Role of Side-Chain Free Volume on the Electrochemical Behavior of Poly(propylenedioxythiophenes).

Mixed ionic/electronic conducting polymers are versatile systems for, e.g., energy storage, heat management (exploiting electrochromism), and biosensing, all of which require electrochemical doping, i.e., the electrochemical oxidation or reduction of their macromolecular backbones. Electrochemical doping is achieved via electro-injection of charges (i.e., electronic carriers), stabilized via migration of counterions from a supporting electrolyte. Since the choice of the polymer side-chain functionalization influences electrolyte and/or ion sorption and desorption, it in turn affects redox properties, and, thus, electrochemically induced mixed conduction. However, our understanding of how side-chain versus backbone design can increase ion flow while retaining high electronic transport remains limited. Hence, heuristic design approaches have typically been followed. Herein, we consider the redox and swelling behavior of three poly(propylenedioxythiophene) derivatives, P(ProDOT)s, substituted with different side-chain motifs, and demonstrate that passive swelling is controlled by the surface polarity of P(ProDOT) films. In contrast, active swelling under operando conditions (i.e., under an applied bias) is dictated by the local side-chain free volume on the length scale of a monomer unit. Such insights deliver important design criteria toward durable soft electrochemical systems for diverse energy and biosensing platforms and new understanding into electrochemical conditioning ("break-in") in many conducting polymers.

Synthesis and Characterization of Ionene-Polyamide Materials as Candidates for New Gas Separation Membranes.

A new family of six ionenes containing aromatic amide linkages has been synthesized from ready available starting materials at scales up to ~50 g. These ionene-polyamides are all constitutional isomers and vary only in the regiochemistry of the amide linkages (para, meta) and xylyl linkages (ortho, meta, para) which are present in the polymer backbone. This paper details the synthesis of these ionenes and associated characterizations. Ionene-polyamides exhibit relatively low melting points (~150 oC) allowing them to be readily processed into films and other objects. These ionene-polyamide materials are being developed for further study as polymer membranes for the separations of gases such as CO2, N2, CH4 and H2.

Developing a self-healing supramolecular nucleoside hydrogel.

Low molecular weight gelator hydrogels provide a viable alternative to traditional polymer based drug delivery platforms, owing to their tunable stability and in most cases inherent biocompatibility. Here we report the first self-healing nucleoside hydrogel using N4-octanoyl-2'-deoxycytidine (0.5% w/v) for drug delivery. The hydrogel's cross-linked nanofibrillar structure, was characterised using oscillatory rheology and confirmed using SEM and TEM imaging. The potential of this gel for drug delivery was explored in vitro using fluorescently labelled tracers. Cell viability assays were conducted using pancreatic cell lines which tolerated the gels well; whilst no adverse effects on the viability or proliferation of cells were observed for fibroblast cell lines.

Gelation properties of self-assembling N-acyl modified cytidine derivatives.

In this study we report the synthesis of new cytidine derived gelators possessing acyl chains of different lengths. These low molecular weight gelators were shown to form self-supporting gels at 0.5% (w/v) in binary systems of aqueous miscible polar organic solvent and water. The representative gels were studied using rheology and their fibrillar structure confirmed by TEM imaging and FTIR. We further demonstrated the use of these gels as potential drug delivery platforms by monitoring release characteristics of both high and low molecular weight fluorescently labelled tracers.

Shock wave therapy (Orthotripsy) in musculoskeletal disorders.

Extracorporeal shock wave therapy, which now is used routinely for urolithiasis, has gained increasing acceptance in Europe for some musculoskeletal problems and has led to the inception of clinical studies in the United States. The authors have reviewed the available literature to assess the biologic effects of shock waves on human musculoskeletal tissues, the credibility of published studies on therapeutic applications, and the potential for more widespread application of this modality to various skeletal and near-skeletal disorders. The primary advantage of extracorporeal shock wave therapy is its noninvasive nature and seemingly minimal complications when applied to musculoskeletal tissues.

Shock wave therapy for chronic proximal plantar fasciitis.

Three hundred two patients with chronic heel pain caused by proximal plantar fasciitis were enrolled in a study to assess the treatment effects consequent to administration of electrohydraulicall-generated extracorporeal shock waves. Symptoms had been present from 6 months to 18 years. Each treated patient satisfied numerous inclusion and exclusion criteria before he or she was accepted into this study, which was approved by the Food and Drug Administration as a randomized, double-blind evaluation of the efficacy of shock wave therapy for this disorder. Overall, at the predetermined evaluation period 3 months after one treatment, 56% more of the treated patients had a successful result by all four of the evaluation criteria when compared with the patients treated with a placebo. This difference was significant and corroborated the fact that this difference in the results was specifically attributable to the shock wave treatment, rather than any natural improvement caused by the natural history of the condition. The current study showed that the directed application of electrohydraulic-generated shock waves to the insertion of the plantar fascia onto the calcaneus is a safe and effective nonsurgical method for treating chronic, recalcitrant heel pain syndrome that has been present for at least 6 months and has been refractory to other commonly used nonoperative therapies. This technology, when delivered using the OssaTron (High Medical Technology, Kreuz-lingen, Switzerland), has been approved by the Food and Drug Administration specifically for the treatment of chronic proximal plantar fasciitis. The results suggest that this therapeutic modality should be considered before any surgical options, and even may be preferable to cortisone injection, which has a recognized risk of rupture of the plantar fascia and recurrence of symptoms.

Antibody response to human papovavirus JC (JCV) and simian virus 40 (SV40) T antigens in SV40 T antigen-transgenic mice.

Human papovavirus JC (JCV) and simian virus 40 (SV40) genomes share approximately 69% homology; and there is antigenic cross-reactivity between JCV and SV40 tumor or T antigens. In order to determine whether a selective immune response to JCV T antigen could be demonstrated, transgenic mice (SV11+) that express SV40 T antigen in the choroid plexus and are partially tolerant to antigenic determinants on SV40 T antigen were immunized with SV40 or JCV T antigens and their antibody responses were analyzed. The results show that SV11+ mice responded as well as their nontransgenic litter mates to JCV T antigen. Monoclonal antibodies were derived from hybridomas generated from immunized mice which reacted specifically with epitopes in the amino and carboxy terminal halves on JCV T antigen. These studies show that transgenic mice expressing SV40 T antigen are capable of responding to determinants not shared between JCV and SV40 T antigen.

Regulation of hexose transport in aortic endothelial cells by vascular permeability factor and tumor necrosis factor-alpha, but not by insulin.

Vascular permeability factor (VPF) is mitogenic for bovine aortic endothelial (BAE) cells, whereas tumor necrosis factor (TNF) is cytostatic and was found to completely block the mitogenic response to VPF. In contrast to the apparently antagonistic mitogenic effects that these two factors elicit, chronic exposure of BAE cells to either VPF of TNF resulted in significant (about 3-fold) increases in the rates of hexose transport. The concentrations required for half-maximal stimulation were 2 ng/ml (40 pM) for TNF and 4 ng/ml (100 pM) for VPF. Exposure to both factors simultaneously resulted in a greater stimulation of transport (about 7-fold) than exposure to either factor alone. Northern blot analysis indicated that the amount of message for the GLUT-1/erythrocyte form of the glucose transporter was specifically increased by treatment with VPF (5-fold), TNF (25-fold), or to both cytokines together (35-fold). Expression of mRNAs for the insulin-sensitive muscle/adipose transporter (GLUT-4), brain/fetal skeletal muscle transporter (GLUT-3), or the hepatic transporter (GLUT-2) were not detected in either control or treated cells. Acute or chronic exposure to insulin (10(-9) to 10(-6) M) did not activate hexose transport in BAE cells. Thus, glucose transport in aortic endothelial cells can be up-regulated by either VPF, a growth stimulator, or by TNF, a growth inhibitor, but not by insulin. The additive effect of the two cytokines together may be important in the control of increased glucose metabolism at sites of inflammation.