ABA triblock copolymers: from controlled synthesis to controlled function

The ABA amphiphilic block copolymers, poly(hydroxyethyl methacrylate-hlock-methylphenylsilane-block-hydroxyethyl methacrylate) (PHEMA-PMPS-PHEMA) and poly[oligo(ethylene glycol) methyl ether methacrylate-block-methylphenylsilane-block-oligo(ethylene glycol). methyl ether methacrylate] (POEGMA-PMPS-POEGMA) were successfully synthesised via atom transfer radical polymerisation (ATRP). Macroinitiators suitable for the ATRP of oligo(ethylene glycol) methyl ether methacrylate and 2-hydroxyethyl methacrylate were synthesised from the condensation reaction of alpha,omega-dihalopolymethylphenylsilane and 2'-hydroxyethyl 2-bromo-2-methylpropanoate. The copolymers were characterised using H-1 NMR and C-13 NMR spectroscopy and molecular weight characteristics were determined using size exclusion chromatography and H-1 NMR. The aggregation behaviour of some of the copolymers in water was studied using transmission and scanning electron microscopy and dynamic light scattering. These revealed the prevalent aggregate species to be micelles. Larger aggregates of 300-1000 nm diameter were also observed. The UV induced degradation of the aggregates was studied by UV-Vis spectroscopy. The thermal behaviour of selected copolymers was studied by differential scanning calorimetry and microphase separation of the two components was demonstrated

Lamellar organic thin films through self-assembly and molecular recognition

Molecular clips possessing U-shaped cavities have been functionalized on their convex side with long aliphatic tails. These molecules form dimers which self-assemble into malleable lamellar thin films. Upon addition of a guest (methyl 3,5-dihydroxybenzoate), a 1:1 host-guest complex is formed, which prohibits clip dimerization. As a result, the lamellar structure of the material is lost. Complexation of 3,5-dihydroxybenzoic acid in the clip results in host-guest complexes which dimerize by hydrogen bonding interactions between the carboxylic acid functions of the bound guests. This dimerization restores the lamellar type architecture of the material

Rapid photo-crosslinking of fumaric acid monoethyl ester-functionalized poly(trimethylene carbonate) oligomers for drug delivery applications

Photo-crosslinkable, fumaric acid monoethyl ester-functionalized poly(trimethylene carbonate) oligomers were synthesized and copolymerized with N-vinyl pyrrolidone (NVP) and vinyl acetate (VAc) to form biodegradable polymer networks. The copolymerization reactions were much faster than homopolymerization of the fumarate end-groups of the macromers. The hydrophilicity of the networks could by varied by mixing NVP and VAc at different ratios. The prepared network extracts were compatible with NIH 3T3 fibroblasts. Release of vitamin B12, used as a model drug, could be tuned by varying network hydrophilicity and macromer molecular weight. A more hydrophilic and less densely crosslinked network resulted in faster release.\ud \u

Influence of electron-beam irradiation on plasticity-controlled and crack-growth-controlled failure in high-density polyethylene

In the present study, the influence of electron-beam irradiation on plasticity-controlled and crack-growth-controlled failure in high-density polyethylene (HDPE) is investigated and the effect of both molecular weight distribution (MWD) and short chain branching (SCB) content are taken into account. Size exclusion chromatography (SEC) is used to study the evolution of the MWD of the sol fraction as a function of irradiation dose. Here, it is seen that chains shorter than the percolation threshold (5 kDa) are largely unaffected by electron beam radiation, while the fraction of longest chains (M > 300 kDa) is nearly entirely incorporated into the cross-linked network. Both yield stress and Young's modulus increased with irradiation dose, where the magnitude of the increase appears to be connected to the gel fraction. The (fatigue) crack growth kinetics of the grades changed relatively little with irradiation dose, which is unexpected. Furthermore, convergence of the crack growth kinetics parameter to a narrow range of values could be observed for the investigated grades at relatively high gel fractions. This would imply that the crack growth kinetics become increasingly independent of the MWD upon irradiation cross-linking, which could be attributed to a shift in the underlying crack growth mechanism from chain slip to chain scission

Influence of electron‐beam irradiation on plasticity‐controlled and crack‐growth‐controlled failure in high‐density polyethylene

In the present study, the influence of electron-beam irradiation on plasticity-controlled and crack-growth-controlled failure in high-density polyethylene (HDPE) is investigated and the effect of both molecular weight distribution (MWD) and short chain branching (SCB) content are taken into account. Size exclusion chromatography (SEC) is used to study the evolution of the MWD of the sol fraction as a function of irradiation dose. Here, it is seen that chains shorter than the percolation threshold (5 kDa) are largely unaffected by electron beam radiation, while the fraction of longest chains (M > 300 kDa) is nearly entirely incorporated into the cross-linked network. Both yield stress and Young's modulus increased with irradiation dose, where the magnitude of the increase appears to be connected to the gel fraction. The (fatigue) crack growth kinetics of the grades changed relatively little with irradiation dose, which is unexpected. Furthermore, convergence of the crack growth kinetics parameter to a narrow range of values could be observed for the investigated grades at relatively high gel fractions. This would imply that the crack growth kinetics become increasingly independent of the MWD upon irradiation cross-linking, which could be attributed to a shift in the underlying crack growth mechanism from chain slip to chain scission.ISSN:2642-4169ISSN:2642-415

Atrium-targeted drug delivery through an amiodarone-eluting bilayered patch

ObjectiveClinical studies have demonstrated the efficacy of oral and intravenous amiodarone therapy to prevent postoperative atrial fibrillation. However, because of significant extracardiac side effects, only high-risk patients are eligible for prophylactic amiodarone therapy. This study addressed the hypothesis that atrium-specific drug delivery through an amiodarone-eluting epicardial patch reduces vulnerability to atrial tachyarrhythmias, whereas ventricular and plasma drug concentrations are minimized.MethodsRight atrial epicardiums of goats were fitted with electrodes and a bilayered patch (poly[ethylene glycol]–based matrix and poly[lactide-co-caprolactone] backing layer) loaded with amiodarone (10 mg per patch, n = 10) or without drug (n = 6). Electrophysiologic parameters (atrial effective refractory period, conduction time, and rapid atrial response to burst pacing) and amiodarone levels in plasma and tissue were measured during 1 month's follow-up.ResultsEpicardial application of amiodarone-eluting patches produced persistently higher drug concentrations in the right atrium than in the left atrium, ventricles, and extracardiac tissues by 2 to 4 orders of magnitude. Atrial effective refractory period and conduction time increased, whereas rapid atrial response inducibility decreased significantly (P < .05) during the 1-month follow-up compared with that seen in animals treated with drug-free patches. Amiodarone concentrations in plasma remained undetectably low (<10 ng/mL).ConclusionsAtrium-specific drug delivery through an amiodarone-eluting patch produces therapeutic atrial drug concentrations, whereas ventricular and systemic drug levels are minimized. This study demonstrates that sustained targeted drug delivery to a specific heart chamber is feasible and might reduce the risk for ventricular and extracardiac adverse effects. Epicardial application of amiodarone-eluting patches is a promising strategy to prevent postoperative atrial fibrillation

Fatigue-Crack Propagation of High-Density Polyethylene Homopolymers: Influence of Molecular Weight Distribution and Temperature

The present study focuses on the influence of the molecular weight distribution (MWD) on the crack-growth kinetics of fatigue-crack propagation in high-density polyethylene (HDPE) homopolymers. Compact-tension specimens of HDPE homopolymer grades, with polydispersities ranging from 2 to 45 and weight-averaged molar mass ranging from 49 to 450 kg/mol, are tested in cyclic loading at temperatures ranging between 23 and 92 °C. Through a variation of sample thickness, linear elastic-fracture mechanics is shown to apply for the chosen geometry (compact tension). It was found that the crack-propagation kinetics obey the Paris–Erdogan law, for which the Paris–Erdogan exponent m is (highly) similar for all grades tested (m = 3.9), implying that the Paris–Erdogan prefactor A is the governing parameter for the crack-growth kinetics. Relatively poor correlations are observed when the prefactor A is plotted as a function of both the tie-molecule fraction derived from the theoretical model by Huang and Brown, J. Mater. Sci.1988,23, 3648, and the average number of effective physical cross-links per chain as derived by Tervoort et al., Macromolecules2002,35, 8467. A far better correlation is observed between prefactor A and the weight-average molecular weight (Mw), which improved further when Mw is corrected for the width of the MWD, taking into account the z-average molecular weight Mz, through the ratio Mz/Mw. A power-law correlation of prefactor A with Mw and the width-corrected Mw reveals slopes of −3.4 and −3.3, respectively. Because a molecular slip within the fibrils would require chain transport through the crystalline blocks, the temperature dependence of the fatigue-crack-growth kinetics is investigated to identify the underlying molecular processes. This investigation reveals the existence of a high-temperature and a low-temperature deformation process, both of which can be related to chain-slip mechanisms through their respective activation energies (125 and 50 kJ/mole), as their activation energies are considerably lower than that required for chain scission (430 kJ/mol). This, combined with the power-law exponent of −3.4, would suggest a possible connection between the underlying failure mechanisms of craze fibrils and reptation-like dynamics. Furthermore, experiments at elevated temperatures on a selection of homopolymer grades suggest that the MWD has no influence on the temperature dependence of fatigue-crack propagation for HDPE homopolymers.ISSN:1520-5835ISSN:0024-929