International Journal of Molecular Sciences

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2 pages, 178 KiB

Open AccessEditorial

Editorial of Special Issue “The Self-Assembly and Design of Polyfunctional Nanosystems 2.0”

by Ruslan Kashapov and Lucia Zakharova

Int. J. Mol. Sci. 2022, 23(8), 4437; https://doi.org/10.3390/ijms23084437 - 18 Apr 2022

Viewed by 1268

Abstract

The intention of this Special Issue, entitled “The Self-Assembly and Design of Polyfunctional Nanosystems 2 [...] Full article

(This article belongs to the Special Issue The Self-Assembly and Design of Polyfunctional Nanosystems 2.0)

4 pages, 165 KiB

Open AccessEditorial

The Self-Assembly and Design of Polyfunctional Nanosystems

by Ruslan Kashapov and Lucia Zakharova

Int. J. Mol. Sci. 2021, 22(4), 2223; https://doi.org/10.3390/ijms22042223 - 23 Feb 2021

Cited by 1 | Viewed by 1993

Abstract

The current task of the molecular sciences is to create unique nanostructured materials with a given structure and with specific physicochemical properties on the basis of the existing wide range of molecules of natural and synthetic origin. A promising and inexpensive way to [...] Read more.

The current task of the molecular sciences is to create unique nanostructured materials with a given structure and with specific physicochemical properties on the basis of the existing wide range of molecules of natural and synthetic origin. A promising and inexpensive way to obtain nanostructured materials is the spontaneous self-assembly of molecular building blocks during random collisions in real dispersive systems in solution and at interfaces. This editorial aims to summarize the major points from the 11 scientific papers that contributed to the special issue “The Self-Assembly and Design of Polyfunctional Nanosystems”, assessing the modern self-assembly potential and strategies for maintaining sustainable development of the nanoindustry. Full article

(This article belongs to the Special Issue The Self-Assembly and Design of Polyfunctional Nanosystems)

Research

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11 pages, 4771 KiB

Open AccessArticle

Engineering Achiral Liquid Crystalline Polymers for Chiral Self-Recovery

by Tengfei Miao, Xiaoxiao Cheng, Yilin Qian, Yaling Zhuang and Wei Zhang

Int. J. Mol. Sci. 2021, 22(21), 11980; https://doi.org/10.3390/ijms222111980 - 5 Nov 2021

Cited by 4 | Viewed by 2210

Abstract

Flexible construction of permanently stored supramolecular chirality with stimulus-responsiveness remains a big challenge. Herein, we describe an efficient method to realize the transfer and storage of chirality in intrinsically achiral films of a side-chain polymeric liquid crystal system by combining chiral doping and [...] Read more.

Flexible construction of permanently stored supramolecular chirality with stimulus-responsiveness remains a big challenge. Herein, we describe an efficient method to realize the transfer and storage of chirality in intrinsically achiral films of a side-chain polymeric liquid crystal system by combining chiral doping and cross-linking strategy. Even the helical structure was destroyed by UV light irradiation, the memorized chiral information in the covalent network enabled complete self-recovery of the original chiral superstructure. These results allowed the building of a novel chiroptical switch without any additional chiral source in multiple types of liquid crystal polymers, which may be one of the competitive candidates for use in stimulus-responsive chiro-optical devices. Full article

(This article belongs to the Special Issue The Self-Assembly and Design of Polyfunctional Nanosystems 2.0)

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17 pages, 6760 KiB

Open AccessArticle

Design of High-Relaxivity Polyelectrolyte Nanocapsules Based on Citrate Complexes of Gadolinium(III) of Unusual Composition

by Evgenia Burilova, Alexander Solodov, Julia Shayimova, Julia Zhuravleva, Darya Shurtakova, Vladimir Evtjugin, Elena Zhiltsova, Lucia Zakharova, Ruslan Kashapov and Rustem Amirov

Int. J. Mol. Sci. 2021, 22(21), 11590; https://doi.org/10.3390/ijms222111590 - 27 Oct 2021

Cited by 5 | Viewed by 2232

Abstract

Through nuclear magnetic relaxation and pH-metry, the details of the complexation of gadolinium(III) ions with citric acid (H₄L) in water and aqueous solutions of cationic polyelectrolytes are established. It is shown that the presence of poly(ethylene imine) (PEI) in solution affects [...] Read more.

Through nuclear magnetic relaxation and pH-metry, the details of the complexation of gadolinium(III) ions with citric acid (H₄L) in water and aqueous solutions of cationic polyelectrolytes are established. It is shown that the presence of poly(ethylene imine) (PEI) in solution affects magnetic relaxation behavior of gadolinium(III) complexes with citric acid (Cit) to a greater extent than polydiallyldimethylammonium chloride (PDDC). A large increase in relaxivity (up to 50 mM⁻¹s⁻¹) in the broad pH range (4–8) is revealed for the gadolinium(III)–citric acid–PEI system, which is particularly strong in the case of PEI with the molecular weight of 25 and 60 kDa. In weakly acidic medium (pH 3–7), the presence of PEI results in the formation of two tris-ligand associates [Gd(H₂L)₃]³⁻ and [Gd(H₂L)₂(HL)]⁴⁻, which do not exist in aqueous medium. In weakly alkaline medium (pH 7–10), formation of ternary complexes Gd(III)–Cit–PEI with the Gd(III)–to–Cit ratio of 1:2 is evidenced. Using transmission electron microscopy (TEM) and dynamic light scattering techniques (DLS), the formation of the particles with the size of 50–100 nm possessing narrow molecular-mass distribution (PDI 0.08) is determined in the solution containing associate of PEI with tris-ligand complex [Gd(H₂L)₂(HL)]⁴⁻. Full article

(This article belongs to the Special Issue The Self-Assembly and Design of Polyfunctional Nanosystems 2.0)

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17 pages, 6893 KiB

Open AccessArticle

Increased Protein Encapsulation in Polymersomes with Hydrophobic Membrane Anchoring Peptides in a Scalable Process

by Michael Mertz and Kathrin Castiglione

Int. J. Mol. Sci. 2021, 22(13), 7134; https://doi.org/10.3390/ijms22137134 - 1 Jul 2021

Cited by 12 | Viewed by 2945

Abstract

Hollow vesicles made from a single or double layer of block-copolymer molecules, called polymersomes, represent an important technological platform for new developments in nano-medicine and nano-biotechnology. A central aspect in creating functional polymersomes is their combination with proteins, especially through encapsulation in the [...] Read more.

Hollow vesicles made from a single or double layer of block-copolymer molecules, called polymersomes, represent an important technological platform for new developments in nano-medicine and nano-biotechnology. A central aspect in creating functional polymersomes is their combination with proteins, especially through encapsulation in the inner cavity of the vesicles. When producing polymersomes by techniques such as film rehydration, significant proportions of the proteins used are trapped in the vesicle lumen, resulting in high encapsulation efficiencies. However, because of the difficulty of scaling up, such methods are limited to laboratory experiments and are not suitable for industrial scale production. Recently, we developed a scalable polymersome production process in stirred-tank reactors, but the statistical encapsulation of proteins resulted in fairly low encapsulation efficiencies of around 0.5%. To increase encapsulation in this process, proteins were genetically fused with hydrophobic membrane anchoring peptides. This resulted in encapsulation efficiencies of up to 25.68%. Since proteins are deposited on the outside and inside of the polymer membrane in this process, two methods for the targeted removal of protein domains by proteolysis with tobacco etch virus protease and intein splicing were evaluated. This study demonstrates the proof-of-principle for production of protein-functionalized polymersomes in a scalable process. Full article

(This article belongs to the Special Issue The Self-Assembly and Design of Polyfunctional Nanosystems 2.0)

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18 pages, 4986 KiB

Open AccessArticle

Self-Assembling Systems Based on Pillar[5]arenes and Surfactants for Encapsulation of Diagnostic Dye DAPI

by Anastasia Nazarova, Arthur Khannanov, Artur Boldyrev, Luidmila Yakimova and Ivan Stoikov

Int. J. Mol. Sci. 2021, 22(11), 6038; https://doi.org/10.3390/ijms22116038 - 3 Jun 2021

Cited by 17 | Viewed by 3547

Abstract

In this paper, we report the development of the novel self-assembling systems based on oppositely charged Pillar[5]arenes and surfactants for encapsulation of diagnostic dye DAPI. For this purpose, the aggregation behavior of synthesized macrocycles and surfactants in the presence of Pillar[5]arenes functionalized by [...] Read more.

In this paper, we report the development of the novel self-assembling systems based on oppositely charged Pillar[5]arenes and surfactants for encapsulation of diagnostic dye DAPI. For this purpose, the aggregation behavior of synthesized macrocycles and surfactants in the presence of Pillar[5]arenes functionalized by carboxy and ammonium terminal groups was studied. It has been demonstrated that by varying the molar ratio in Pillar[5]arene-surfactant systems, it is possible to obtain various types of supramolecular systems: host–guest complexes at equimolar ratio of Pillar[5]arene-surfactant and interpolyelectrolyte complexes (IPECs) are self-assembled materials formed in aqueous medium by two oppositely charged polyelectrolytes (macrocycle and surfactant micelles). It has been suggested that interaction of Pillar[5]arenes with surfactants is predominantly driven by cooperative electrostatic interactions. Synthesized stoichiometric and non-stoichiometric IPECs specifically interact with DAPI. UV-vis, luminescent spectroscopy and molecular docking data show the structural feature of dye-loaded IPEC and key role of the electrostatic, π–π-stacking, cation–π interactions in their formation. Such a strategy for the design of supramolecular Pillar[5]arene-surfactant systems will lead to a synergistic interaction of the two components and will allow specific interaction with the third component (drug or fluorescent tag), which will certainly be in demand in pharmaceuticals and biomedical diagnostics. Full article

(This article belongs to the Special Issue The Self-Assembly and Design of Polyfunctional Nanosystems 2.0)

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16 pages, 3507 KiB

Open AccessArticle

Polyamidoamine Dendrimers Decorated Multifunctional Polydopamine Nanoparticles for Targeted Chemo- and Photothermal Therapy of Liver Cancer Model

by Bartosz F. Grześkowiak, Damian Maziukiewicz, Agata Kozłowska, Ahmet Kertmen, Emerson Coy and Radosław Mrówczyński

Int. J. Mol. Sci. 2021, 22(2), 738; https://doi.org/10.3390/ijms22020738 - 13 Jan 2021

Cited by 30 | Viewed by 3901

Abstract

The development of multifunctional drug delivery systems combining two or more nanoparticle-mediated therapies for efficient cancer treatment is highly desired. To face this challenge, a photothermally active polydopamine (PDA) nanoparticle-based platform was designed for the loading of chemotherapeutic drug and targeting of cancer [...] Read more.

The development of multifunctional drug delivery systems combining two or more nanoparticle-mediated therapies for efficient cancer treatment is highly desired. To face this challenge, a photothermally active polydopamine (PDA) nanoparticle-based platform was designed for the loading of chemotherapeutic drug and targeting of cancer cells. PDA spheres were first functionalized with polyamidoamine (PAMAM) dendrimers followed by the conjugation with polyethylene glycol (PEG) moieties and folic acid (FA) targeting ligand. The anticancer drug doxorubicin (DOX) was then absorbed on the particle surface. We performed the physico-chemical characterization of this versatile material and we assessed further its possible application in chemo- and photothermal therapy using liver cancer cell model. These nanoparticles exhibited high near-infrared photothermal conversion efficacy and allowed for loading of the drug, which upon release in specifically targeted cancer cells suppressed their growth. Using cell proliferation, membrane damage, apoptosis, and oxidative stress assays we demonstrated high performance of this nanosystem in cancer cell death induction, providing a novel promising approach for cancer therapy. Full article

(This article belongs to the Special Issue The Self-Assembly and Design of Polyfunctional Nanosystems 2.0)

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18 pages, 6136 KiB

Open AccessArticle

Peptide–Peptide Co-Assembly: A Design Strategy for Functional Detection of C-peptide, A Biomarker of Diabetic Neuropathy

by Kiat Hwa Chan, Jaehong Lim, Joo Eun Jee, Jia Hui Aw and Su Seong Lee

Int. J. Mol. Sci. 2020, 21(24), 9671; https://doi.org/10.3390/ijms21249671 - 18 Dec 2020

Cited by 11 | Viewed by 3094

Abstract

Diabetes-related neuropathy is a debilitating condition that may be averted if it can be detected early. One possible way this can be achieved at low cost is to utilise peptides to detect C-peptide, a biomarker of diabetic neuropathy. This depends on peptide-peptide co-assembly, [...] Read more.

Diabetes-related neuropathy is a debilitating condition that may be averted if it can be detected early. One possible way this can be achieved at low cost is to utilise peptides to detect C-peptide, a biomarker of diabetic neuropathy. This depends on peptide-peptide co-assembly, which is currently in a nascent stage of intense study. Instead, we propose a bead-based triple-overlay combinatorial strategy that can preserve inter-residue information during the screening process for a suitable complementary peptide to co-assemble with C-peptide. The screening process commenced with a pentapeptide general library, which revealed histidine to be an essential residue. Further screening with seven tetrapeptide focused libraries led to a table of self-consistent peptide sequences that included tryptophan and lysine at high frequencies. Three complementary nonapeptides (9mer com-peptides), wpkkhfwgq (Trp-D), kwkkhfwgq (Lys-D), and KWKKHFWGQ (Lys-L) (as a negative control) were picked from this table for co-assembly studies with C-peptide. Attenuated total reflectance Fourier transform infrared (ATR-FTIR) and circular dichroism (CD) spectroscopies were utilized to study inter-peptide interactions and changes in secondary structures respectively. ATR-FTIR studies showed that there is indeed inter-peptide interaction between C-peptide and the tryptophan residues of the 9mer com-peptides. CD studies of unaggregated and colloidal C-peptide with the 9mer com-peptides suggest that the extent of co-assembly of C-peptide with Trp-D is greatest, followed by Lys-D and Lys-L. These results are promising and indicate that the presented strategy is viable for designing and evaluating longer complementary peptides, as well as complementary peptides for co-assembly with other polypeptides of interest and importance. We discuss the possibility of designing complementary peptides to inhibit toxic amyloidosis with this approach. Full article

(This article belongs to the Special Issue The Self-Assembly and Design of Polyfunctional Nanosystems)

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18 pages, 3487 KiB

Open AccessArticle

Coacervate Thermoresponsive Polysaccharide Nanoparticles as Delivery System for Piroxicam

by Dorota Lachowicz, Agnieszka Kaczyńska, Anna Bodzon-Kulakowska, Anna Karewicz, Roma Wirecka, Michał Szuwarzyński and Szczepan Zapotoczny

Int. J. Mol. Sci. 2020, 21(24), 9664; https://doi.org/10.3390/ijms21249664 - 18 Dec 2020

Cited by 6 | Viewed by 2694

Abstract

Low water solubility frequently compromises the therapeutic efficacy of drugs and other biologically active molecules. Here, we report on coacervate polysaccharide nanoparticles (CPNs) that can transport and release a model hydrophobic drug, piroxicam, to the cells in response to changes in temperature. The [...] Read more.

Low water solubility frequently compromises the therapeutic efficacy of drugs and other biologically active molecules. Here, we report on coacervate polysaccharide nanoparticles (CPNs) that can transport and release a model hydrophobic drug, piroxicam, to the cells in response to changes in temperature. The proposed, temperature-responsive drug delivery system is based on ionic derivatives of natural polysaccharides—curdlan and hydroxypropyl cellulose. Curdlan was modified with trimethylammonium groups, while the anionic derivative of hydroxypropyl cellulose was obtained by the introduction of styrenesulfonate groups. Thermally responsive nanoparticles of spherical shape and average hydrodynamic diameter in the range of 250–300 nm were spontaneously formed in water from the obtained ionic polysaccharides as a result of the coacervation process. Their morphology was visualized using SEM and AFM. The size and the surface charge of the obtained objects could be tailored by adjusting the polycation/polyanion ratio. Piroxicam (PIX) was effectively entrapped inside the nanoparticles. The release profile of the drug from the CPNs-PIX was found to be temperature-dependent in the range relevant for biomedical applications. Full article

(This article belongs to the Special Issue The Self-Assembly and Design of Polyfunctional Nanosystems)

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20 pages, 2350 KiB

Open AccessArticle

Self-Assembly of pH-Labile Polymer Nanoparticles for Paclitaxel Prodrug Delivery: Formulation, Characterization, and Evaluation

by Shani L. Levit, Narendar Reddy Gade, Thomas D. Roper, Hu Yang and Christina Tang

Int. J. Mol. Sci. 2020, 21(23), 9292; https://doi.org/10.3390/ijms21239292 - 5 Dec 2020

Cited by 13 | Viewed by 3225

Abstract

The efficacy of paclitaxel (PTX) is limited due to its poor solubility, poor bioavailability, and acquired drug resistance mechanisms. Designing paclitaxel prodrugs can improve its anticancer activity and enable formulation of nanoparticles. Overall, the aim of this work is to improve the potency [...] Read more.

The efficacy of paclitaxel (PTX) is limited due to its poor solubility, poor bioavailability, and acquired drug resistance mechanisms. Designing paclitaxel prodrugs can improve its anticancer activity and enable formulation of nanoparticles. Overall, the aim of this work is to improve the potency of paclitaxel with prodrug synthesis, nanoparticle formation, and synergistic formulation with lapatinib. Specifically, we improve potency of paclitaxel by conjugating it to α-tocopherol (vitamin E) to produce a hydrophobic prodrug (Pro); this increase in potency is indicated by the 8-fold decrease in half maximal inhibitory concentration (IC₅₀) concentration in ovarian cancer cell line, OVCA-432, used as a model system. The efficacy of the paclitaxel prodrug was further enhanced by encapsulation into pH-labile nanoparticles using Flash NanoPrecipitation (FNP), a rapid, polymer directed self-assembly method. There was an 1100-fold decrease in IC₅₀ concentration upon formulating the prodrug into nanoparticles. Notably, the prodrug formulations were 5-fold more potent than paclitaxel nanoparticles. Finally, the cytotoxic effects were further enhanced by co-encapsulating the prodrug with lapatinib (LAP). Formulating the drug combination resulted in synergistic interactions as indicated by the combination index (CI) of 0.51. Overall, these results demonstrate this prodrug combined with nanoparticle formulation and combination therapy is a promising approach for enhancing paclitaxel potency. Full article

(This article belongs to the Special Issue The Self-Assembly and Design of Polyfunctional Nanosystems)

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19 pages, 3812 KiB

Open AccessArticle

Self-Assembly of Supramolecular Architectures by the Effect of Amino Acid Residues of Quaternary Ammonium Pillar[5]arenes

by Anastasia Nazarova, Dmitriy Shurpik, Pavel Padnya, Timur Mukhametzyanov, Peter Cragg and Ivan Stoikov

Int. J. Mol. Sci. 2020, 21(19), 7206; https://doi.org/10.3390/ijms21197206 - 29 Sep 2020

Cited by 17 | Viewed by 2959

Abstract

Novel water-soluble multifunctional pillar[5]arenes containing amide-ammonium-amino acid moiety were synthesized. The compounds demonstrated a superior ability to bind (1S)-(+)-10-camphorsulfonic acid (S-CSA) and methyl orange dye depending on the nature of the substituent, resulting in the formation one-to-one complexes with both guests. [...] Read more.

Novel water-soluble multifunctional pillar[5]arenes containing amide-ammonium-amino acid moiety were synthesized. The compounds demonstrated a superior ability to bind (1S)-(+)-10-camphorsulfonic acid (S-CSA) and methyl orange dye depending on the nature of the substituent, resulting in the formation one-to-one complexes with both guests. The formation of host-guest complexes was confirmed by ultraviolet (UV), circular dichroism (CD) and ¹H NMR spectroscopy. This work demonstrates the first case of using S-CSA as a chiral template for the non-covalent self-assembly of architectures based on pillar[5]arenes. It was shown that pillar[5]arenes with glycine or L-alanine fragments formed aggregates with average hydrodynamic diameters (d) of 165 and 238 nm, respectively. It was established that the addition of S-CSA to the L-alanine-containing derivative led to the formation of micron-sized aggregates with d of 713 nm. This study may advance the design novel stereoselective catalysts and transmembrane amino acid channels. Full article

(This article belongs to the Special Issue The Self-Assembly and Design of Polyfunctional Nanosystems)

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15 pages, 7811 KiB

Open AccessArticle

Soft Nanoonions: A Dynamic Overview onto Catanionic Vesicles Temperature-Driven Transition

by Gesmi Milcovich, Filipe E. Antunes, Mario Grassi and Fioretta Asaro

Int. J. Mol. Sci. 2020, 21(18), 6804; https://doi.org/10.3390/ijms21186804 - 16 Sep 2020

Cited by 3 | Viewed by 2673

Abstract

Catanionic vesicles are emerging interesting structures for bioapplications. They self-generate by a pairing of oppositely charged ionic surfactants that assemble into hollow structures. Specifically, the anionic-cationic surfactant pair assumes a double-tailed zwitterionic behavior. In this work, the multilamellar-to-unilamellar thermal transition of several mixed [...] Read more.

Catanionic vesicles are emerging interesting structures for bioapplications. They self-generate by a pairing of oppositely charged ionic surfactants that assemble into hollow structures. Specifically, the anionic-cationic surfactant pair assumes a double-tailed zwitterionic behavior. In this work, the multilamellar-to-unilamellar thermal transition of several mixed aqueous systems, with a slight excess of the anionic one, were investigated. Interestingly, it was found that the anionic counterion underwent a dissociation as a consequence of a temperature increase, leading to the mentioned thermal transition. The present work proposed the spectroscopic techniques, specifically multinuclear NMR and PGSTE (pulsed gradient stimulated echo), as a key tool to study such systems, with high accuracy and effectiveness, while requiring a small amount of the sample. The results presented herein evidence encouraging perspectives, forecasting the application of the studied vesicular nanoreservoirs, for e.g., drug delivery. Full article

(This article belongs to the Special Issue The Self-Assembly and Design of Polyfunctional Nanosystems)

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7 pages, 1628 KiB

Open AccessArticle

Dairy-Inspired Coatings for Bone Implants from Whey Protein Isolate-Derived Self-Assembled Fibrils

by Rebecca Rabe, Ute Hempel, Laurine Martocq, Julia K. Keppler, Jenny Aveyard and Timothy E. L. Douglas

Int. J. Mol. Sci. 2020, 21(15), 5544; https://doi.org/10.3390/ijms21155544 - 3 Aug 2020

Cited by 10 | Viewed by 3379

Abstract

To improve the integration of a biomaterial with surrounding tissue, its surface properties may be modified by adsorption of biomacromolecules, e.g., fibrils. Whey protein isolate (WPI), a dairy industry by-product, supports osteoblastic cell growth. WPI’s main component, β-lactoglobulin, forms fibrils in acidic solutions. [...] Read more.

To improve the integration of a biomaterial with surrounding tissue, its surface properties may be modified by adsorption of biomacromolecules, e.g., fibrils. Whey protein isolate (WPI), a dairy industry by-product, supports osteoblastic cell growth. WPI’s main component, β-lactoglobulin, forms fibrils in acidic solutions. In this study, aiming to develop coatings for biomaterials for bone contact, substrates were coated with WPI fibrils obtained at pH 2 or 3.5. Importantly, WPI fibrils coatings withstood autoclave sterilization and appeared to promote spreading and differentiation of human bone marrow stromal cells (hBMSC). In the future, WPI fibrils coatings could facilitate immobilization of biomolecules with growth stimulating or antimicrobial properties. Full article

(This article belongs to the Special Issue The Self-Assembly and Design of Polyfunctional Nanosystems)

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11 pages, 2438 KiB

Open AccessArticle

Bispicolyamine-Based Supramolecular Polymeric Gels Induced by Distinct Different Driving Forces with and Without Zn²⁺

by Jaehyeon Park, Ka Young Kim, Seok Gyu Kang, Shim Sung Lee, Ji Ha Lee and Jong Hwa Jung

Int. J. Mol. Sci. 2020, 21(13), 4617; https://doi.org/10.3390/ijms21134617 - 29 Jun 2020

Cited by 3 | Viewed by 2678

Abstract

Metal-coordination polymeric gels are interesting areas as organic/inorganic hybrid supramolecular materials. The bispicolylamine (BPA) based gelator (1) showed excellent gelation with typical fibrillar morphology in acetonitrile. Upon complexing 1 with Zn²⁺, complexes ([1 + Zn + ACN]²⁺ [...] Read more.

Metal-coordination polymeric gels are interesting areas as organic/inorganic hybrid supramolecular materials. The bispicolylamine (BPA) based gelator (1) showed excellent gelation with typical fibrillar morphology in acetonitrile. Upon complexing 1 with Zn²⁺, complexes ([1 + Zn + ACN]²⁺ and [1 + zinc trifluoromethanesulfonate (ZnOTf)]⁺) with four coordination numbers were formed, which determine the gel structure significantly. A gel-sol transition was induced, driven by the ratio of the two metal complexes produced. Through nuclear magnetic resonance analysis, the driving forces in the gel formation (i.e., hydrogen-bonding and π–π stacking) were observed in detail. In the absence and the presence of Zn²⁺, the intermolecular hydrogen-bonds and π–π stacking were the primary driving forces in the gel formation, respectively. In addition, the supramolecular gels exhibited a monolayer lamellar structure irrespective of Zn²⁺. Conclusively, the gels’ elasticity and viscosity reduced in the presence of Zn²⁺. Full article

(This article belongs to the Special Issue The Self-Assembly and Design of Polyfunctional Nanosystems)

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14 pages, 1877 KiB

Open AccessArticle

Characterization and Evaluation of Ternary Complexes of Ascorbic Acid with γ-Cyclodextrin and Poly(vinyl Alcohol)

by Phennapha Saokham, Kanokporn Burapapadh, Pitsiree Praphanwittaya and Thorsteinn Loftsson

Int. J. Mol. Sci. 2020, 21(12), 4399; https://doi.org/10.3390/ijms21124399 - 20 Jun 2020

Cited by 12 | Viewed by 2996

Abstract

Ascorbic acid (AA) is a general antioxidant used in aqueous pharmaceutical formulations. However, in aqueous solutions, AA is unstable and easily oxidized when exposed to air, light and/or heat. Cyclodextrins are well known for their ability to form inclusion complexes with various compounds [...] Read more.

Ascorbic acid (AA) is a general antioxidant used in aqueous pharmaceutical formulations. However, in aqueous solutions, AA is unstable and easily oxidized when exposed to air, light and/or heat. Cyclodextrins are well known for their ability to form inclusion complexes with various compounds to improve their solubility and stability. Previous studies demonstrate that cyclodextrins preserve the antioxidant capacity of AA but data for γ-cyclodextrin (γCD) have not been reported. Poly(vinyl alcohol) (PVA) is a hydrophilic polymer widely used as a drug matrix in various pharmaceutical fields, but its application for drug stabilization is limited. This study aimed to investigate the protective ability of γCD on AA through the formation of ternary complexes with PVA. Binary (i.e., AA/γCD, AA/PVA and γCD/PVA) and ternary (i.e., AA/γCD/PVA) complexes were first confirmed. It was reported that those complexes were formed through interactions between the heterocyclic ring of AA, hydroxyl group of PVA and hydrophobic cavity of γCD. The hydrodynamic diameter of complexes was then studied. It was found that the diameter of γCD/PVA complexes increased with respect to the concentration of γCD. Higher γCD concentrations also resulted in increasing hydrodynamic diameters of the ternary complex. The presence of AA in ternary complexes interfered with the aggregation tendency of γCD/PVA binary complexes. Furthermore, the antioxidant capacity of AA in binary and ternary complexes was investigated. It was found that the presence of γCD preserved the antioxidant activity of AA, whereas PVA showed a contrasting effect. The influence of γCD and PVA concentration on antioxidant capacity was then studied through central composite design (CCD). Even though the concentration of γCD significantly affected the inhibition efficiency of the ternary complex, the insignificant influence of PVA could not be ignored. A promising protective ternary complex should consist of an optimized concentration of PVA and a high concentration of γCD. Full article

(This article belongs to the Special Issue The Self-Assembly and Design of Polyfunctional Nanosystems)

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17 pages, 3017 KiB

Open AccessArticle

Modeling the Effect of Composition on Formation of Aerosolized Nanoemulsion System Encapsulating Docetaxel and Curcumin Using D-Optimal Mixture Experimental Design

by Azren Aida Asmawi, Norazlinaliza Salim, Emilia Abdulmalek and Mohd Basyaruddin Abdul Rahman

Int. J. Mol. Sci. 2020, 21(12), 4357; https://doi.org/10.3390/ijms21124357 - 19 Jun 2020

Cited by 15 | Viewed by 3002

Abstract

The synergistic anticancer effect of docetaxel (DTX) and curcumin (CCM) has emerged as an attractive therapeutic candidate for lung cancer treatment. However, the lack of optimal bioavailability because of high toxicity, low stability, and poor solubility has limited their clinical success. Given this, [...] Read more.

The synergistic anticancer effect of docetaxel (DTX) and curcumin (CCM) has emerged as an attractive therapeutic candidate for lung cancer treatment. However, the lack of optimal bioavailability because of high toxicity, low stability, and poor solubility has limited their clinical success. Given this, an aerosolized nanoemulsion system for pulmonary delivery is recommended to mitigate these drawbacks. In this study, DTX- and CCM-loaded nanoemulsions were optimized using the D-optimal mixture experimental design (MED). The effect of nanoemulsion compositions towards two response variables, namely, particle size and aerosol size, was studied. The optimized formulations for both DTX- and CCM-loaded nanoemulsions were determined, and their physicochemical and aerodynamic properties were evaluated as well. The MED models achieved the optimum formulation for DTX- and CCM-loaded nanoemulsions containing a 6.0 wt% mixture of palm kernel oil ester (PKOE) and safflower seed oils (1:1), 2.5 wt% of lecithin, 2.0 wt% mixture of Tween 85 and Span 85 (9:1), and 2.5 wt% of glycerol in the aqueous phase. The actual values of the optimized formulations were in line with the predicted values obtained from the MED, and they exhibited desirable attributes of physicochemical and aerodynamic properties for inhalation therapy. Thus, the optimized formulations have potential use as a drug delivery system for a pulmonary application. Full article

(This article belongs to the Special Issue The Self-Assembly and Design of Polyfunctional Nanosystems)

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Review

Jump to: Editorial, Research

50 pages, 7775 KiB

Open AccessReview

Nanocarriers for Biomedicine: From Lipid Formulations to Inorganic and Hybrid Nanoparticles

by Ruslan Kashapov, Alsu Ibragimova, Rais Pavlov, Dinar Gabdrakhmanov, Nadezda Kashapova, Evgenia Burilova, Lucia Zakharova and Oleg Sinyashin

Int. J. Mol. Sci. 2021, 22(13), 7055; https://doi.org/10.3390/ijms22137055 - 30 Jun 2021

Cited by 55 | Viewed by 5610

Abstract

Encapsulation of cargoes in nanocontainers is widely used in different fields to solve the problems of their solubility, homogeneity, stability, protection from unwanted chemical and biological destructive effects, and functional activity improvement. This approach is of special importance in biomedicine, since this makes [...] Read more.

Encapsulation of cargoes in nanocontainers is widely used in different fields to solve the problems of their solubility, homogeneity, stability, protection from unwanted chemical and biological destructive effects, and functional activity improvement. This approach is of special importance in biomedicine, since this makes it possible to reduce the limitations of drug delivery related to the toxicity and side effects of therapeutics, their low bioavailability and biocompatibility. This review highlights current progress in the use of lipid systems to deliver active substances to the human body. Various lipid compositions modified with amphiphilic open-chain and macrocyclic compounds, peptide molecules and alternative target ligands are discussed. Liposome modification also evolves by creating new hybrid structures consisting of organic and inorganic parts. Such nanohybrid platforms include cerasomes, which are considered as alternative nanocarriers allowing to reduce inherent limitations of lipid nanoparticles. Compositions based on mesoporous silica are beginning to acquire no less relevance due to their unique features, such as advanced porous properties, well-proven drug delivery efficiency and their versatility for creating highly efficient nanomaterials. The types of silica nanoparticles, their efficacy in biomedical applications and hybrid inorganic-polymer platforms are the subject of discussion in this review, with current challenges emphasized. Full article

(This article belongs to the Special Issue The Self-Assembly and Design of Polyfunctional Nanosystems 2.0)

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27 pages, 8272 KiB

Open AccessReview

Antimicrobial Polymer−Based Assemblies: A Review

by Ana Maria Carmona-Ribeiro and Péricles Marques Araújo

Int. J. Mol. Sci. 2021, 22(11), 5424; https://doi.org/10.3390/ijms22115424 - 21 May 2021

Cited by 22 | Viewed by 4859

Abstract

An antimicrobial supramolecular assembly (ASA) is conspicuous in biomedical applications. Among the alternatives to overcome microbial resistance to antibiotics and drugs, ASAs, including antimicrobial peptides (AMPs) and polymers (APs), provide formulations with optimal antimicrobial activity and acceptable toxicity. AMPs and APs have been [...] Read more.

An antimicrobial supramolecular assembly (ASA) is conspicuous in biomedical applications. Among the alternatives to overcome microbial resistance to antibiotics and drugs, ASAs, including antimicrobial peptides (AMPs) and polymers (APs), provide formulations with optimal antimicrobial activity and acceptable toxicity. AMPs and APs have been delivered by a variety of carriers such as nanoparticles, coatings, multilayers, hydrogels, liposomes, nanodisks, lyotropic lipid phases, nanostructured lipid carriers, etc. They have similar mechanisms of action involving adsorption to the cell wall, penetration across the cell membrane, and microbe lysis. APs, however, offer the advantage of cheap synthetic procedures, chemical stability, and improved adsorption (due to multipoint attachment to microbes), as compared to the expensive synthetic routes, poor yield, and subpar in vivo stability seen in AMPs. We review recent advances in polymer−based antimicrobial assemblies involving AMPs and APs. Full article

(This article belongs to the Special Issue The Self-Assembly and Design of Polyfunctional Nanosystems 2.0)

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47 pages, 14558 KiB

Open AccessReview

Self-Assembly of Amphiphilic Compounds as a Versatile Tool for Construction of Nanoscale Drug Carriers

by Ruslan Kashapov, Gulnara Gaynanova, Dinar Gabdrakhmanov, Denis Kuznetsov, Rais Pavlov, Konstantin Petrov, Lucia Zakharova and Oleg Sinyashin

Int. J. Mol. Sci. 2020, 21(18), 6961; https://doi.org/10.3390/ijms21186961 - 22 Sep 2020

Cited by 66 | Viewed by 8813

Abstract

This review focuses on synthetic and natural amphiphilic systems prepared from straight-chain and macrocyclic compounds capable of self-assembly with the formation of nanoscale aggregates of different morphology and their application as drug carriers. Since numerous biological species (lipid membrane, bacterial cell wall, mucous [...] Read more.

This review focuses on synthetic and natural amphiphilic systems prepared from straight-chain and macrocyclic compounds capable of self-assembly with the formation of nanoscale aggregates of different morphology and their application as drug carriers. Since numerous biological species (lipid membrane, bacterial cell wall, mucous membrane, corneal epithelium, biopolymers, e.g., proteins, nucleic acids) bear negatively charged fragments, much attention is paid to cationic carriers providing high affinity for encapsulated drugs to targeted cells. First part of the review is devoted to self-assembling and functional properties of surfactant systems, with special attention focusing on cationic amphiphiles, including those bearing natural or cleavable fragments. Further, lipid formulations, especially liposomes, are discussed in terms of their fabrication and application for intracellular drug delivery. This section highlights several features of these carriers, including noncovalent modification of lipid formulations by cationic surfactants, pH-responsive properties, endosomal escape, etc. Third part of the review deals with nanocarriers based on macrocyclic compounds, with such important characteristics as mucoadhesive properties emphasized. In this section, different combinations of cyclodextrin platform conjugated with polymers is considered as drug delivery systems with synergetic effect that improves solubility, targeting and biocompatibility of formulations. Full article

(This article belongs to the Special Issue The Self-Assembly and Design of Polyfunctional Nanosystems)

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36 pages, 6646 KiB

Open AccessReview

Supramolecular Chirality in Azobenzene-Containing Polymer System: Traditional Postpolymerization Self-Assembly Versus In Situ Supramolecular Self-Assembly Strategy

by Xiaoxiao Cheng, Tengfei Miao, Yilin Qian, Zhengbiao Zhang, Wei Zhang and Xiulin Zhu

Int. J. Mol. Sci. 2020, 21(17), 6186; https://doi.org/10.3390/ijms21176186 - 27 Aug 2020

Cited by 26 | Viewed by 6442

Abstract

Recently, the design of novel supramolecular chiral materials has received a great deal of attention due to rapid developments in the fields of supramolecular chemistry and molecular self-assembly. Supramolecular chirality has been widely introduced to polymers containing photoresponsive azobenzene groups. On the one [...] Read more.

Recently, the design of novel supramolecular chiral materials has received a great deal of attention due to rapid developments in the fields of supramolecular chemistry and molecular self-assembly. Supramolecular chirality has been widely introduced to polymers containing photoresponsive azobenzene groups. On the one hand, supramolecular chiral structures of azobenzene-containing polymers (Azo-polymers) can be produced by nonsymmetric arrangement of Azo units through noncovalent interactions. On the other hand, the reversibility of the photoisomerization also allows for the control of the supramolecular organization of the Azo moieties within polymer structures. The construction of supramolecular chirality in Azo-polymeric self-assembled system is highly important for further developments in this field from both academic and practical points of view. The postpolymerization self-assembly strategy is one of the traditional strategies for mainly constructing supramolecular chirality in Azo-polymers. The in situ supramolecular self-assembly mediated by polymerization-induced self-assembly (PISA) is a facile one-pot approach for the construction of well-defined supramolecular chirality during polymerization process. In this review, we focus on a discussion of supramolecular chirality of Azo-polymer systems constructed by traditional postpolymerization self-assembly and PISA-mediated in situ supramolecular self-assembly. Furthermore, we will also summarize the basic concepts, seminal studies, recent trends, and perspectives in the constructions and applications of supramolecular chirality based on Azo-polymers with the hope to advance the development of supramolecular chirality in chemistry. Full article

(This article belongs to the Special Issue The Self-Assembly and Design of Polyfunctional Nanosystems)

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