Polymer colloidal motors with photodynamic-regulated propulsion.

Artificial colloidal motors capable of converting various external energy into mechanical motion, have emerged as attractive photosensitizer (PS) nanocarriers with good deliverability for photodynamic therapy. However, photoactivated 3O2-to-1O2 transformation as the most crucial energy transfer of the photodynamic process itself is still challenging to convert into autonomous transport. Herein, we report on PS-loaded thiophane-containing semiconducting conjugated polymer (SCP)-based polymer colloidal motors with asymmetric geometry for photodynamic-regulated propulsion in the liquid. The asymmetrical presence of the SCP phases within the colloidal motors would lead to significant differences in the 3O2-to-1O2 transformation and 1O2 release manners between asymmetrical polymer phases, spontaneously creating asymmetrical osmotic pressure gradients across the nanoparticles for powering the self-propelled motion under photodynamic regulation. This photoactivated energy-converting behavior can be also combined with the photothermal conversion of the SCP phases to create two energy gradients exerting diffusiophoretic/thermophoretic force on the colloidal motors for achieving multimode synergistic propulsion. This unique motile feature endows the light-driven PS nanocarriers with good permeability against various physiological barriers in the tumor microenvironment for enhancing antitumor efficacy, showing great potential in phototherapy.

Performance and Stability of Aemion and Aemion+ Membranes in Zero-Gap CO2 Electrolyzers with Mild Anolyte Solutions.

The dependence of performance and stability of a zero-gap CO2 electrolyzer on the properties of the anion exchange membrane (AEM) is examined. This work firstly assesses the influence of the anolyte when using an Aemion membrane and then shows that when using 10 mM KHCO3 , a CO2 electrolyzer using a next-generation Aemion+ membrane can achieve lower cell voltages and longer lifetimes due to increased water permeation. The impact of lower permselectivity of Aemion+ on water transport is also discussed. Using Aemion+, a cell voltage of 3.17 V at 200 mA cm-2 is achieved at room temperature, with a faradaic efficiency of >90 %. Stable CO2 electrolysis at 100 mA cm-2 is demonstrated for 100 h, but with reduced lifetime at 300 mA cm-2 . However, the lifetime of the cell at high current densities is shown to be increased by improving water transport characteristics of the AEM and reducing dimensional swelling, as well as by improving cathode design to reduce localized dehydration of the membrane.

Engineered Organic Nanorockets with Light-Driven Ultrafast Transportability for Antitumor Therapy.

Nanomedicines confront various complicated physiological barriers limiting the accumulation and deep penetration in the tumor microenvironment, which seriously restricts the efficacy of antitumor therapy. Self-propelled nanocarriers assembled with kinetic engines can translate external energy into orientated motion for tumor penetration. However, achieving a stable ultrafast permeability at the tumor site remains challenging. Here, sub-200 nm photoactivated completely organic nanorockets (NRs), with asymmetric geometry conveniently assembled from photothermal semiconducting polymer payload and thermo-driven macromolecular propulsion through a straightforward nanoprecipitation process, are presented. The artificial NRs can be remotely manipulated by 808 nm near-infrared light to trigger the photothermal conversion and Curtius rearrangement reaction within the particles for robustly pushing nitrogen out into the solution. Such a two-stage light-to-heat-to-chemical energy transition effectively powers the NRs for an ultrafast (≈300 µm s-1 ) and chemical medium-independent self-propulsion in the liquid media. That endows the NRs with high permeability against physiological barriers in the tumor microenvironment to directionally deliver therapeutic agents to target lesions for elevating tumor accumulation, deep penetration, and cellular uptake, resulting in a significant enhancement of antitumor efficacy. This work will inspire the design of advanced kinetic systems for powering intelligent nanomachines in biomedical applications.

Large-area patterning of full-color quantum dot arrays beyond 1000 pixels per inch by selective electrophoretic deposition.

Colloidal quantum dot (QD) emitters show great promise in the development of next-generation displays. Although various solution-processed techniques have been developed for nanomaterials, high-resolution and uniform patterning technology amicable to manufacturing is still missing. Here, we present large-area, high-resolution, full-color QD patterning utilizing a selective electrophoretic deposition (SEPD) technique. This technique utilizes photolithography combined with SEPD to achieve uniform and fast fabrication, low-cost QD patterning in large-area beyond 1,000 pixels-per-inch. The QD patterns only deposited on selective electrodes with precisely controlled thickness in a large range, which could cater for various optoelectronic devices. The adjustable surface morphology, packing density and refractive index of QD films enable higher efficiency compared to conventional solution-processed methods. We further demonstrate the versatility of our approach to integrate various QDs into large-area arrays of full-color emitting pixels and QLEDs with good performance. The results suggest a manufacture-viable technology for commercialization of QD-based displays.

Ex-Situ Evaluation of Commercial Polymer Membranes for Vanadium Redox Flow Batteries (VRFBs).

Polymer membranes play a vital role in vanadium redox flow batteries (VRFBs), acting as a separator between the two compartments, an electronic insulator for maintaining electrical neutrality of the cell, and an ionic conductor for allowing the transport of ionic charge carriers. It is a major influencer of VRFB performance, but also identified as one of the major factors limiting the large-scale implementation of VRFB technology in energy storage applications due to its cost and durability. In this work, five (5) high-priority characteristics of membranes related to VRFB performance were selected as major considerable factors for membrane screening before in-situ testing. Eight (8) state-of-the-art of commercially available ion exchange membranes (IEMs) were specifically selected, evaluated and compared by a set of ex-situ assessment approaches to determine the possibility of the membranes applied for VRFB. The results recommend perfluorosulfonic acid (PFSA) membranes and hydrocarbon anion exchange membranes (AEMs) as the candidates for further in-situ testing, while one hydrocarbon cation exchange membrane (CEM) is not recommended for VRFB application due to its relatively high VO2+ ion crossover and low mechanical stability during/after the chemical stability test. This work could provide VRFB researchers and industry a valuable reference for selecting the polymer membrane materials before VRFB in-situ testing.

Superior Proton Exchange Membrane Fuel Cell (PEMFC) Performance Using Short-Side-Chain Perfluorosulfonic Acid (PFSA) Membrane and Ionomer.

Optimization of the ionomer materials in catalyst layers (CLs) which sometimes is overlooked has been equally crucial as selection of the membranes in membrane electrode assembly (MEA) for achieving a superior performance in proton exchange membrane fuel cells (PEMFCs). Four combinations of the MEAs composed of short-side-chain (SSC) and long-side-chain (LSC) perfluorosulfonic acid (PFSA) polymers as membrane and ionomer materials have been prepared and tested under various temperatures and humidity conditions, aiming to investigate the effects of different side chain polymer in membranes and CLs on fuel cell performance. It is discovered that SSC PFSA polymer used as membrane and ionomer in CL yields better fuel cell performance than LSC PFSA polymer, especially at high temperature and low RH conditions. The MEA with the SSC PFSA employed both as a membrane and as an ionomer in cathode CL demonstrates the best cell performance amongst the investigated MEAs. Furthermore, various electrochemical diagnoses have been applied to fundamentally understand the contributions of the different resistances to the overall cell performance. It is illustrated that the charge transfer resistance (Rct) made the greatest contribution to the overall cell resistance and then membrane resistance (Rm), implying that the use of the advanced ionomer in CL could lead to more noticeable improvement in cell performance than only the substitution as the membrane.

Effects of 1, 2, 4-Triazole Additive on PEM Fuel Cell Conditioning.

Melt processing is one of the essential technologies for the mass production of polymer electrolyte membranes (PEM) at low cost. Azoles have been widely used in PEM to improve their conductivity at a relatively low humidity and recently as bifunctional additives in a melt blowing processing for PEM mass production. In this work, we attempted to assess the effect of 1, 2, 4-triazole additive in membranes and in catalyst layers on PEM fuel cell conditioning. Various characterization tools including electrochemical impedance spectroscopy (EIS), cyclic voltammetry (CV) and conditioning with constant current were applied to diagnose the temporary electrochemical reaction effect and the permanent performance loss caused by the triazole additives. It was found that triazole additives in membranes could migrate into the catalyst layers and significantly affect the open circuit voltage (OCV) and the conditioning. The effect could be partially or completely removed/cleaned either through longer conditioning time or via CV cycling, which depends on the amount of additives remaining in the membrane. The findings provide valuable scientific insights on the relevance of post treatment steps during membrane production and overcoming fuel cell contamination issues due to residual additive in the membranes and understanding the quality control needed for fuel cell membranes by melt blowing processing.

Flocculation performance of anionic starch in oil sand tailings.

A series of carboxymethyl starches (CMSs), with various degrees of substitution from 0.1 to 0.79, were synthesized and selected as a model to study the feasibility of using natural polymers as flocculants for oil sand tailings treatment. The flocculation performance of modified CMS in kaolin clay suspensions and oil sand tailings was evaluated in terms of settling rate, solids content, capillary suction time, and specific resistance to filtration of the sediment phase. It was found that the synthesized CMS effectively accelerates settling of kaolin suspensions and oil sand fine tailings, thus demonstrating the feasibility of this application.

Expression levels of microRNA-199 and hypoxia-inducible factor-1 alpha in brain tissue of patients with intractable epilepsy.

OBJECTIVES: During the last decade, experimental evidence has demonstrated an important role of hypoxia, which leads to neuronal cell death and angiogenesis, in the mechanisms of seizure precipitation and recurrence. MicroRNA-199 targets hypoxia-inducible factor-1alpha (HIF-1α), which has recently been implicated in the pathophysiology of the hypoxic state and brain injury. However, little is known about the roles of MicroRNA-199 and HIF-1α in the human epileptogenic process. DESIGN AND METHODS: In this study, we investigated the expression of miR-199a-5p, miR-199b-5p and HIF-1α using real-time PCR, immunohistochemistry and western blots in the temporal neocortex of twenty four patients with intractable epilepsy and twelve control subjects. RESULTS: Compared with the control group, the expression of miR-199a-5p and miR-199b-5p was significantly lower in epileptic brain tissues (p < 0.05). The levels of HIF-1α mRNA and protein were highly up-regulated in epileptic brain tissues compared with those of control subjects (p < 0.05). CONCLUSION: These data suggest that the abnormal expression of miR-199 and HIF-1α in epileptic brain tissue may be involved in the pathophysiology of human epilepsy and that the expression of HIF-1α may be regulated by miR-199. These findings may provide new insights into the treatment of epilepsy.

Glucagon receptor antibody completely suppresses type 1 diabetes phenotype without insulin by disrupting a novel diabetogenic pathway.

Insulin monotherapy can neither maintain normoglycemia in type 1 diabetes (T1D) nor prevent the long-term damage indicated by elevated glycation products in blood, such as glycated hemoglobin (HbA1c). Here we find that hyperglycemia, when unaccompanied by an acute increase in insulin, enhances itself by paradoxically stimulating hyperglucagonemia. Raising glucose from 5 to 25 mM without insulin enhanced glucagon secretion ∼two- to fivefold in InR1-G9 α cells and ∼18-fold in perfused pancreata from insulin-deficient rats with T1D. Mice with T1D receiving insulin treatment paradoxically exhibited threefold higher plasma glucagon during hyperglycemic surges than during normoglycemic intervals. Blockade of glucagon action with mAb Ac, a glucagon receptor (GCGR) antagonizing antibody, maintained glucose below 100 mg/dL and HbA1c levels below 4% in insulin-deficient mice with T1D. In rodents with T1D, hyperglycemia stimulates glucagon secretion, up-regulating phosphoenolpyruvate carboxykinase and enhancing hyperglycemia. GCGR antagonism in mice with T1D normalizes glucose and HbA1c, even without insulin.

Adeno-associated virus-mediated osteoprotegerin gene transfer protects against joint destruction in a collagen-induced arthritis rat model.

OBJECTIVE: To evaluate the in vivo joint protection effect of recombinant adeno-associated virus-mediated gene transfer of human osteoprotegerin (rAAV-hOPG). METHODS: Collagen-induced arthritis (CIA) rat model was established. CIA rats were randomly divided into three groups: CIA control group (PBS), rAAV-EGFP (enhanced green fluorescent protein) group and rAAV-hOPG (100 µL/d) group, which received corresponding intra-articular injection treatment. The thickness of the palms and soles, arthritis index, radiological score, pathological score, bone damage factor and protein expression of inflammatory factors were measured and compared with normal control group rats. RESULTS: Positive fluorescence of frozen section confirmed that rAAV-hOPG was efficiently transduced into the synovial tissues of test rats. In rAAV-hOPG group compared with CIA control group, the radiological score was 30.18% lower (P<0.05); the expression of OPG protein was 93.41% higher (P<0.05); the expression of matrix metalloproteinase-3 (MMP-3) protein was 35.38% lower (P<0.05); however, the expression of IL-1ß was not significant; the scores of pannus and inflammation in rAAV-hOPG group have no significant difference. CONCLUSION: These results suggest that adeno-associated virus-mediated transfer of human osteoprotegerin is effectively transducted into the synovial tissues of CIA model, and protects against articular cartilage and bone destruction, but has no obvious efficiency on inflammation. The results also demonstrate that gene transfer using rAAV-hOPG may be a feasible and effective therapeutic candidate to treat or prevent joint destruction in inflammatory arthritis.

Water, proton, and oxygen transport in high IEC, short side chain PFSA ionomer membranes: consequences of a frustrated network.

The effect of ion exchange capacity (IEC) on the water sorption properties of high IEC, short side chain (SSC) PFSA ionomer membranes, and the relationships between water content, proton conductivity, proton mobility, water permeation, oxygen diffusion, and oxygen permeation are investigated. SSC PFSA ionomer membranes possessing 1.3, 1.4, and 1.5 mmol g(-1) IEC are compared to a series of long side chain (LSC) PFSA ionomer membranes ranging in IEC from 0.9 to 1.13 mmol g(-1). At 25 °C, fully-hydrated SSC ionomer membranes are characterized as possessing higher water contents (56-75 vol%), moderate λ values (15-18), high analytical acid concentrations (2-2.8 M), and moderate conductivity (88-115 mS/cm); but lower than anticipated effective proton mobility. Complementary measurements of water permeability, oxygen diffusion, and oxygen permeability also yield lower than expected values given their much higher water contents. Potential benefits afforded by reducing the side chain length of PFSA ionomer membranes, such as increased crystallinity, higher IEC, and high hydrated acid concentration are offset by a less-developed, frustrated hydrophilic percolation network, which provides a motivation for future improvements of transport properties for this class of material.

Polyethylene glycolated recombinant TNF receptor I improves insulitis and reduces incidence of spontaneous and cyclophosphamide-accelerated diabetes in nonobese diabetic mice.

We have conducted three studies to examine the role of TNFalpha in islet destruction in female nonobese diabetic mouse (NOD) mice, a model of human autoimmune diabetes, using polyethylene glycolated (PEGylated) soluble TNF receptor type I (PEG sTNF-RI) as TNFalpha antagonist. PEG sTNF-RI (3 mg/kg, sc) was given every other day to NOD mice from age wk 8 for 12 wk (study 1), from age wk 12 for 8 wk (study 2), or from age wk 8 for 3 wk, with cyclophosphamide (6 mg/mouse) injected at wk 9 to accelerate the onset of diabetes (study 3). Diabetic incidence was reduced (control vs. PEG sTNF-RI) from 68.7% (11 of 16) to 18.3% (3 of 16) in study 1, from 84.6% (11 of 13) to 28.5% (4 of 14) in study 2, and from 66.6% (8 of 12) to 23.1% (3 of 13) in study 3, respectively. The incidence of insulitis was also reduced from 91.6% (11 of 12) to 12.5% (2 of 16) in study 1 and from 100% (7 of 7) to 16.6% (2 of 12) in study 2 by PEG sTNF-RI. PEG sTNF-RI also largely preserved islet insulin content, reduced mRNA of inducible nitric oxide synthase and IL-6 in pancreases, and lowered plasma corticosterone, glycerol, and free fatty acid levels. These results confirm a pathogenic role of TNFalpha in mediating insulitis in NOD mice and suggest the prophylactic and therapeutic potential of PEG sTNF-RI for human autoimmune diabetes.