation results are in a very good agreement with osmotic pressure measurements in sodium polystyrene sulfonate, DNA, polyacrylic acid, sodium polyanetholesulfonic acid, polyvinylbenzoic acid, and polydiallyldimethylammonium chloride solutions. Full article

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Open AccessArticle

Stimuli-Responsive Polyelectrolyte Brushes As a Matrix for the Attachment of Gold Nanoparticles: The Effect of Brush Thickness on Particle Distribution

by Stephanie Christau, Stefan Thurandt, Zuleyha Yenice and Regine Von Klitzing

Polymers 2014, 6(7), 1877-1896; https://doi.org/10.3390/polym6071877 - 27 Jun 2014

Cited by 43 | Viewed by 10172

Abstract

The effect of brush thickness on the loading of gold nanoparticles (AuNPs) within stimuli-responsive poly-(N,N-(dimethylamino ethyl) methacrylate) (PDMAEMA) polyelectrolyte brushes is reported. Atom transfer radical polymerization (ATRP) was used to grow polymer brushes via a “grafting from” approach. The brush thickness was tuned [...] Read more.

The effect of brush thickness on the loading of gold nanoparticles (AuNPs) within stimuli-responsive poly-(N,N-(dimethylamino ethyl) methacrylate) (PDMAEMA) polyelectrolyte brushes is reported. Atom transfer radical polymerization (ATRP) was used to grow polymer brushes via a “grafting from” approach. The brush thickness was tuned by varying the polymerization time. Using a new type of sealed reactor, thick brushes were synthesized. A systematic study was performed by varying a single parameter (brush thickness), while keeping all other parameters constant. AuNPs of 13 nm in diameter were attached by incubation. X-ray reflectivity, electron scanning microscopy and ellipsometry were used to study the particle loading, particle distribution and interpenetration of the particles within the brush matrix. A model for the structure of the brush/particle hybrids was derived. The particle number densities of attached AuNPs depend on the brush thickness, as do the optical properties of the hybrids. An increasing particle number density was found for increasing brush thickness, due to an increased surface roughness. Full article

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Open AccessArticle

The Effect of Salt on the Complex Coacervation of Vinyl Polyelectrolytes

by Sarah L. Perry, Yue Li, Dimitrios Priftis, Lorraine Leon and Matthew Tirrell

Polymers 2014, 6(6), 1756-1772; https://doi.org/10.3390/polym6061756 - 16 Jun 2014

Cited by 209 | Viewed by 21039

Abstract

Complex coacervation is an electrostatically-driven phase separation phenomenon that is utilized in a wide range of everyday applications and is of great interest for the creation of self-assembled materials. Here, we utilized turbidity to characterize the effect of salt type on coacervate formation [...] Read more.

Complex coacervation is an electrostatically-driven phase separation phenomenon that is utilized in a wide range of everyday applications and is of great interest for the creation of self-assembled materials. Here, we utilized turbidity to characterize the effect of salt type on coacervate formation using two vinyl polyelectrolytes, poly(acrylic acid sodium salt) (pAA) and poly(allylamine hydrochloride) (pAH), as simple models for industrial and biological coacervates. We confirmed the dominant role of salt valence on the extent of coacervate formation, while demonstrating the presence of significant secondary effects, which can be described by Hofmeister-like behavior. These results revealed the importance of ion-specific interactions, which are crucial for the informed design of coacervate-based materials for use in complex ionic environments, and can enable more detailed theoretical investigations on the role of subtle electrostatic and thermodynamic effects in complex coacervation. Full article

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Open AccessArticle

A Coarse-Grained DNA Model Parameterized from Atomistic Simulations by Inverse Monte Carlo

by Nikolay Korolev, Di Luo, Alexander P. Lyubartsev and Lars Nordenskiöld

Polymers 2014, 6(6), 1655-1675; https://doi.org/10.3390/polym6061655 - 30 May 2014

Cited by 48 | Viewed by 11686

Abstract

Computer modeling of very large biomolecular systems, such as long DNA polyelectrolytes or protein-DNA complex-like chromatin cannot reach all-atom resolution in a foreseeable future and this necessitates the development of coarse-grained (CG) approximations. DNA is both highly charged and mechanically rigid semi-flexible polymer [...] Read more.

Computer modeling of very large biomolecular systems, such as long DNA polyelectrolytes or protein-DNA complex-like chromatin cannot reach all-atom resolution in a foreseeable future and this necessitates the development of coarse-grained (CG) approximations. DNA is both highly charged and mechanically rigid semi-flexible polymer and adequate DNA modeling requires a correct description of both its structural stiffness and salt-dependent electrostatic forces. Here, we present a novel CG model of DNA that approximates the DNA polymer as a chain of 5-bead units. Each unit represents two DNA base pairs with one central bead for bases and pentose moieties and four others for phosphate groups. Charges, intra- and inter-molecular force field potentials for the CG DNA model were calculated using the inverse Monte Carlo method from all atom molecular dynamic (MD) simulations of 22 bp DNA oligonucleotides. The CG model was tested by performing dielectric continuum Langevin MD simulations of a 200 bp double helix DNA in solutions of monovalent salt with explicit ions. Excellent agreement with experimental data was obtained for the dependence of the DNA persistent length on salt concentration in the range 0.1–100 mM. The new CG DNA model is suitable for modeling various biomolecular systems with adequate description of electrostatic and mechanical properties. Full article

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Open AccessArticle

Development of a Biocompatible Layer-by-Layer Film System Using Aptamer Technology for Smart Material Applications

by Amanda Foster and Maria C. DeRosa

Polymers 2014, 6(5), 1631-1654; https://doi.org/10.3390/polym6051631 - 23 May 2014

Cited by 9 | Viewed by 8638

Abstract

Aptamers are short, single-stranded nucleic acids that fold into well-defined three dimensional (3D) structures that allow for binding to a target molecule with affinities and specificities that can rival or in some cases exceed those of antibodies. The compatibility of aptamers with nanostructures [...] Read more.

Aptamers are short, single-stranded nucleic acids that fold into well-defined three dimensional (3D) structures that allow for binding to a target molecule with affinities and specificities that can rival or in some cases exceed those of antibodies. The compatibility of aptamers with nanostructures such as thin films, in combination with their affinity, selectivity, and conformational changes upon target interaction, could set the foundation for the development of novel smart materials. In this study, the development of a biocompatible aptamer-polyelectrolyte film system was investigated using a layer-by-layer approach. Using fluorescence microscopy, we demonstrated the ability of the sulforhodamine B aptamer to bind its cognate target while sequestered in a chitosan-hyaluronan film matrix. Studies using Ultraviolet-visible (UV-Vis) spectrophotometry also suggest that deposition conditions such as rinsing time and volume play a strong role in the internal film interactions and growth mechanisms of chitosan-hyaluronan films. The continued study and development of aptamer-functionalized thin films provides endless new opportunities for novel smart materials and has the potential to revolutionize the field of controlled release. Full article

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Open AccessArticle

Structure of Microgels with Debye–Hückel Interactions

by Hideki Kobayashi and Roland G. Winkler

Polymers 2014, 6(5), 1602-1617; https://doi.org/10.3390/polym6051602 - 23 May 2014

Cited by 57 | Viewed by 10114

Abstract

The structural properties of model microgel particles are investigated by molecular dynamics simulations applying a coarse-grained model. A microgel is comprised of a regular network of polymers internally connected by tetra-functional cross-links and with dangling ends at its surface. The self-avoiding polymers are [...] Read more.

The structural properties of model microgel particles are investigated by molecular dynamics simulations applying a coarse-grained model. A microgel is comprised of a regular network of polymers internally connected by tetra-functional cross-links and with dangling ends at its surface. The self-avoiding polymers are modeled as bead-spring linear chains. Electrostatic interactions are taken into account by the Debye–Hückel potential. The microgels exhibit a quite uniform density under bad solvent conditions with a rather sharp surface. With increasing Debye length, structural inhomogeneities appear, their surface becomes fuzzy and, at very large Debye lengths, well defined again. Similarly, the polymer conformations change from a self-avoiding walk to a rod-like behavior. Thereby, the average polymer radius of gyration follows a scaling curve in terms of polymer length and persistence length, with an asymptotic rod-like behavior for swollen microgels and self-avoiding walk behavior for weakly swollen gel particles. Full article

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463 KiB

Open AccessReview

Structures and Synthesis of Zwitterionic Polymers

by André Laschewsky

Polymers 2014, 6(5), 1544-1601; https://doi.org/10.3390/polym6051544 - 23 May 2014

Cited by 353 | Viewed by 36847

Abstract

The structures and synthesis of polyzwitterions (“polybetaines”) are reviewed, emphasizing the literature of the past decade. Particular attention is given to the general challenges faced, and to successful strategies to obtain polymers with a true balance of permanent cationic and anionic groups, thus [...] Read more.

The structures and synthesis of polyzwitterions (“polybetaines”) are reviewed, emphasizing the literature of the past decade. Particular attention is given to the general challenges faced, and to successful strategies to obtain polymers with a true balance of permanent cationic and anionic groups, thus resulting in an overall zero charge. Also, the progress due to applying new methodologies from general polymer synthesis, such as controlled polymerization methods or the use of “click” chemical reactions is presented. Furthermore, the emerging topic of responsive (“smart”) polyzwitterions is addressed. The considerations and critical discussions are illustrated by typical examples. Full article

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Open AccessArticle

pH and Salt Effects on the Associative Phase Separation of Oppositely Charged Polyelectrolytes

by Prateek K. Jha, Priyanka S. Desai, Jingyi Li and Ronald G. Larson

Polymers 2014, 6(5), 1414-1436; https://doi.org/10.3390/polym6051414 - 16 May 2014

Cited by 110 | Viewed by 15435

Abstract

The classical Voorn-Overbeek thermodynamic theory of complexation and phase separation of oppositely charged polyelectrolytes is generalized to account for the charge accessibility and hydrophobicity of polyions, size of salt ions, and pH variations. Theoretical predictions of the effects of pH and salt concentration [...] Read more.

The classical Voorn-Overbeek thermodynamic theory of complexation and phase separation of oppositely charged polyelectrolytes is generalized to account for the charge accessibility and hydrophobicity of polyions, size of salt ions, and pH variations. Theoretical predictions of the effects of pH and salt concentration are compared with published experimental data and experiments we performed, on systems containing poly(acrylic acid) (PAA) as the polyacid and poly(N,N-dimethylaminoethyl methacrylate) (PDMAEMA) or poly(diallyldimethyl ammonium chloride) (PDADMAC) as the polybase. In general, the critical salt concentration below which the mixture phase separates, increases with degree of ionization and with the hydrophobicity of polyelectrolytes. We find experimentally that as the pH is decreased below 7, and PAA monomers are neutralized, the critical salt concentration increases, while the reverse occurs when pH is raised above 7. We predict this asymmetry theoretically by introducing a large positive Flory parameter (= 0.75) for the interaction of neutral PAA monomers with water. This large positive Flory parameter is supported by molecular dynamics simulations, which show much weaker hydrogen bonding between neutral PAA and water than between charged PAA and water, while neutral and charged PDMAEMA show similar numbers of hydrogen bonds. This increased hydrophobicity of neutral PAA at reduced pH increases the tendency towards phase separation despite the reduction in charge interactions between the polyelectrolytes. Water content and volume of coacervate are found to be a strong function of the pH and salt concentration. Full article

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660 KiB

Open AccessReview

Does Electrical Conductivity of Linear Polyelectrolytes in Aqueous Solutions Follow the Dynamic Scaling Laws? A Critical Review and a Summary of the Key Relations

by Cesare Cametti

Polymers 2014, 6(4), 1207-1231; https://doi.org/10.3390/polym6041207 - 22 Apr 2014

Cited by 10 | Viewed by 7516

Abstract

In this review, we focus on the electrical conductivity of aqueous polyelectrolyte solutions in the light of the dynamic scaling laws, recently proposed by Dobrynin and Rubinstein, to take into account the polymer conformations in different concentration regimes, both in good and poor [...] Read more.

In this review, we focus on the electrical conductivity of aqueous polyelectrolyte solutions in the light of the dynamic scaling laws, recently proposed by Dobrynin and Rubinstein, to take into account the polymer conformations in different concentration regimes, both in good and poor solvent conditions. This approach allows us to separate contributions due to polymer conformation from those due to the ionic character of the chain, and offers the possibility to extend the validity of the Manning conductivity model to dilute and semidilute regimes. The electrical conductivity in the light of the scaling approach compares reasonably well with the observed values for different polyelectrolytes in aqueous solutions, over an extended concentration range, from the dilute to the semidilute regime. Full article

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2011

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813 KiB

Open AccessArticle

Behavior of Na⁺-Polystyrene Sulfonate at the Interface with Single-Walled Carbon Nanotubes (SWNTs) and Its Implication to SWNT Suspension Stability

by Tabbetha Dobbins, Richard Chevious and Yuri Lvov

Polymers 2011, 3(2), 942-954; https://doi.org/10.3390/polym3020942 - 14 Jun 2011

Cited by 14 | Viewed by 10211

Abstract

The assembly of sodium polystyrene sulfonate (Na⁺-PSS) at the surface of single-walled carbon nanotubes (SWNTs) in pH 3 aqueous solution is described. Rather than forming linear or sheet-like chain morphologies over SWNT surfaces, Na⁺-PSS adopts a spherically collapsed conformation [...] Read more.

The assembly of sodium polystyrene sulfonate (Na⁺-PSS) at the surface of single-walled carbon nanotubes (SWNTs) in pH 3 aqueous solution is described. Rather than forming linear or sheet-like chain morphologies over SWNT surfaces, Na⁺-PSS adopts a spherically collapsed conformation believed to be the result of cation (either Na⁺ or H⁺) condensation onto the ionized polymer chain. It is well reported that cations (and also anions) adsorb preferentially onto single-walled and multi-walled carbon nanotube surfaces leading to an increased ion concentration in the near surface regions relative to the bulk solution. This work provides experimental evidence for preferentially absorbed cation condensation onto PSS anions until those cations are spaced at distances corresponding to the Bjerrum length ( _B), as defined by the Manning theory of ion condensation, at the SWNT surface. The resulting electrostearic repulsions allow the SWNTs to remain suspended for days. Furthermore , coulombic repulsion among SWNT bundles after cation adsorption alone is not sufficient to form stable suspensions—but rather the stearic repulsions associated with spherically collapsed PSS at the nanotube surface is responsible for suspension stability. It is believed that the ultrasonic agitation drives cations into the small spaces between SWNT bundles and coulombic potential attracts the PSS to those regions. Full article

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Open AccessArticle

Using Light Scattering to Screen Polyelectrolytes (PEL) Performance in Flocculation

by Maria G. Rasteiro, Ineide Pinheiro, Fernando A. P. Garcia, Paulo Ferreira and David Hunkeler

Polymers 2011, 3(2), 915-927; https://doi.org/10.3390/polym3020915 - 27 May 2011

Cited by 19 | Viewed by 8288

Abstract

Flocculation of precipitated calcium carbonate (PCC) was monitored using light diffraction spectroscopy (LDS). Four cationic polyacrylamides of high molar mass and with different degrees of branching, all copolymers of acrylamide (AM) and acryloyloxyethyltrimethyl ammonium chloride (Q9), were tested. LDS supplied information about the [...] Read more.

Flocculation of precipitated calcium carbonate (PCC) was monitored using light diffraction spectroscopy (LDS). Four cationic polyacrylamides of high molar mass and with different degrees of branching, all copolymers of acrylamide (AM) and acryloyloxyethyltrimethyl ammonium chloride (Q9), were tested. LDS supplied information about the kinetic curves for flocs growth and also for the flocs structure evolution. Flocculation kinetics, flocs size and structure, flocs resistance and reflocculation capacity could be correlated with the degree of branching of the polyelectrolytes (PEL). Furthermore, PEL with different degrees of branching corresponded to different values for the intrinsic viscosity, indicating differences in the polymer conformation, which explained well the performance differences in flocculation. Full article

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359 KiB

Open AccessArticle

Counterion Condensation and Effective Charge of PAMAM Dendrimers

by Ute Böhme, Anja Klenge, Brigitte Hänel and Ulrich Scheler

Polymers 2011, 3(2), 812-819; https://doi.org/10.3390/polym3020812 - 27 Apr 2011

Cited by 27 | Viewed by 8470

Abstract

PAMAM dendrimers are used as a model system to investigate the effects of counterion condensation and the effective charge for spherical polyelectrolytes. Because of their amino groups, PAMAM dendrimers are weak polyelectrolytes. Lowering the pH results in an increasing protonation of the amino [...] Read more.

PAMAM dendrimers are used as a model system to investigate the effects of counterion condensation and the effective charge for spherical polyelectrolytes. Because of their amino groups, PAMAM dendrimers are weak polyelectrolytes. Lowering the pH results in an increasing protonation of the amino groups which is monitored via the proton chemical shifts of the adjacent CH₂ groups. The effective charge is determined from a combination of diffusion and electrophoresis NMR. The fraction of the charges, which are effective for the interaction with an external electric field or other charges, decreases with increasing generation (size) of the dendrimers. Full article

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530 KiB

Open AccessArticle

Polyelectrolyte Complex Nanoparticles of Poly(ethyleneimine) and Poly(acrylic acid): Preparation and Applications

by Martin Müller, Bernd Keßler, Johanna Fröhlich, Sebastian Poeschla and Bernhard Torger

Polymers 2011, 3(2), 762-778; https://doi.org/10.3390/polym3020762 - 12 Apr 2011

Cited by 52 | Viewed by 12577

Abstract

In this contribution we outline polyelectrolyte (PEL) complex (PEC) nanoparticles, prepared by mixing solutions of the low cost PEL components poly(ethyleneimine) (PEI) and poly(acrylic acid) (PAC). It was found, that the size and internal structure of PEI/PAC particles can be regulated by process, [...] Read more.

In this contribution we outline polyelectrolyte (PEL) complex (PEC) nanoparticles, prepared by mixing solutions of the low cost PEL components poly(ethyleneimine) (PEI) and poly(acrylic acid) (PAC). It was found, that the size and internal structure of PEI/PAC particles can be regulated by process, media and structural parameters. Especially, mixing order, mixing ratio, PEL concentration, pH and molecular weight, were found to be sensible parameters to regulate the size (diameter) of spherical PEI/PAC nanoparticles, in the range between 80–1,000 nm, in a defined way. Finally, applications of dispersed PEI/PAC particles as additives for the paper making process, as well as for drug delivery, are outlined. PEI/PAC nanoparticles mixed directly on model cellulose film showed a higher adsorption level applying the mixing order 1. PAC 2. PEI compared to 1. PEI 2. PAC. Surface bound PEI/PAC nanoparticles were found to release a model drug compound and to stay immobilized due to the contact with the aqueous release medium. Full article

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Open AccessArticle

Phase Diagrams of the Aqueous Two-Phase Systems of Poly(ethylene glycol)/Sodium Polyacrylate/Salts

by Hans-Olof Johansson, Eloi Feitosa and Adalberto Pessoa Junior

Polymers 2011, 3(1), 587-601; https://doi.org/10.3390/polym3010587 - 9 Mar 2011

Cited by 63 | Viewed by 14475

Abstract

Aqueous two-phase systems consisting of polyethylene glycol (PEG), sodium polyacrylate (NaPAA), and a salt have been studied. The effects of the polymer size, salt type (NaCl, Na₂SO₄, sodium adipate and sodium azelate) and salt concentrations on the position of [...] Read more.

Aqueous two-phase systems consisting of polyethylene glycol (PEG), sodium polyacrylate (NaPAA), and a salt have been studied. The effects of the polymer size, salt type (NaCl, Na₂SO₄, sodium adipate and sodium azelate) and salt concentrations on the position of the binodal curve were investigated. The investigated PEG molecules had a molar mass of 2,000 to 8,000 g/mol, while that of NaPAA was 8,000 g/mol. Experimental phase diagrams, and tie lines and calculated phase diagrams, based on Flory-Huggins theory of polymer solutions are presented. Due to strong enthalpic and entropic balancing forces, the hydrophobicity of the added salt has a strong influence on the position of the binodal, which could be reproduced by model calculations. Full article

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2010

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3974 KiB

Open AccessArticle

Polyelectrolytes: Influence on Evaporative Self-Assembly of Particles and Assembly of Multilayers with Polymers, Nanoparticles and Carbon Nanotubes

by Irina Marchenko, Alexey Yashchenok, Sergey German, Olga Inozemtseva, Dmitry Gorin, Tatiana Bukreeva, Helmuth Mohwald and Andre Skirtach

Polymers 2010, 2(4), 690-708; https://doi.org/10.3390/polym2040690 - 9 Dec 2010

Cited by 9 | Viewed by 12135

Abstract

Assembling polyelectrolyte multilayers in a bottom-up approach is reported for polymers, particles, nanoparticles, and carbon nanotubes. Effects of polyelectrolyte multilayers on evaporative self-assembly of particles, which are of interest to a number of applications including photonic crystals, films and substrates, are investigated. Polyelectrolyte [...] Read more.

Assembling polyelectrolyte multilayers in a bottom-up approach is reported for polymers, particles, nanoparticles, and carbon nanotubes. Effects of polyelectrolyte multilayers on evaporative self-assembly of particles, which are of interest to a number of applications including photonic crystals, films and substrates, are investigated. Polyelectrolyte multilayer coatings bring multifunctionality to spherical particles and planar films. Studying the construction of polyelectrolyte assemblies is convenient in the planar layout: it is reported here for incorporation of gold and magnetic nanoparticles as well as of carbon nanotubes. Gold nanoparticles concentration is controlled within the films. Potential applications of both spherical structures and planar films are highlighted. Full article

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Open AccessArticle

Glucan Particle Encapsulated Rifampicin for Targeted Delivery to Macrophages

by Ernesto Soto, Yun Seong Kim, Jinhee Lee, Hardy Kornfeld and Gary Ostroff

Polymers 2010, 2(4), 681-689; https://doi.org/10.3390/polym2040681 - 6 Dec 2010

Cited by 67 | Viewed by 10871

Abstract

Glucan particles (GPs) are 2–4 mm spherical, hollow, porous shells extracted from Baker’s yeast, Saccharomyces cerevisae. The surface of the GPs is composed primarily of 1,3-b-glucan and the particles are efficiently phagocytosed via receptor-mediated cell uptake by macrophages, phagocytic cells expressing glucan receptors. [...] Read more.

Glucan particles (GPs) are 2–4 mm spherical, hollow, porous shells extracted from Baker’s yeast, Saccharomyces cerevisae. The surface of the GPs is composed primarily of 1,3-b-glucan and the particles are efficiently phagocytosed via receptor-mediated cell uptake by macrophages, phagocytic cells expressing glucan receptors. The hollow cavity of the GPs allows for efficient absorption and encapsulation of payload molecules. Rifampicin (Rif), a drug used in tuberculosis treatment, was encapsulated by precipitation in GPs and trapped using a calcium alginate or chitosan hydrogel to seal the pores of GPs and slow Rif release. Unplugged GP formulations immediately released Rif following particle resuspension in aqueous buffer. Alginate and chitosan sealing of GPs loaded with Rif was able to extend drug release for 24–72 h. GP-Rif formulations containing 10% w/w Rif/GP plugged with a calcium alginate hydrogel were effective at reducing colony forming units of M. tuberculosis strain mc²6020 in infected bone marrow macrophages ~80–90% at 24 and 72 hours. The amount of Rif delivered in the GP formulations was below the free Rif minimal inhibitory concentration demonstrating that GP targeted Rif delivery to macrophages enhances Rif antimicrobial effects. Full article

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Open AccessReview

Biological and Biomimetic Comb Polyelectrolytes

by Thomas Andrew Waigh and Aristeidis Papagiannopoulos

Polymers 2010, 2(2), 57-70; https://doi.org/10.3390/polym2020057 - 26 May 2010

Cited by 10 | Viewed by 10435

Abstract

Some new phenomena involved in the physical properties of comb polyelectrolyte solutions are reviewed. Special emphasis is given to synthetic biomimetic materials, and the structures formed by these molecules are compared with those of naturally occurring glycoprotein and proteoglycan solutions. Developments in the [...] Read more.

Some new phenomena involved in the physical properties of comb polyelectrolyte solutions are reviewed. Special emphasis is given to synthetic biomimetic materials, and the structures formed by these molecules are compared with those of naturally occurring glycoprotein and proteoglycan solutions. Developments in the determination of the structure and dynamics (viscoelasticity) of comb polymers in solution are also covered. Specifically the appearance of multi-globular structures, helical instabilities, liquid crystalline phases, and the self-assembly of the materials to produce hierarchical comb morphologies is examined. Comb polyelectrolytes are surface active and a short review is made of some recent experiments in this area that relate to their morphology when suspended in solution. We hope to emphasize the wide variety of phenomena demonstrated by the vast range of naturally occurring comb polyelectrolytes and the challenges presented to synthetic chemists designing biomimetic materials. Full article

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