Polymers2014, 6(10), 2552-2572; doi:10.3390/polym6102552 - published 30 September 2014 Show/Hide Abstract
Abstract: In this paper, we propose a simple one-pot methodology for proceeding from atom transfer reaction-induced conventional free radical polymerization (AT-FRP) to atom transfer self-condensing vinyl polymerization (AT-SCVP) through manipulation of the catalyst phase homogeneity (i.e., CuBr/2,2'-bipyridine (CuBr/Bpy)) in a mixture of styrene (St), 4-vinyl benzyl chloride (VBC), and ethyl 2-bromoisobutyrate. Tests of the solubilities of CuBr/Bpy and CuBr2/Bpy under various conditions revealed that both temperature and solvent polarity were factors affecting the solubility of these copper complexes. Accordingly, we obtained different polymer topologies when performing AT-SCVP in different single solvents. We investigated two different strategies to control the polymer topology in one-pot: varying temperature and varying solvent polarity. In both cases, different fractions of branching revealed the efficacy of varying the polymer topology. To diversify the functionality of the peripheral space, we performed chain extensions of the resulting hyperbranched poly(St-co-VBC) macroinitiator (name as: hbPSt MI) with either St or tBA(tert-butyl acrylate). The resulting hyperbranched core star polymer had high molecular weights (hbPSt-g-PSt: Mn = 25,000, Đ = 1.77; hbPSt-g-PtBA: Mn = 27,000, Đ = 1.98); hydrolysis of the tert-butyl groups of the later provided a hyperbranched core star polymer featuring hydrophilic poly(acrylic acid) segments.
Polymers2014, 6(10), 2526-2551; doi:10.3390/polym6102526 - published 29 September 2014 Show/Hide Abstract
Abstract: Tissue contacting surfaces of medical devices initiate a host inflammatory response, characterized by adsorption of blood proteins and inflammatory cells triggering the release of cytokines, reactive oxygen species (ROS) and reactive nitrogen species (RNS), in an attempt to clear or isolate the foreign object from the body. This normal host response contributes to device-associated pathophysiology and addressing device biocompatibility remains an unmet need. Although widespread attempts have been made to render the device surfaces unreactive, the establishment of a completely bioinert coating has been untenable and demonstrates the need to develop strategies based upon the molecular mechanisms that define the interaction between host cells and synthetic surfaces. In this review, we discuss a family of transmembrane receptors, known as immunoreceptor tyrosine-based inhibitory motif (ITIM)-containing receptors, which show promise as potential targets to address aberrant biocompatibility. These receptors repress the immune response and ensure that the intensity of an immune response is appropriate for the stimuli. Particular emphasis will be placed on the known ITIM-containing receptor, Signal Regulatory Protein Alpha (SIRPα), and its cognate ligand CD47. In addition, this review will discuss the potential of other ITIM-containing proteins as targets for addressing the aberrant biocompatibility of polymeric biomaterials.
Polymers2014, 6(10), 2510-2525; doi:10.3390/polym6102510 - published 29 September 2014 Show/Hide Abstract
Abstract: The aim of this work is to evaluate the potential of cryogels to be used as scaffolds in tissue engineering. Scaffolds based on the α-tricalcium phosphate reinforced PDMAEMA (Poly(dimethyl aminoethyl methacrylate))/PHEMA (poly(hydroxyethyl methacrylate)) system were prepared and human trabecular bone-derived cells (HTBs) and bone marrow derived-mesenchymal stem cells (BM-MSCs) cultured on them. Several features, such as porosity, pore shape, molecular weight between crosslinks and mesh size, are studied. The most suitable PDMAEMA/PHEMA ratio for cell proliferation has been assessed and the viability, adhesion, proliferation and expression of osteoblastic biochemical markers are evaluated. The PDMAEMA/PHEMA ratio influences the scaffolds porosity. Values between 53% ± 5.7% for a greater content in PHEMA and 75% ± 5.5% for a greater content in PDMAEMA have been obtained. The polymer ratio also modifies the pore shape. A greater content in PDMAEMA leads also to bigger network mesh size. Each of the compositions were non-cytotoxic, the seeded cells remained viable for both BM-MSCs and HTBs. Thus, and based on the structural analysis, specimens with a greater content in PDMAEMA seem to provide a better structural environment for their use as scaffolds for tissue engineering. The α-tricalcium phosphate incorporation into the composition seems to favor the expression of the osteogenic phenotype.
Polymers2014, 6(9), 2473-2509; doi:10.3390/polym6092473 - published 25 September 2014 Show/Hide Abstract
Abstract: Organic photovoltaic cells (OPVs) have been a hot topic for research during the last decade due to their promising application in relieving energy pressure and environmental problems caused by the increasing combustion of fossil fuels. Much effort has been made toward understanding the photovoltaic mechanism, including evolving chemical structural motifs and designing device structures, leading to a remarkable enhancement of the power conversion efficiency of OPVs from 3% to over 15%. In this brief review, the advanced progress and the state-of-the-art performance of OPVs in very recent years are summarized. Based on several of the latest developed approaches to accurately detect the separation of electron-hole pairs in the femtosecond regime, the theoretical interpretation to exploit the comprehensive mechanistic picture of energy harvesting and charge carrier generation are discussed, especially for OPVs with bulk and multiple heterojunctions. Subsequently, the novel structural designs of the device architecture of OPVs embracing external geometry modification and intrinsic structure decoration are presented. Additionally, some approaches to further increase the efficiency of OPVs are described, including thermotics and dynamics modification methods. Finally, this review highlights the challenges and prospects with the aim of providing a better understanding towards highly efficient OPVs.
Polymers2014, 6(9), 2451-2472; doi:10.3390/polym6092451 - published 25 September 2014 Show/Hide Abstract
Abstract: The release of monovalent potassium and divalent calcium ions from zwitterionic phosphorylcholine containing poly(2-hydroxyethyl methacrylate) (pHEMA)-based hydrogels was studied and the effects of polymer swelling, ion valence and temperature were investigated. For comparison, ions were loaded during hydrogel formulation or loaded by partitioning following construct synthesis. Using the Koshmeyer-Peppas release model, the apparent diffusion coefficient, Dapp, and diffusional exponents, n, were Dapp (pre-K+) = 2.03 × 10−5, n = 0.4 and Dapp (post-K+) = 1.86 × 10−5, n = 0.33 respectively, indicative of Fickian transport. The Dapp (pre-Ca2+) = 3.90 × 10−6, n = 0.60 and Dapp (post-Ca2+) = 2.85 × 10−6, n = 0.85, respectively, indicative of case II and anomalous transport. Results indicate that divalent cations form cation-polyelectrolyte anion polymer complexes while monovalent ions do not. Temperature dependence of potassium ion release was shown to follow an Arrhenius-type relation with negative apparent activation energy of −19 ± 15 while calcium ion release was temperature independent over the physiologically relevant range (25–45 °C) studied. The negative apparent activation energy may be due to temperature dependent polymer swelling. No effect of polymer swelling on the diffusional exponent or rate constant was found suggesting polymer relaxation occurs independent of polymer swelling.
Polymers2014, 6(9), 2435-2450; doi:10.3390/polym6092435 - published 24 September 2014 Show/Hide Abstract
Abstract: This article reports a simultaneous synthesis of polyaniline (PANI) and nickel (Ni) nanoparticles embedded in polyvinyl alcohol (PVA) film matrix by gamma radiolytic method. The mechanism of formation of PANI and Ni nanoparticles were proposed via oxidation of aniline and reduction of Ni ions, respectively. The effects of dose and Ni ions concentration on structural, optical, and electrical properties of the final PVA/PANI/Ni nanocomposites film were carefully examined. The structural and morphological studies show the presence of PANI with irregular granular microstructure and Ni nanoparticles with spherical shape and diameter less than 60 nm. The average particle size of Ni nanoparticles decreased with increasing dose and decreasing of precursor concentration due to increase of nucleation process over aggregation process during gamma irradiation. The optical absorption spectra showed that the absorption peak of Ni nanoparticles at about 390 nm shifted to lower wavelength and the absorbance increased with increasing dose. The formation of PANI was also revealed at 730 nm absorption peak with the absorbance increasing by the increase of dose. The electrical conductivity increased with increasing of dose and chlorine concentration due to number of polarons formation increases in the PVA/PANI/Ni nanocomposites.