Poroelastic indentation of mechanically confined hydrogel layers

We report on the poroelastic indentation response of hydrogel thin films geometrically confined within contacts with rigid spherical probes of radii in the millimeter range. Poly(PEGMA) (poly(ethylene glycol)) methyl ether methacrylate), poly(DMA) (dimethylacrylamide) and poly(NIPAM) (\textit{N}-isopropylacrylamide) gel films with thickness less than 15 $\mu$m were grafted onto glass substrates using a thiol-ene click chemistry route. Changes in the indentation depth under constant applied load were monitored over time as a function of the film thickness and the radius of curvature of the probe using an interferometric method. In addition, shear properties of the indented films were measured using a lateral contact method. In the case of poly(PEGMA) films, we show that poroelastic indentation behavior is adequately described within the framework of an approximate contact model derived within the limits of confined contact geometries. This model provides simple scaling laws for the characteristic poroelastic time and the equilibrium indentation depth. Conversely, deviations from this model are evidenced for poly(DMA) and poly(NIPAM) films. From lateral contact experiments, these deviations are found to result from strong changes in the shear properties as a result of glass transition (poly(DMA)) or phase separation (poly(NIPAM)) phenomena induced by the drainage of the confined films squeezed between the rigid substrates

Multicompartment thermoresponsive gels: Does the length of the hydrophobic side group matter?

Multicompartment thermoresponsive gels are novel materials with fascinating self-assembly and interesting applications. The aim of this study was to investigate for the first time the effect of the length of the alkyl side group of a hydrophobic monomer on the thermoresponsive and self-assembly behaviour of terpolymers. Specifically twelve well-defined terpolymers based on the hydrophilic monomers 2-(dimethylamino)ethyl methacrylate (DMAEMA) and poly(ethylene glycol) methyl ether methacrylate (PEGMA), and on the hydrophobic monomer ethyl-, n-butyl or n-hexyl methacrylate (EtMA, BuMA or HMA) of varying architectures (ABC, ACB, BAC and statistical) were synthesised using Group Transfer Polymerisation. The A, B and C blocks were based on PEGMA, the alkyl containing methacrylate monomer, and DMAEMA, respectively. The molecular weights (MWs) and compositions of the polymers were kept the same. The polymers and their precursors were characterised in terms of their MWs, MW distributions and compositions. Aqueous solutions of the polymers were studied by turbidimetry, hydrogen ion titration, light scattering and rheology to determine their cloud points, pKas, hydrodynamic diameters and thermoresponsive behaviour and investigate the effect of the architecture and the hydrophobic alkyl side group of the terpolymers. It was found that the pKas and the Tgs were mostly affected by the hydrophobicity of the side groups and not by the architecture, while the cloud points and the sol-gel transition of the polymers were affected by both the length of the alkyl side group and the polymer architecture. Interestingly the sharpest sol-gel transitions and stable multicompartment hydrogels were observed for the ABC triblock copolymers with the short alkyl-side groups even though the sol-gel transition occurred at higher temperatures

A heparin-mimicking polymer conjugate stabilizes basic fibroblast growth factor.

Basic fibroblast growth factor (bFGF) is a protein that plays a crucial role in diverse cellular functions, from wound healing to bone regeneration. However, a major obstacle to the widespread application of bFGF is its inherent instability during storage and delivery. Here, we describe the stabilization of bFGF by covalent conjugation with a heparin-mimicking polymer, a copolymer consisting of styrene sulfonate units and methyl methacrylate units bearing poly(ethylene glycol) side chains. The bFGF conjugate of this polymer retained bioactivity after synthesis and was stable to a variety of environmentally and therapeutically relevant stressors--such as heat, mild and harsh acidic conditions, storage and proteolytic degradation--unlike native bFGF. Following the application of stress, the conjugate was also significantly more active than the control conjugate system in which the styrene sulfonate units were omitted from the polymer structure. This research has important implications for the clinical use of bFGF and for the stabilization of heparin-binding growth factors in general

Surface grafting of electrospun fibers using ATRP and RAFT for the control of biointerfacial interactions

BACKGROUND The ability to present signalling molecules within a low fouling 3D environment that mimics the extracellular matrix is an important goal for a range of biomedical applications, both in vitro and in vivo. Cell responses can be triggered by non-specific protein interactions occurring on the surface of a biomaterial, which is an undesirable process when studying specific receptor-ligand interactions. It is therefore useful to present specific ligands of interest to cell surface receptors in a 3D environment that minimizes non-specific interactions with biomolecules, such as proteins. METHOD In this study, surface-initiated atom transfer radical polymerization (SI-ATRP) of poly(ethylene glycol)-based monomers was carried out from the surface of electrospun fibers composed of a styrene/vinylbenzyl chloride copolymer. Surface initiated radical addition-fragmentation chain transfer (SI-RAFT) polymerisation was also carried out to generate bottle brush copolymer coatings consisting of poly(acrylic acid) and poly(acrylamide). These were grown from surface trithiocarbonate groups generated from the chloromethyl styrene moieties existing in the original synthesised polymer. XPS was used to characterise the surface composition of the fibers after grafting and after coupling with fluorine functional XPS labels. RESULTS Bottle brush type coatings were able to be produced by ATRP which consisted of poly(ethylene glycol) methacrylate and a terminal alkyne-functionalised monomer. The ATRP coatings showed reduced non-specific protein adsorption, as a result of effective PEG incorporation and pendant alkynes groups existing as part of the brushes allowed for further conjugation of via azide-alkyne Huisgen 1,3-dipolar cycloaddition. In the case of RAFT, carboxylic acid moieties were effectively coupled to an amine label via amide bond formation. In each case XPS analysis demonstrated that covalent immobilisation had effectively taken place. CONCLUSION Overall, the studies presented an effective platform for the preparation of 3D scaffolds which contain effective conjugation sites for attachment of specific bioactive signals of interest, as well as actively reducing non-specific protein interactions.This research was supported by the Cooperative Research Centre for Polymers (CRCP)

Platelet deposition studies on copolyether urethanes modified with poly(ethylene oxide)

Pellethane ® 2363 80A films and tubings were chemically modified and the effect of these modifications on platelet deposition was studied. Grafting of high molecular weight poly(ethylene oxide) and graft polymerization of methoxy poly(ethylene glycol) 400 methacrylate resulted in surfaces with a good water wettability. The increased hydrophilicity of these modified surfaces could be demonstrated by contact angle measurements. The platelet deposition was investigated with tubings in a capillary flow system, using different types of perfusates. Platelet deposition from a buffer-containing perfusate on surfaces modified with either high molecular weight poly(ethylene oxide) or methoxy poly(ethylene glycol) 400 methacrylate was almost absent and less than on Pellethane 2363 80A. Using a citrated plasmacontaining perfusate the amount of deposited platelets on Pellethane 2363 80A modified with high molecular weight poly(ethylene oxide) was low and about the same as on unmodified surfaces. However, a marked reduced platelet deposition compared to unmodified Pellethane 2363 80A was found when the platelets were activated by Ca2+ ionophore. The improved blood compatibility of the modified Pellethane 2363 80A tubings obviously indicates the favourable effect of the presence of grafted PEO on the surface

Structure-property relationships for polycarboxylate ether superplasticizers by means of RAFT polymerization

Hypothesis: Polycarboxylate ether (PCE) comb-copolymers are widely used as water reducing agents in the concrete industry while maintaining a high fluidity via the polymer adsorption to the cement particles. PCE copolymers with a broad range of structures are well established by Free radical polymerization, however, understanding the structure-property relationship is still complex due to the high polydispersity of PCE copolymers prepared by conventional polymerization. The influence of different structural parameters using well-defined polymeric structures is yet to be explored. Experiments: In this study, two different types of comb-like random copolymers, namely polycarboxylate ether (PCE; poly(oligo(ethylene glycol) methyl ether methacrylate/methacrylic acid)) and polysulfonate ether (PSE; poly(oligo(ethylene glycol) methyl ether acrylate/sodium 4-styrenesulfonate)), were synthesized by RAFT polymerization to enable the synthesis of polymers with controlled features. The effect of charge types and side chain lengths on the adsorption, rheology, and dispersing ability of cement pastes have been studied. Findings: RAFT polymerization could be used to prepare PCE random copolymers with good control over the polymer molecular weight and narrow polydispersity (D < 1.3). Results revealed that the zeta-potential values depend on both the charge type and side chain lengths. Copolymers containing SO3- exhibited higher absolute negative zeta-potential values than COO- while PCE copolymers with shorter side chains developed higher absolute negative zeta-potential values. On the other hand, the adsorption study demonstrated that decreasing the side chain lengths lead to higher adsorption of PCE copolymers while Copolymers with COO- groups were found to be adsorbed more than SO3- counterparts. These results are further confirmed with the rheological studies and it is found that the shorter the side chain, the lower the yield stress and the higher the dispersion of cement pastes but to a limited effect. Additionally, the charge types have a major influence on the performance of superplasticizers. This study could make further progress in establishing superplasticizers with controlled architectures for better performance

Pegmatites of Southern California

For many years the southern California region has attracted the attention of geologists interested in pegmatites and pegmatite deposits, largely because of the well-known gem and lithium occurrences in San Diego and Riverside Counties. These world-famous pegmatites have been so often noted or described in the literature that they commonly are regarded as typical of the pegmatites in the region, even though this actually is far from the case. More than 90 percent of all published contributions on California pegmatites deal with the gem-bearing dikes of San Diego County alone! It is the main purpose of this brief paper to summarize the distribution, occurrence, composition, and structure of all the known pegmatites in southern California, and to discuss several aspects of their geologic and economic significance. Much of the information has been obtained from the published record, a sampling of which is included in the list of references at the end of the paper. In larger part, however, the writer has found it necessary to draw from the results of his own observations, many of which were made in reconnaissance and hence are not wholly satisfactory as a background for generalizations. This qualification with respect to basic data plainly underlies the summary and discussions that follow

Dually sensitive dextran-based micelles for methotrexate delivery

Temperature-sensitive polymeric micelles were prepared from dextran grafted with poly(N-isopropylacrylamide) (PNIPAAm) or polyethylene glycol methyl ether (PEGMA) via controlled radical polymerization and evaluated as delivery systems of the anticancer drug methotrexate (MTX). Polymer-grafting was carried out after introduction of initiating groups onto the polysaccharide backbone, without the need for protection of hydroxyl groups and avoiding the use of toxic solvents. Temperature-responsive dextran-based copolymers were designed to exhibit self-aggregation behaviour, affinity for MTX and high cellular internalization. In addition, some grafted polymers incorporated 2-aminoethyl methacrylate to reinforce MTX encapsulation in the micelles by means of ionic interactions. Dextran-based micelles were cytocompatible and had an appropriate size to be used as drug carriers. MTX release was dependent on the pH and temperature. The combination of poly(2-aminoethylmethacrylate) and PNIPAAm with the dextran backbone permitted the complete release of MTX at normal physiological temperature. Co-polymer micelles were highly internalized by tumour cells (CHO-K1) and, when loaded with MTX, led to enhanced cytotoxicity compared to the free drug