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7312 KiB

Open AccessFeature PaperArticle

Binding of the GTPase Sar1 to a Lipid Membrane Monolayer: Insertion and Orientation Studied by Infrared Reflection–Absorption Spectroscopy

by Christian Schwieger, Annette Meister, Sebastian Daum, Alfred Blume and Kirsten Bacia

Polymers 2017, 9(11), 612; https://doi.org/10.3390/polym9110612 - 14 Nov 2017

Cited by 7 | Viewed by 5201

Abstract

Membrane-interacting proteins are polyphilic polymers that engage in dynamic protein–protein and protein–lipid interactions while undergoing changes in conformation, orientation and binding interfaces. Predicting the sites of interactions between such polypeptides and phospholipid membranes is still a challenge. One example is the small eukaryotic [...] Read more.

Membrane-interacting proteins are polyphilic polymers that engage in dynamic protein–protein and protein–lipid interactions while undergoing changes in conformation, orientation and binding interfaces. Predicting the sites of interactions between such polypeptides and phospholipid membranes is still a challenge. One example is the small eukaryotic GTPase Sar1, which functions in phospholipid bilayer remodeling and vesicle formation as part of the multimeric coat protein complex (COPII). The membrane interaction of Sar1 is strongly dependent on its N-terminal 23 amino acids. By monolayer adsorption experiments and infrared reflection-absorption spectroscopy (IRRAS), we elucidate the role of lipids in inducing the amphipathicity of this N-terminal stretch, which inserts into the monolayer as an amphipathic helix (AH). The AH inserting angle is determined and is consistent with the philicities and spatial distribution of the amino acid monomers. Using an advanced method of IRRAS data evaluation, the orientation of Sar1 with respect to the lipid layer prior to the recruitment of further COPII proteins is determined. The result indicates that only a slight reorientation of the membrane-bound Sar1 is needed to allow coat assembly. The time-course of the IRRAS analysis corroborates a role of slow GTP hydrolysis in Sar1 desorption from the membrane. Full article

(This article belongs to the Special Issue From Amphiphilic to Polyphilic Polymers)

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3838 KiB

Open AccessArticle

An Asymmetrical Glycerol Diether Bolalipid with Protonable Phosphodimethylethanolamine Headgroup: The Impact of pH on Aggregation Behavior and Miscibility with DPPC

by Thomas Markowski, Sindy Müller, Bodo Dobner, Annette Meister, Alfred Blume and Simon Drescher

Polymers 2017, 9(11), 573; https://doi.org/10.3390/polym9110573 - 3 Nov 2017

Cited by 6 | Viewed by 6097

Abstract

Investigations regarding the self-assembly of (bola)phospholipids in aqueous media are crucial to understand the complex relationship between chemical structure of lipids and the shape and size of their aggregates in water. Here, we introduce a new asymmetrical glycerol diether bolaphospholipid, the compound Me [...] Read more.

Investigations regarding the self-assembly of (bola)phospholipids in aqueous media are crucial to understand the complex relationship between chemical structure of lipids and the shape and size of their aggregates in water. Here, we introduce a new asymmetrical glycerol diether bolaphospholipid, the compound Me₂PE-Gly(2C16)C32-OH. This bolalipid contains a long (C32) ω-hydroxy alkyl chain bond to glycerol in the sn-3 position, a C16 alkyl chain at the sn-2 position, and a protonable phosphodimethylethanolamine (Me₂PE) headgroup at the sn-1 position of the glycerol. The aggregation behavior of this bolalipid was studied as a function of temperature and pH using transmission electron microscopy (TEM), differential scanning calorimetry (DSC), and Fourier transform infrared (FTIR) spectroscopy. We show that this bolalipid aggregates into condensed lamellar sheets in acidic milieu and in large sheet-like aggregates at neutral pH-value. By contrast, at a pH-value of 10, where the Me₂PE headgroup is only partially protonated, small lipid disks with diameter 50–100 nm were additionally found. Moreover, the miscibility of this asymmetrical bolalipid with the bilayer-forming phosphatidylcholine DPPC was investigated by means of DSC and TEM. The incorporation of bolalipids into phospholipid membranes could result in stabilized liposomes applicable for drug delivery purposes. We show that mixtures of DPPC and Me₂PE-Gly(2C16)C32-OH form large lamellar aggregates at pH of 5, 7, and 10. However, closed lipid vesicles (liposomes) with an increased thermal stability were not found. Full article

(This article belongs to the Special Issue From Amphiphilic to Polyphilic Polymers)

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9056 KiB

Open AccessArticle

Effect of Perfluoroalkyl Endgroups on the Interactions of Tri-Block Copolymers with Monofluorinated F-DPPC Monolayers

by Syed W. H. Shah, Christian Schwieger, Zheng Li, Jörg Kressler and Alfred Blume

Polymers 2017, 9(11), 555; https://doi.org/10.3390/polym9110555 - 25 Oct 2017

Cited by 4 | Viewed by 4378

Abstract

We studied the interaction of amphiphilic and triphilic polymers with monolayers prepared from F-DPPC (1-palmitoyl-2-(16-fluoropalmitoyl)-sn-glycero-3-phosphocholine), a phospholipid with a single fluorine atom at the terminus of the sn-2 chain, an analogue of dipalmitoyl-phosphatidylcholine (DPPC). The amphiphilic block copolymers contained a [...] Read more.

We studied the interaction of amphiphilic and triphilic polymers with monolayers prepared from F-DPPC (1-palmitoyl-2-(16-fluoropalmitoyl)-sn-glycero-3-phosphocholine), a phospholipid with a single fluorine atom at the terminus of the sn-2 chain, an analogue of dipalmitoyl-phosphatidylcholine (DPPC). The amphiphilic block copolymers contained a hydrophobic poly(propylene oxide) block flanked by hydrophilic poly(glycerol monomethacrylate) blocks (GP). F-GP was derived from GP by capping both termini with perfluoro-n-nonyl segments. We first studied the adsorption of GP and F-GP to lipid monolayers of F-DPPC. F-GP was inserted into the monolayer up to a surface pressure Π of 42.4 mN m⁻¹, much higher than GP (32.5 mN m⁻¹). We then studied isotherms of lipid-polymer mixtures co-spread at the air-water interface. With increasing polymer content in the mixture a continuous shift of the onset of the liquid-expanded (LE) to liquid-condensed (LC) transition towards higher molecular and higher area per lipid molecule was observed. F-GP had a larger effect than GP indicating that it needed more space. At a Π-value of 32 mN m⁻¹, GP was excluded from the mixed monolayer, whereas F-GP stayed in F-DPPC monolayers up to 42 mN m⁻¹. F-GP is thus more stably anchored in the monolayer up to higher surface pressures. Images of mixed monolayers were acquired using different fluorescent probes and showed the presence of perfluorinated segments of F-GP at LE-LC domain boundaries. Full article

(This article belongs to the Special Issue From Amphiphilic to Polyphilic Polymers)

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2266 KiB

Open AccessArticle

Arborescent Unimolecular Micelles: Poly(γ-Benzyl l-Glutamate) Core Grafted with a Hydrophilic Shell by Copper(I)-Catalyzed Azide–Alkyne Cycloaddition Coupling

by Mario Gauthier and Greg Whitton

Polymers 2017, 9(10), 540; https://doi.org/10.3390/polym9100540 - 23 Oct 2017

Cited by 2 | Viewed by 4975

Abstract

Amphiphilic copolymers were obtained by grafting azide-terminated polyglycidol, poly(ethylene oxide), or poly(2-hydroxyethyl acrylate) chain segments onto alkyne-functionalized arborescent poly(γ-benzyl l-glutamate) (PBG) cores of generations G1–G3 via copper(I)-catalyzed azide–alkyne Huisgen cycloaddition (CuAAC) coupling. The alkyne functional groups on the arborescent PBG substrates were [...] Read more.

Amphiphilic copolymers were obtained by grafting azide-terminated polyglycidol, poly(ethylene oxide), or poly(2-hydroxyethyl acrylate) chain segments onto alkyne-functionalized arborescent poly(γ-benzyl l-glutamate) (PBG) cores of generations G1–G3 via copper(I)-catalyzed azide–alkyne Huisgen cycloaddition (CuAAC) coupling. The alkyne functional groups on the arborescent PBG substrates were either distributed randomly or located exclusively at the end of the chains added in the last grafting cycle of the core synthesis. The location of these coupling sites influenced the ability of the arborescent copolymers to form unimolecular micelles in aqueous environments: The chain end grafting approach provided enhanced dispersibility in aqueous media and favored the formation of unimolecular micelles in comparison to random grafting. This is attributed to a better defined core-shell morphology for the copolymers with end-grafted shell segments. Aqueous solubility also depended on the type of material used for the shell chains. Coupling by CuAAC opens up possibilities for grafting a broad range of polymers on the arborescent substrates under mild conditions. Full article

(This article belongs to the Special Issue From Amphiphilic to Polyphilic Polymers)

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3889 KiB

Open AccessArticle

Cluster Formation of Polyphilic Molecules Solvated in a DPPC Bilayer

by Xiang-Yang Guo, Christopher Peschel, Tobias Watermann, Guido Falk von Rudorff and Daniel Sebastiani

Polymers 2017, 9(10), 488; https://doi.org/10.3390/polym9100488 - 6 Oct 2017

Cited by 2 | Viewed by 5110

Abstract

We analyse the initial stages of cluster formation of polyphilic additive molecules which are solvated in a dipalmitoylphosphatidylcholine (DPPC) lipid bilayer. Our polyphilic molecules comprise an aromatic (trans-bilayer) core domain with (out-of-bilayer) glycerol terminations, complemented with a fluorophilic and an alkyl side chain, [...] Read more.

We analyse the initial stages of cluster formation of polyphilic additive molecules which are solvated in a dipalmitoylphosphatidylcholine (DPPC) lipid bilayer. Our polyphilic molecules comprise an aromatic (trans-bilayer) core domain with (out-of-bilayer) glycerol terminations, complemented with a fluorophilic and an alkyl side chain, both of which are confined within the aliphatic segment of the bilayer. Large-scale molecular dynamics simulations (1

μ

s total duration) of a set of six of such polyphilic additives reveal the initial steps towards supramolecular aggregation induced by the specific philicity properties of the molecules. For our intermediate system size of six polyphiles, the transient but recurrent formation of a trimer is observed on a characteristic timescale of about 100 ns. The alkane/perfluoroalkane side chains show a very distinct conformational distribution inside the bilayer thanks to their different philicity, despite their identical anchoring in the trans-bilayer segment of the polyphile. The diffusive mobility of the polyphilic additives is about the same as that of the surrounding lipids, although it crosses both bilayer leaflets and tends to self-associate. Full article

(This article belongs to the Special Issue From Amphiphilic to Polyphilic Polymers)

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948 KiB

Open AccessCommunication

Vesicles in Multiple Shapes: Fine-Tuning Polymersomes’ Shape and Stability by Setting Membrane Hydrophobicity

by Jens Gaitzsch, Lea Messager, Eloise Morecroft and Wolfgang Meier

Polymers 2017, 9(10), 483; https://doi.org/10.3390/polym9100483 - 2 Oct 2017

Cited by 9 | Viewed by 7334

Abstract

Amphiphilic block-copolymers are known to self-assemble into micelles and vesicles. In this paper, we discuss the multiple options between and beyond these boundaries using amphiphilic AB diblock and ABC triblock copolymers. We adjust the final structure reached by the composition of the mixture, [...] Read more.

Amphiphilic block-copolymers are known to self-assemble into micelles and vesicles. In this paper, we discuss the multiple options between and beyond these boundaries using amphiphilic AB diblock and ABC triblock copolymers. We adjust the final structure reached by the composition of the mixture, by the preparation temperature, and by varying the time-scale of formation. This leads to the formation of vesicles and micelles, but also internal micelles in larger sheets, lamellar vesicles, and closed tubes, thus broadening the amount of self-assembly structures available and deepening our understanding of them. Full article

(This article belongs to the Special Issue From Amphiphilic to Polyphilic Polymers)

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2910 KiB

Open AccessFeature PaperArticle

Effects of Lateral and Terminal Chains of X-Shaped Bolapolyphiles with Oligo(phenylene ethynylene) Cores on Self-Assembly Behavior. Part 2: Domain Formation by Self-Assembly in Lipid Bilayer Membranes

by Stefan Werner, Jan Ebenhan, Marco Poppe, Silvio Poppe, Helgard Ebert, Carsten Tschierske and Kirsten Bacia

Polymers 2017, 9(10), 476; https://doi.org/10.3390/polym9100476 - 29 Sep 2017

Cited by 3 | Viewed by 4645

Abstract

Supramolecular self-assembly of membrane constituents within a phospholipid bilayer creates complex functional platforms in biological cells that operate in intracellular signaling, trafficking and membrane remodeling. Synthetic polyphilic compounds of macromolecular or small size can be incorporated into artificial phospholipid bilayers. Featuring three or [...] Read more.

Supramolecular self-assembly of membrane constituents within a phospholipid bilayer creates complex functional platforms in biological cells that operate in intracellular signaling, trafficking and membrane remodeling. Synthetic polyphilic compounds of macromolecular or small size can be incorporated into artificial phospholipid bilayers. Featuring three or four moieties of different philicities, they reach beyond ordinary amphiphilicity and open up avenues to new functions and interaction concepts. Here, we have incorporated a series of X-shaped bolapolyphiles into DPPC (1,2-dipalmitoyl-sn-glycero-3-phosphocholine) bilayers of giant unilamellar vesicles. The bolapolyphiles consist of a rod-like oligo(phenylene ethynylene) (OPE) core, hydrophilic glycerol-based headgroups with or without oligo(ethylene oxide) expansions at both ends and two lateral alkyl chains attached near the center of the OPE core. In the absence of DPPC and water, the compounds showed thermotropic liquid-crystalline behavior with a transition between polyphilic and amphiphilic assembly (see part 1 in this issue). In DPPC membranes, various trends in the domain morphologies were observed upon structure variations, which entailed branched alkyl chains of various sizes, alkyl chain semiperfluorination and size expansion of the headgroups. Observed effects on domain morphology are interpreted in the context of the bulk behavior (part 1) and of a model that was previously developed based on spectroscopic and physicochemical data. Full article

(This article belongs to the Special Issue From Amphiphilic to Polyphilic Polymers)

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13767 KiB

Open AccessFeature PaperArticle

Effects of Lateral and Terminal Chains of X-Shaped Bolapolyphiles with Oligo(phenylene ethynylene) Cores on Self-Assembly Behaviour. Part 1: Transition between Amphiphilic and Polyphilic Self-Assembly in the Bulk

by Silvio Poppe, Marco Poppe, Helgard Ebert, Marko Prehm, Changlong Chen, Feng Liu, Stefan Werner, Kirsten Bacia and Carsten Tschierske

Polymers 2017, 9(10), 471; https://doi.org/10.3390/polym9100471 - 26 Sep 2017

Cited by 18 | Viewed by 7764

Abstract

Polyphilic self-assembly leads to compartmentalization of space and development of complex structures in soft matter on different length scales, reaching from the morphologies of block copolymers to the liquid crystalline (LC) phases of small molecules. Whereas block copolymers are known to form membranes [...] Read more.

Polyphilic self-assembly leads to compartmentalization of space and development of complex structures in soft matter on different length scales, reaching from the morphologies of block copolymers to the liquid crystalline (LC) phases of small molecules. Whereas block copolymers are known to form membranes and interact with phospholipid bilayers, liquid crystals have been less investigated in this respect. Here, series of bolapolyphilic X-shaped molecules were synthesized and investigated with respect to the effect of molecular structural parameters on the formation of LC phases (part 1), and on domain formation in phospholipid bilayer membranes (part 2). The investigated bolapolyphiles are based on a rod-like π-conjugated oligo(phenylene ethynylene) (OPE) core with two glycerol groups being either directly attached or separated by additional ethylene oxide (EO) units to both ends. The X-shape is provided by two lateral alkyl chains attached at opposite sides of the OPE core, being either linear, branched, or semiperfluorinated. In this report, the focus is on the transition from polyphilic (triphilic or tetraphilic) to binary amphiphilic self-assembly. Polyphilic self-assembly, i.e., segregation of all three or four incorporated units into separate nano-compartments, leads to the formation of hexagonal columnar LC phases, representing triangular honeycombs. A continuous transition from the well-defined triangular honeycomb structures to simple hexagonal columnar phases, dominated by the arrangement of polar columns on a hexagonal lattice in a mixed continuum formed by the lipophilic chains and the OPE rods, i.e., to amphiphilic self-assembly, was observed by reducing the length and volume of the lateral alkyl chains. A similar transition was found upon increasing the length of the EO units involved in the polar groups. If the lateral alkyl chains are enlarged or replaced by semiperfluorinated chains, then the segregation of lateral chains and rod-like cores is retained, even for enlarged polar groups, i.e., the transition from polyphilic to amphiphilic self-assembly is suppressed. Full article

(This article belongs to the Special Issue From Amphiphilic to Polyphilic Polymers)

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2267 KiB

Open AccessArticle

Acid-Labile Surfactants Based on Poly(ethylene glycol), Carbon Dioxide and Propylene Oxide: Miniemulsion Polymerization and Degradation Studies

by Markus Scharfenberg, Sarah Wald, Frederik R. Wurm and Holger Frey

Polymers 2017, 9(9), 422; https://doi.org/10.3390/polym9090422 - 6 Sep 2017

Cited by 9 | Viewed by 7780

Abstract

Partially degradable, nonionic AB and ABA type di- and triblock copolymers based on poly(propylene carbonate) and poly(ethylene glycol) blocks were synthesized via immortal copolymerization of carbon dioxide and propylene oxide, using mPEG or PEG as a macroinitiator, and (R,R)-(salcy)-CoOBzF [...] Read more.

Partially degradable, nonionic AB and ABA type di- and triblock copolymers based on poly(propylene carbonate) and poly(ethylene glycol) blocks were synthesized via immortal copolymerization of carbon dioxide and propylene oxide, using mPEG or PEG as a macroinitiator, and (R,R)-(salcy)-CoOBzF₅ as a catalyst in a solvent-free one-pot procedure. The amphiphilic surfactants were prepared with molecular weights (M_n) between 2800 and 10,000 g·mol⁻¹ with narrow molecular weight distributions (1.03–1.09). The copolymers were characterized using ¹H-, ¹³C- and DOSY-NMR spectroscopy and size exclusion chromatography (SEC). Surface-active properties were determined by surface tension measurements (critical micelle concentration, CMC; CMC range: 1–14 mg·mL⁻¹). Degradation of the acid-labile polycarbonate blocks was investigated in aqueous solution using online ¹H-NMR spectroscopy and SEC. The amphiphilic polymers were used as surfactants in a direct miniemulsion polymerization for poly(styrene) (PS) nanoparticles with mean diameter of 270 to 940 nm. The usage of an acid-triggered precipitation of the emulsion simplified the separation of the particles from the surfactant and purification of the nanoparticles. Full article

(This article belongs to the Special Issue From Amphiphilic to Polyphilic Polymers)

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4107 KiB

Open AccessArticle

Constraining Polymers into β-Turns: Miscibility and Phase Segregation Effects in Lipid Monolayers

by Stefanie Deike, Marlen Malke, Bob-Dan Lechner and Wolfgang H. Binder

Polymers 2017, 9(8), 369; https://doi.org/10.3390/polym9080369 - 17 Aug 2017

Cited by 2 | Viewed by 5343

Abstract

Abstract: Investigation of model biomembranes and their interactions with natural or synthetic macromolecules are of great interest to design membrane systems with specific properties such as drug-delivery. Here we study the behavior of amphiphilic β-turn mimetic polymer conjugates at the air–water interface [...] Read more.

Abstract: Investigation of model biomembranes and their interactions with natural or synthetic macromolecules are of great interest to design membrane systems with specific properties such as drug-delivery. Here we study the behavior of amphiphilic β-turn mimetic polymer conjugates at the air–water interface and their interactions with lipid model membranes. For this endeavor we synthesized two different types of conjugates containing either hydrophobic polyisobutylene (PIB, M_n = 5000 g·mol⁻¹) or helical poly(n-hexyl isocyanate) (PHIC, M_n = 4000 g·mol⁻¹), both polymers being immiscible, whereas polyisobutylene as a hydrophobic polymer can incorporate into lipid membranes. The conjugates were investigated using Langmuir-film techniques coupled with epifluorescence microscopy and AFM (Atomic Force Microscopy), in addition to their phase behavior in mixed lipid/polymer membranes composed of DPPC (dipalmitoyl-sn-glycero-3-phosphocholine). It was found that the DPPC monolayers are strongly disturbed by the presence of the polymer conjugates and that domain formation of the polymer conjugates occurs at high surface pressures (π > 30 mN·m⁻¹). Full article

(This article belongs to the Special Issue From Amphiphilic to Polyphilic Polymers)

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2107 KiB

Open AccessArticle

Probing the Nanoscopic Thermodynamic Fingerprint of Paramagnetic Ligands Interacting with Amphiphilic Macromolecules

by Jörg Reichenwallner, Christian Schwieger and Dariush Hinderberger

Polymers 2017, 9(8), 324; https://doi.org/10.3390/polym9080324 - 31 Jul 2017

Cited by 6 | Viewed by 5625

Abstract

Self-assembly of macromolecules with ligands is an intricate dynamic process that depends on a wide variety of parameters and forms the basis of many essential biological processes. We elucidate the underlying energetic processes of self-assembly in a model system consisting of amphiphilic core-shell [...] Read more.

Self-assembly of macromolecules with ligands is an intricate dynamic process that depends on a wide variety of parameters and forms the basis of many essential biological processes. We elucidate the underlying energetic processes of self-assembly in a model system consisting of amphiphilic core-shell polymers interacting with paramagnetic, amphiphilic ligand molecules from temperature-dependent continuous wave electron paramagnetic resonance (CW EPR) spectroscopy subsequent to spectral simulation. The involved processes as observed from the ligands’ point of view are either based on temperature-dependent association constants (K_A,j,k) or dynamic rotational regime interconversion (IC) constants (K_IC,j,k). The interconversion process describes a transition from Brownian (b₁) towards free (b₂) diffusion of ligand. Both processes exhibit non-linear van’t Hoff (lnK vs. T⁻¹) plots in the temperature range of liquid water and we retrieve decisive dynamic information of the system from the energetic fingerprints of ligands on the nanoscale, especially from the temperature-dependent interconversion heat capacity (∆C°_P,IC). Full article

(This article belongs to the Special Issue From Amphiphilic to Polyphilic Polymers)

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Review

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4193 KiB

Open AccessFeature PaperReview

(Cryo)Transmission Electron Microscopy of Phospholipid Model Membranes Interacting with Amphiphilic and Polyphilic Molecules

by Annette Meister and Alfred Blume

Polymers 2017, 9(10), 521; https://doi.org/10.3390/polym9100521 - 19 Oct 2017

Cited by 24 | Viewed by 15907

Abstract

Lipid membranes can incorporate amphiphilic or polyphilic molecules leading to specific functionalities and to adaptable properties of the lipid bilayer host. The insertion of guest molecules into membranes frequently induces changes in the shape of the lipid matrix that can be visualized by [...] Read more.

Lipid membranes can incorporate amphiphilic or polyphilic molecules leading to specific functionalities and to adaptable properties of the lipid bilayer host. The insertion of guest molecules into membranes frequently induces changes in the shape of the lipid matrix that can be visualized by transmission electron microscopy (TEM) techniques. Here, we review the use of stained and vitrified specimens in (cryo)TEM to characterize the morphology of amphiphilic and polyphilic molecules upon insertion into phospholipid model membranes. Special emphasis is placed on the impact of novel synthetic amphiphilic and polyphilic bolalipids and polymers on membrane integrity and shape stability. Full article

(This article belongs to the Special Issue From Amphiphilic to Polyphilic Polymers)

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2060 KiB

Open AccessReview

Synthesis and Application of Aurophilic Poly(Cysteine) and Poly(Cysteine)-Containing Copolymers

by David Ulkoski and Carmen Scholz

Polymers 2017, 9(10), 500; https://doi.org/10.3390/polym9100500 - 11 Oct 2017

Cited by 10 | Viewed by 9170

Abstract

The redox capacity, as well as the aurophilicity of the terminal thiol side groups, in poly(Cysteine) lend a unique characteristic to this poly(amino acid) or polypeptide. There are two major application fields for this polymer: (i) biomedical applications in drug delivery and surface [...] Read more.

The redox capacity, as well as the aurophilicity of the terminal thiol side groups, in poly(Cysteine) lend a unique characteristic to this poly(amino acid) or polypeptide. There are two major application fields for this polymer: (i) biomedical applications in drug delivery and surface modification of biomedical devices and (ii) as coating for electrodes to enhance their electrochemical sensitivity. The intended application determines the synthetic route for p(Cysteine). Polymers to be used in biomedical applications are typically polymerized from the cysteine N-carboxyanhydride by a ring-opening polymerization, where the thiol group needs to be protected during the polymerization. Advances in this methodology have led to conditions under which the polymerization progresses as living polymerization, which allows for a strict control of the molecular architecture, molecular weight and polydispersity and the formation of block copolymers, which eventually could display polyphilic properties. Poly(Cysteine) used as electrode coating is typically polymerized onto the electrode by cyclic voltammetry, which actually produces a continuous, pinhole-free film on the electrode via the formation of covalent bonds between the amino group of Cysteine and the carbon of the electrode. This resulting coating is chemically very different from the well-defined poly(Cysteine) obtained by ring-opening polymerizations. Based on the structure of cysteine a significant degree of cross-linking within the coating deposited by cyclic voltammetry can be assumed. This manuscript provides a detailed discussion of the ring-opening polymerization of cysteine, a brief consideration of the role of glutathione, a key cysteine-containing tripeptide, and examples for the utilization of poly(Cysteine) and poly(Cysteine)-containing copolymers, in both, the biomedical as well as electrochemical realm. Full article

(This article belongs to the Special Issue From Amphiphilic to Polyphilic Polymers)

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9574 KiB

Open AccessReview

Polyphilic Interactions as Structural Driving Force Investigated by Molecular Dynamics Simulation (Project 7)

by Christopher Peschel, Martin Brehm and Daniel Sebastiani

Polymers 2017, 9(9), 445; https://doi.org/10.3390/polym9090445 - 14 Sep 2017

Cited by 2 | Viewed by 5566

Abstract

We investigated the effect of fluorinated molecules on dipalmitoylphosphatidylcholine (DPPC) bilayers by force-field molecular dynamics simulations. In the first step, we developed all-atom force-field parameters for additive molecules in membranes to enable an accurate description of those systems. On the basis of this [...] Read more.

We investigated the effect of fluorinated molecules on dipalmitoylphosphatidylcholine (DPPC) bilayers by force-field molecular dynamics simulations. In the first step, we developed all-atom force-field parameters for additive molecules in membranes to enable an accurate description of those systems. On the basis of this force field, we performed extensive simulations of various bilayer systems containing different additives. The additive molecules were chosen to be of different size and shape, and they included small molecules such as perfluorinated alcohols, but also more complex molecules. From these simulations, we investigated the structural and dynamic effects of the additives on the membrane properties, as well as the behavior of the additive molecules themselves. Our results are in good agreement with other theoretical and experimental studies, and they contribute to a microscopic understanding of interactions, which might be used to specifically tune membrane properties by additives in the future. Full article

(This article belongs to the Special Issue From Amphiphilic to Polyphilic Polymers)

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8573 KiB

Open AccessReview

Poly(phenylene ether) Based Amphiphilic Block Copolymers

by Edward N. Peters

Polymers 2017, 9(9), 433; https://doi.org/10.3390/polym9090433 - 8 Sep 2017

Cited by 12 | Viewed by 9915

Abstract

Polyphenylene ether (PPE) telechelic macromonomers are unique hydrophobic polyols which have been used to prepare amphiphilic block copolymers. Various polymer compositions have been synthesized with hydrophilic blocks. Their macromolecular nature affords a range of structures including random, alternating, and di- and triblock copolymers. [...] Read more.

Polyphenylene ether (PPE) telechelic macromonomers are unique hydrophobic polyols which have been used to prepare amphiphilic block copolymers. Various polymer compositions have been synthesized with hydrophilic blocks. Their macromolecular nature affords a range of structures including random, alternating, and di- and triblock copolymers. New macromolecular architectures can offer tailored property profiles for optimum performance. Besides reducing moisture uptake and making the polymer surface more hydrophobic, the PPE hydrophobic segment has good compatibility with polystyrene (polystyrene-philic). In general, the PPE contributes to the toughness, strength, and thermal performance. Hydrophilic segments go beyond their affinity for water. Improvements in the interfacial adhesion between polymers and polar substrates via hydrogen bonding and good compatibility with polyesters (polyester-philic) have been exhibited. The heterogeneity of domains in these PPE based block copolymer offers important contributions to diverse applications. Full article

(This article belongs to the Special Issue From Amphiphilic to Polyphilic Polymers)

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5619 KiB

Open AccessReview

Applications of Solid-State NMR Spectroscopy for the Study of Lipid Membranes with Polyphilic Guest (Macro)Molecules

by Ruth Bärenwald, Anja Achilles, Frank Lange, Tiago Mendes Ferreira and Kay Saalwächter

Polymers 2016, 8(12), 439; https://doi.org/10.3390/polym8120439 - 16 Dec 2016

Cited by 15 | Viewed by 9662

Abstract

The incorporation of polymers or smaller complex molecules into lipid membranes allows for property modifications or the introduction of new functional elements. The corresponding molecular-scale details, such as changes in dynamics or features of potential supramolecular structures, can be studied by a variety [...] Read more.

The incorporation of polymers or smaller complex molecules into lipid membranes allows for property modifications or the introduction of new functional elements. The corresponding molecular-scale details, such as changes in dynamics or features of potential supramolecular structures, can be studied by a variety of solid-state NMR techniques. Here, we review various approaches to characterizing the structure and dynamics of the guest molecules as well as the lipid phase structure and dynamics by different high-resolution magic-angle spinning proton and ¹³C NMR experiments as well as static ³¹P NMR experiments. Special emphasis is placed upon the incorporation of novel synthetic polyphilic molecules such as shape-persistent T- and X-shaped molecules as well as di- and tri-block copolymers. Most of the systems studied feature dynamic heterogeneities, for instance those arising from the coexistence of different phases; possibilities for a quantitative assessment are of particular concern. Full article

(This article belongs to the Special Issue From Amphiphilic to Polyphilic Polymers)

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