Browse
Submit Data
Databases
API
Help

Dataset Information

31 Views

0 Connections

0 Citations

0 Reanalyses

0 Downloads

Omics score: 0

"Pore-Like" Effects of Super-Molecular Self-Assembly on Molecular Diffusion of Poly(Ethylene Oxide)-Poly(Propylene Oxide)-Poly(Ethylene Oxide) in Water.

ABSTRACT: Molecular diffusion of triblock copolymers poly(ethylene oxide)-poly(propylene oxide)-poly(ethylene oxide) in water was studied with the help of Pulsed Field Gradient NMR in the broad range of polymer weight fractions from 0.09 to 0.8. Owing to amphiphilic nature of the molecules, these block copolymers exhibit rich self-organization properties when mixed with water. In particular, at ambient temperatures they form micelles and three liquid crystalline mesophases: cubic, hexagonal, and lamellar. The corresponding super-molecular structure formations were studied with the same block copolymer and at the same temperature. Self-assembly of molecules was shown to produce "pore-like" effects on their self-diffusion properties by imposing severe constraints on the dimensionality of propagation. Diffusion in the hexagonal phase was shown to be quasi one-dimensional in the direction parallel to the long axis of the ordered molecular rods. In the lamellar phase, diffusion was found to be quasi two-dimensional, in the plane of the lamellar structures. The observed diffusion anisotropy was attributed to the effects of the specific molecular ordering on the mesoscopic length scale.

SUBMITTER: Ulrich K

PROVIDER: S-EPMC5458975 | biostudies-other | 2012 May

REPOSITORIES: biostudies-other

ACCESS DATA

Json Xml

Similar Datasets

Influence of the Headgroup on the Interaction of Poly(ethylene oxide)-Poly(propylene oxide) Block Copolymers with Lipid Bilayers.

Project description:The lipid headgroup plays an important role in the association of polymers with lipid bilayer membranes. Herein, we report how a glycerol headgroup versus a choline headgroup affects the interaction of poly(ethylene oxide)-b-poly(propylene oxide) (PEO-PPO) block copolymers with lipid bilayer vesicles. Unilamellar vesicles composed of phosphatidylcholine and phosphatidylglycerol at various molar ratios were used as model membranes. The interactions between the block copolymers and lipid bilayers were quantified by pulsed-field gradient nuclear magnetic resonance (PFG-NMR) based on the distinctly different mobilities of free and bound polymers. All the investigated polymer species showed significantly higher binding with 1-palmitoyl-2-oleoyl-sn-glycero-3-phospho-(1'-rac-glycerol) sodium salt (POPG) liposomes than with 1-palmitoyl-2-oleoyl-sn-glycero-3-phosphocholine (POPC) liposomes, indicating stronger association with the glycerol headgroup compared to the choline headgroup. This effect did not become significant until the composition of mixed POPC/POPG liposomes contained more than 20 mol % POPG. A plausible explanation for the enhanced polymer binding with POPG invokes the role of hydrogen bonding between the glycerol headgroup and the ether moieties of the polymers.

| S-EPMC7302449 | biostudies-literature

Poly[(ethylene oxide)-co-(methylene ethylene oxide)]: A hydrolytically-degradable poly(ethylene oxide) platform.

Project description:A facile method for imparting hydrolytic degradability to poly(ethylene oxide) (PEO), compatible with current PEGylation strategies, is presented. By incorporating methylene ethylene oxide (MEO) units into the parent PEO backbone, complete degradation was defined by the molar incorporation of MEO, and the structure of the degradation byproducts was consistent with an acid-catalyzed vinyl-ether hydrolysis mechanism. The hydrolytic degradation of poly[(ethylene oxide)-co-(methylene ethylene oxide)] was pH-sensitive, with degradation at pH 5 being significantly faster than at pH 7.4 at 37 °C in PBS buffer while long-term stability could be obtained in either the solid-state or at pH 7.4 at 6 °C.

| S-EPMC3509790 | biostudies-literature

Structure-Property Relationships of Poly(ethylene carbonate) and Poly(propylene carbonate).

Project description:Conformational characteristics of poly(ethylene carbonate) (PEC) and poly(propylene carbonate) (PPC) have been revealed via molecular orbital (MO) calculations and nuclear magnetic resonance (NMR) experiments on model compounds with the same bond sequences as those of the polycarbonates. Bond conformations derived from the MO calculations on the models were in exact agreement with those from the NMR experiments. Both PEC and PPC were indicated to adopt distorted conformations including a number of gauche bonds and cover themselves with negative charges, thus failing to form a regular packing and remaining amorphous. The MO data were applied to the refined rotational isomeric state (RIS) calculations to yield configurational properties such as the characteristic ratio, its temperature coefficient, the configurational entropy, and average geometrical parameters of unperturbed PEC and PPC chains. In the RIS calculations on PPC, the regio- and stereosequences were generated according to the Bernoulli trial or Markov stochastic process. In consequence, it was shown that the configurational properties of PPC do not depend significantly on its regio- and stereoregularities. The internal energy contribution to rubberlike chain elasticity, calculated from the temperature coefficient of the characteristic ratio, has indicated the possibility that PEC and PPC will behave as elastomers. The practical applications and potential utilizations of the polycarbonates are discussed on the basis of the conformational characteristics and configurational properties.

| S-EPMC6641952 | biostudies-literature

Accelerated wound healing by injectable star poly(ethylene glycol)-b-poly(propylene sulfide) scaffolds loaded with poorly water-soluble drugs.

Project description:Injectable hydrogel matrices take the shape of a wound cavity and serve as scaffold for tissue repair and regeneration. Yet these materials are generally hydrophilic, limiting the incorporation of poorly water soluble, hydrophobic drugs. Here we show this shortcoming is circumvented through a star-shaped amphiphilic block copolymer comprising poly(ethylene glycol) and poly (propylene sulfide). This star-shaped amphiphilic polymer self-assembles in an aqueous medium into a physically stable hydrogel and effectively dissolves hydrophobic molecules delivering them at therapeutic doses. The self assembled hydrogel is a robust three-dimensional scaffold in vivo effectively promoting cellular infiltration, reducing inflammation, and wound clsoure. When combined with a hydrophobic BRAF inhibitor that promotes paradoxical mitogen-activated protein kinase (MAPK) activation in keratinocytes and wound closure, our self assembled scaffold supported dermal wound closure at a reduced drug dosage compared to administering the drug in dimethyl sulfoxide (DMSO) without a polymeric matrix. This family of star-shaped amphiphilic polymers delivers poorly water soluble active agents at a fraction of generally required dosage for efficacy and supports three-dimensional cell growth at tissue wounds, showing great promise for novel uses of hydrophobic drugs in tissue repair applications.

| S-EPMC6082662 | biostudies-literature

Quantifying Binding of Ethylene Oxide-Propylene Oxide Block Copolymers with Lipid Bilayers.

Project description:Block copolymers composed of poly(ethylene oxide) (PEO) and poly(propylene oxide) (PPO) have been widely used in cell membrane stabilization and permeabilization. To explore the mechanism of interaction between PPO-PEO block copolymers and lipid membranes, we have investigated how polymer structure influences the polymer-lipid bilayer association by varying the overall molecular weight, the hydrophobic and hydrophilic block lengths, and the end-group structure systematically, using 1-palmitoyl-2-oleoyl-sn-glycero-3-phosphocholine (POPC) unilamellar liposomes as model membranes. Pulsed-field-gradient NMR (PFG-NMR) was employed to probe polymer diffusion in the absence and presence of liposomes. The echo decay curves of free polymers in the absence of liposomes are single exponentials, indicative of simple translational diffusion, while in the presence of liposomes, the decays are biexponential, with the slower decay corresponding to polymers bound to liposomes. The binding percentage of polymer to the liposome was quantified by fitting the echo decay curves to a biexponential model. The NMR experiments show that increasing the total molecular weight and hydrophobicity of the polymer can significantly enhance the polymer-lipid bilayer association, as the binding percentage and liposome surface coverage both increase. We hypothesize that the hydrophobic PPO block inserts into the lipid bilayer due to the fact that little molecular exchange between bound and free polymers occurs on the time scale of the diffusion experiments. Additionally, as polymer concentration increases, the liposome surface coverage increases and approaches a limit. These results demonstrate that PFG-NMR is a simple yet powerful method to quantify interactions between polymers and lipid bilayers.

| S-EPMC6055234 | biostudies-literature

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

Project description: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 (Mn) 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.

| S-EPMC6419001 | biostudies-literature

Thermoresponsive Poly(?-Caprolactone)-Poly(Ethylene/Propylene Glycol) Copolymers as Injectable Hydrogels for Cell Therapies.

Project description:Injectable, thermoresponsive hydrogels are promising candidates for the delivery, maintenance and controlled release of adoptive cell therapies. Therefore, there is significant interest in the development of cytocompatible and biodegradable thermoresponsive hydrogels with appropriate gelling characteristics. Towards this end, a series of thermoresponsive copolymers consisting of poly(caprolactone) (PCL), poly(ethylene glycol) (PEG) and poly(propylene glycol) (PPG) segments, with various PEG:PPG ratios, were synthesised via ring-opening polymerisation (ROP) of ?-caprolactone and epoxy-functionalised PEG and PPG derivatives. The resultant PCL-PEG-PPG copolymers were characterised via proton nuclear magnetic resonance (1H NMR) spectroscopy, gel permeation chromatography (GPC) and differential scanning calorimetry (DSC). The thermoresponsive characteristics of the aqueous copolymer solutions at various concentrations was investigated using the inversion method. Whilst all of the copolymers displayed thermoresponsive properties, the copolymer with a ratio of 1:2 PEG:PPG exhibited an appropriate sol-gel transition (28 °C) at a relatively low concentration (10 wt%), and remained a gel at 37 °C. Furthermore, the copolymers were shown to be enzymatically degradable in the presence of lipases and could be used for the encapsulation of CD4+ T-cell lymphocytes. These results demonstrate that the thermoresponsive PCL-PEG-PPG hydrogels may be suitable for use as an adoptive cell therapy (ACT) delivery vehicle.

| S-EPMC7077385 | biostudies-literature

Structurally Diverse Nitric Oxide-Releasing Poly(propylene Imine) Dendrimers.

Project description:Structurally diverse secondary amine-functionalized poly(propylene imine) (PPI) dendrimers capable of tunable nitric oxide (NO) release were synthesized in a straightforward, one-step manner using ring-opening or conjugate-addition reactions with propylene oxide (PO), styrene oxide (SO), acrylonitrile (ACN), poly(ethylene glycol) methyl ether acrylate (average Mn = 480) (PEG) or 1,2-epoxy-9-decene (ED). N-Diazeniumdiolate nitric oxide donors were formed on the resulting secondary amine-functionalized G2-G5 PPI dendrimers by reaction with NO gas in basic solution. The NO storage and release kinetics for the resulting dendritic scaffolds were diverse (0.9-3.8 ?mol NO/mg totals and 0.3 to 4.9 h half lives), illustrating the importance of the exterior chemical modification (e.g., steric environments, hydrophobicity, etc.) on diazeniumdiolate stability/decomposition. Tunable NO release was demonstrated by combining two donor systems on the exterior of one macromolecular scaffold. Additionally, a mathematical model was developed that allows for the simulation of dual NO release kinetics using the NO release data from the two single NO donor systems. The approaches described herein extend the range and scope of NO-releasing macromolecular scaffolds by unlocking a series of materials for use as dopants in biomedical polymers or stand-alone therapeutics depending on the exterior modification.

| S-EPMC3204868 | biostudies-literature

Gold and Cobalt Oxide Nanoparticles Modified Poly-Propylene Poly-Ethylene Glycol Membranes in Poly (ε-Caprolactone) Conduits Enhance Nerve Regeneration in the Sciatic Nerve of Healthy Rats.

Project description:Reconstruction of nerve defects is a clinical challenge. Autologous nerve grafts as the gold standard treatment may result in an incomplete restoration of extremity function. Biosynthetic nerve conduits are studied widely, but still have limitations. Here, we reconstructed a 10 mm sciatic nerve defect in healthy rats and analyzed nerve regeneration in poly (ε-caprolactone) (PCL) conduits longitudinally divided by gold (Au) and gold-cobalt oxide (AuCoO) nanoparticles embedded in poly-propylene poly-ethylene glycol (PPEG) membranes (AuPPEG or AuCoOPPEG) and compared it with unmodified PPEG-membrane and hollow PCL conduits. After 21 days, we detected significantly better axonal outgrowth, together with higher numbers of activated Schwann cells (ATF3-labelled) and higher HSP27 expression, in reconstructed sciatic nerve and in corresponding dorsal root ganglia (DRG) in the AuPPEG and AuCoOPPEG groups; whereas the number of apoptotic Schwann cells (cleaved caspase 3-labelled) was significantly lower. Furthermore, numbers of activated and apoptotic Schwann cells in the regenerative matrix correlated with axonal outgrowth, whereas HSP27 expression in the regenerative matrix and in DRGs did not show any correlation with axonal outgrowth. We conclude that gold and cobalt-oxide nanoparticle modified membranes in conduits improve axonal outgrowth and increase the regenerative performance of conduits after nerve reconstruction.

| S-EPMC8268459 | biostudies-literature

MICROPATTERNING OF GOLD SUBSTRATES BASED ON POLY(PROPYLENE SULFIDE-BL-ETHYLENE GLYCOL), (PPS-PEG) BACKGROUND PASSIVATION AND THE MOLECULAR-ASSEMBLY PATTERNING BY LIFT-OFF (MAPL) TECHNIQUE.

Project description:Poly(propylene sulfide-bl-ethylene glycol (PPS-PEG) is an amphiphilic block copolymer that spontaneously adsorbs onto gold from solution. This results in the formation of a stable polymeric layer that renders the surface protein resistant when an appropriate architecture is chosen. The established molecular assembly patterning by lift-off (MAPL) technique can convert a prestructured resist film into a pattern of biointeractive chemistry and a noninteractive background. Employing the MAPL technique, we produced a micron-scale PPS-PEG pattern on a gold substrate, and then characterized the patterned structure with Time-of-Flight Secondary Ion Mass Spectrometry (TOF-SIMS) and Atomic Force Microscopy (AFM). Subsequent exposure of the PPS-PEG/gold pattern to protein adsorption (full human serum) was monitored in situ; SPR-imaging (i-SPR) shows a selective adsorption of proteins on gold, but not on PPS-PEG areas. Analysis shows a reduction of serum adsorption up to 93% on the PPS-PEG areas as compared to gold, in good agreement with previous analysis of homogenously adsorbed PPS-PEG on gold. MAPL patterning of PPS-PEG block copolymers is straightforward, versatile and reproducible, and may be incorporated into biosensor-based surface analysis methods.

| S-EPMC2610535 | biostudies-literature

OmicsDI is part of the ELIXIR infrastructure

OmicsDI is an Elixir interoperability service. Learn more ›

Tweets

OmicsDI Databases

PRIDE
PeptideAtlas
MassIVE
JPOST Repository
Physiome Model Repository

EGA
EVA
ENA
LINCS
PAXDB
Cell Collective

MetaboLights
Metabolomics Workbench
MetabolomeExpress
GNPS
BioModels
FAIRDOMHub

ArrayExpress
dbGaP
ExpressionAtlas
GEO
NODE

Information

Databases
Help
API
Contact us
Code on GitHub
Terms of use
Submit Data