Preparation of cross-linked nanoporous poly(ethylene glycol) diacrylate membrane in hexagonal lyotropic liquid crystal phases

Cross-linked poly(ethylene glycol) diacrylate (PEGDA) membranes were prepared by polymerization in periodic nanostructured lyotropic liquid crystals (LLC) hexagonal phases under UV light. A series of membranes were prepared under different purification treatment conditions. Polarized light microscope was employed to determine the LLC phase texture of LLC system before and after polymerization. It is found that the LLC hexagonal structure retained to some degree after polymerization. The interior structures of final membranes were investigated with scanning electron microscope (SEM). The results suggested that purification process affect the structure retention.

Formulation of vanillin cross-linked chitosan nanoparticles and its characterization.

Chitosan nanoparticles were successfully prepared by chemical cross-linking with vanillin. The nanoparticles were spherical in shape with smooth surface, and the average particle size of chitosan nanoparticles was 141 nm. The formulation of chitosan nanoparticles is based on Shiff reaction between aldehyde group of vanillin and amino group of chitosan. Chitosan nanoparticles prepared by crosslinking with vanillin are promising vehicle for the drug delivery of various anticancer drugs in the chemotherapy of cancers.

The boundary lubrication of chemically grafted and cross-linked hyaluronic acid in phosphate buffered saline and lipid solutions measured by the surface forces apparatus

High molecular weight hyaluronic acid (HA) is present in articular joints and synovial fluid at high concentrations; yet despite numerous studies, the role of HA in joint lubrication is still not clear. Free HA in solution does not appear to be a good lubricant, being negatively charged and therefore repelled from most biological, including cartilage, surfaces. Recent enzymatic experiments suggested that mechanically or physically (rather than chemically) trapped HA could function as an “adaptive” or “emergency” boundary lubricant to eliminate wear damage in shearing cartilage surfaces. In this work, HA was chemically grafted to a layer of self-assembled amino-propyl-triethoxy-silane (APTES) on mica and then cross-linked. The boundary lubrication behavior of APTES and of chemically grafted and cross-linked HA in both electrolyte and lipid 1,2-dioleoyl-sn-glycero-3-phosphocholine (DOPC) solutions was tested with a surface forces apparatus (SFA). Despite the high coefficient of friction (COF) of μ ≈ 0.50, the chemically grafted HA gel significantly improved the lubrication behavior of HA, particularly the wear resistance, in comparison to free HA. Adding more DOPC lipid to the solution did not improve the lubrication of the chemically grafted and cross-linked HA layer. Damage of the underlying mica surface became visible at higher loads (pressure >2 MPa) after prolonged sliding times. It has generally been assumed that damage caused by or during sliding, also known as “abrasive friction”, which is the main biomedical/clinical/morphological manifestation of arthritis, is due to a high friction force and, therefore, a large COF, and that to prevent surface damage or wear (abrasion) one should therefore aim to reduce the COF, which has been the traditional focus of basic research in biolubrication, particularly in cartilage and joint lubrication. Here we combine our results with previous ones on grafted and cross-linked HA on lipid bilayers, and lubricin-mediated lubrication, and conclude that for cartilage surfaces, a high COF can be associated with good wear protection, while a low COF can have poor wear resistance. Both of these properties depend on how the lubricating molecules are attached to and organized at the surfaces, as well as the structure and mechanical, viscoelastic, elastic, and physical properties of the surfaces, but the two phenomena are not directly or simply related. We also conclude that to provide both the low COF and good wear protection of joints under physiological conditions, some or all of the four major components of joints—HA, lubricin, lipids, and the cartilage fibrils—must act synergistically in ways (physisorbed, chemisorbed, grafted and/or cross-linked) that are still to be determined.

Structure retention in cross-linked poly(ethylene glycol) diacrylate hydrogel templated from a hexagonal lyotropic liquid crystal by controlling the surface tension

Retaining hexagonal lyotropic liquid crystal (LLC) structures in polymers after surfactant removal and drying is particularly challenging, as the surface tension existing during the drying processes tends to change the morphology. In this study, cross-linked poly(ethylene glycol) diacrylate (PEGDA) hydrogels were prepared in LLC hexagonal phases formed from a dodecyltrimethylammonium bromide (DTAB)/water system. The retention of the hexagonal LLC structures was examined by controlling the surface tension. Polarized light microscopy, X-ray diffraction and small angle X-ray scattering results indicate that the hexagonal LLC structure was successfully formed before polymerization and well retained after polymerization and after surfactant removal when the surface tension forces remained neutral. Controlling the surface tension during the drying process can retain the nanostructures templated from lyotropic liquid crystals which will result in the formation of materials with desired nanostructures.

Retention of the original LLC structure in a cross-linked poly(ethylene glycol) diacrylate hydrogel with reinforcement from a silica network

Cross-linked poly(ethylene glycol) diacrylate (PEGDA) hydrogels with uniformly controlled nanoporous structures templated from hexagonal lyotropic liquid crystals (LLC) represent separation membrane materials with potentially high permeability and selectivity due to their high pore density and narrow pore size distribution. However, retaining LLC templated nanostructures is a challenge as the polymer gels are not strong enough to sustain the surface tension during the drying process. In the current study, cross-linked PEGDA gels were reinforced with a silica network synthesized via an in situ sol-gel method, which assists in the retention of the hexagonal LLC structure. The silica precursor does not obstruct the formation of hexagonal phases. After surfactant removal and drying, these hexagonal structures in samples with a certain amount of tetraethoxysilane (TEOS) loading are well retained while the nanostructures are collapsed in samples without silica reinforcement, leading to the hypothesis that the reinforcement provided by the silica network stabilizes the LLC structure. The study examines the conditions necessary for a sufficient and well dispersed silica network in PEGDA gels that contributes to the retention of original LLC structures, which potentially enables broad applications of these gels as biomedical and membrane materials.

Evaluation of cross-linked enzyme aggregates of Lactobacillus cell-envelope proteinases, for protein degradation

Enzymatic hydrolysis is a widely used approach to improve the functional, nutritionaland physiological properties of food proteins. In this study, cross-linked enzyme aggre-gates (CLEAs) have been prepared from cell-envelope proteinases (CEPs) of Lactobacillusdelbrueckii subsp. lactis 313 and their proteolytic properties have been evaluated using severalfood proteins. We have optimized cross-linking conditions including ammonium sulphateconcentration, incubation temperatures, agitation speed, glutaraldehyde cross-linker con-centration, reaction time and the addition of proteic feeders. Particularly, the presence ofBSA improves retained activity of cross-linked CEP aggregates (CLCEPAs) from 21.5% to 40.9%.Blocking unreacted cross-linking groups on aggregates is important to enhance recyclabil-ity of CLCEPAs. CLCEPAs had attractive thermal stability at 50◦C and it showed enhancedcatalytic activity over long-term storage after lyophilization. We have demonstrated thatCLCEPAs has proteolytic properties on different food proteins including complex (chickenegg albumin, skimmed-milk protein), fractionated (bovine casein, whey protein isolate), andpurified (bovine serum albumin) proteins. Being the first report of CLEAs from lactobacilliCEPs, this study demonstrates the feasibility of using LDL 313 CLCEPAs for degradation ofvarious food proteins.

Covalent/crystallite cross-linked co-network hydrogels : an efficient and simple strategy for mechanically strong and tough hydrogels

Covalent/crystallite cross-linked co-network hydrogels have been prepared using epoxy and PVA through a cyclic freezing-thawing process. The PVA/epoxy hydrogels show enhanced mechanical strength and toughness. PVA/epoxy hydrogels with 4 wt% epoxy loading display maximum tensile strength and toughness of 1.1 MPa and 2838 kJ/m3 respectively. The fracture toughness of PVA/epoxy hydrogels ranges from 160 to 450 J/m2. Radius of gyration and fractal information of the hydrogels were obtained by fitting the SAXS data to the Guinier and power law models. The enhanced mechanical properties are attributed to the increase in covalent bonding and decrease in crystallite distribution with an increase in epoxy content. However a larger hysteresis is shown for PVA/epoxy hydrogels due to irreversible destruction of covalent bonds between epoxy and PVA.

A robust and reproducible procedure for cross-linking thermoset polymers using molecular simulation

Molecular simulation can provide valuable guidance in establishing clear links between structure and function to enable the design of new polymer-based materials. However, molecular simulation of thermoset polymers in particular, such as epoxies, present specific challenges, chiefly in the credible preparation of polymerised samples. Despite this need, a comprehensive, reproducible and robust process for accomplishing this using molecular simulation is still lacking. Here, we introduce a clear and reproducible cross-linking protocol to reliably generate three dimensional epoxy cross-linked polymer structures for use in molecular simulations. This protocol is sufficiently detailed to allow complete reproduction of our results, and is applicable to any general thermoset polymer. Amongst our developments, key features include a reproducible procedure for calculation of partial atomic charges, a reliable process for generating and validating an equilibrated liquid precursor mixture, and establishment of a novel, robust and reproducible protocol for generating the three-dimensional cross-linked solid polymer. We use these structures as input to subsequent molecular dynamics simulations to calculate a range thermo-mechanical properties, which compare favourably with experimental data. Our general protocol provides a benchmark for the process of simulating epoxy polymers, and can be readily translated to prepare and model epoxy samples that are dynamically cross-linked in the presence of surfaces and nanostructures.

Fabrication of conductive elastic nanocomposites via framing intact interconnected graphene networks

Electrically conductive elastic nanocomposites with well-organized graphene architectures offer significant improvement in various properties. However, achieving desirable graphene architectures in cross-linked rubber is challenging due to high viscosity and cross-linked nature of rubber matrices. Here, three dimensional (3D) interconnected graphene networks in natural rubber (NR) matrix are framed with self-assembly integrating latex compounding technology by employing electrostatic adsorption between poly(diallyldimethylammonium chloride) modified graphene (positively charged) and NR latex particles (negatively charged) as the driving force. The 3D graphene structure endows the resulted nanocomposites with excellent electrical conductivity of 7.31. S/m with a graphene content of 4.16. vol.%, extremely low percolation threshold of 0.21. vol.% and also analogous reinforcement in mechanical properties. The developed strategy will provide a practical approach for developing elastic nanocomposites with multi-functional properties. © 2014 Elsevier Ltd.

Bio-inspired hydrogen-bond cross-link strategy toward strong and tough polymeric materials

It remains a huge challenge to create advanced polymeric materials combining high strength, great toughness, and biodegradability so far. Despite enhanced strength and stiffness, biomimetic materials and polymer nanocomposites suffer notably reduced extensibility and toughness when compared to polymer bulk. Silk displays superior strength and toughness via hydrogen bonds (H-bonds) assembly, while cuticles of mussels gain high hardness and toughness via metal complexation cross-linking. Here, we propose a H-bonds cross-linking strategy that can simultaneously strikingly enhance strength, modulus, toughness, and hardness relative to polymer bulk. The H-bond cross-linked poly(vinyl alcohol) exhibits high yield strength (140 MPa), reduced modulus (22.5 GPa) in nanoindention tests, hardness (0.5 GPa), and great extensibility (40%). More importantly, there exist semiquantitive linear relationships between the number of effective H-bond and macroscale properties. This work suggests a promising methodology of designing advanced materials with exceptional mechanical by adding low amounts (1.0 wt %) of small molecules multiamines serving as H-bond cross-linkers.

Functional analysis of natriuretic peptide receptors in the bladder of the toad, bufo marinus

This study aimed to localize and characterize natriuretic peptide binding sites in the urinary bladder of Bufo marinus and to then examine the effect of natriuretic peptides on the bladder vascular tone and water reabsorption in isolated perfused bladder preparations. Specific ¹²⁵I-rat atrial natriuretic peptide (¹²⁵I-rANP) binding sites were present on blood vessels, muscle, and epithelium. In tissue sections and/or isolated membranes, the binding was completely displaced by frog ANP, rat ANP, and porcine C-type natriuretic peptide (CNP; membranes only). However, a reduction in binding was observed after incubation with ¹²⁵I-rANP and 1 μM of the natriuretic peptide receptor-C (NPR-C) ligand C-ANF, but residual binding remained suggesting the presence of two distinct binding sites. Electrophoresis of bladder membranes cross-linked to ¹²⁵I-rANP identified two bands at approximately 70 and 140 kDa that correspond to the monomeric mass of NPR-C and the guanylate cyclase receptors, respectively. Furthermore, the presence of natriuretic peptide receptor-A and NPR-C mRNA in the bladder was demonstrated with reverse transcription–polymerase chain reaction. In addition, rat ANP, frog ANP, and porcine CNP stimulated a significant increase in cGMP generation in bladder membrane preparations, which indicated the presence of guanylate cyclase-linked receptors. In perfused bladder preparations, arginine vasotocin increased perfusion pressure and water permeability. The infusion of frog ANP or porcine CNP failed to alter perfusion pressure or water reabsorption in the presence or absence of arginine vasotocin. This study identified a well-developed natriuretic peptide receptor system in the urinary bladder of B. marinus but the function of the receptors remains unclear.

Synthesis and polymerisation of α,ω-bis(3-pyrrolyl)alkanes

The synthesis, characterisation and polymerisation studies of a homologous series of α,ω-bis(pyrrolyl)alkanes are described. These α,ω-bis(pyrrolyl)alkanes were produced using Friedel–Crafts acylation followed by reduction of the carbonyl group using Red-Al®. Chemical polymerisation of the resultant dimers using FeCl₃ produced poly(α,ω-bis(pyrrolyl)alkane) films, which were characterised by SEM, FTIR and tested for conductivity.