Active nano-CuPt3 electrocatalyst supported on graphene for enhancing reactions at the cathode in all-vanadium redox flow batteries

Graphene-supported monometallic (Pt) and bimetallic (CuPt₃) cubic nanocatalysts have been investigated as new positive electrode materials for improving the VO₂⁺/VO²⁺ redox process occurring in the vanadium redox flow batteries (VRB). High-resolution transmission electron microscopy (HRTEM) and scanning electron microscopy (SEM) have been employed to characterize the electrodes. The presence of the CuPt₃ nanocubes on graphene conferred higher electrocatalytic activity due to the much higher electroactive area compared to that obtained with the Pt nanoparticles. The electrochemical surface area of the nano-(CuPt₃)-decorated graphene electrode was 105% higher compared to non-decorated graphene, being then a promising alternative for improving the VRB.     

Effect of pre‐treatments based on UV photocatalysis and photo‐oxidation on toluene biofiltration performance

BACKGROUND: The integration of UV photocatalysis and biofiltration seems to be a promising combination of technologies for the removal of hydrophobic and poorly biodegradable air pollutants. The influence of pre‐treatments based on UV_{254 nm} photocatalysis and photo‐oxidation on the biofiltration of toluene as a target compound was evaluated in a controlled long‐term experimental study using different system configurations: a standalone biofilter, a combined UV photocatalytic reactor‐biofilter, and a combined UV photo‐oxidation reactor (without catalyst)‐biofilter. RESULTS: Under the operational conditions used (residence time of 2.7 s and toluene concentrations 600–1200 mg C m^?3), relatively low removal efficiencies (6–3%) were reached in the photocatalytic reactor and no degradation of toluene was found when the photo‐oxidation reactor was operated without catalyst. A noticeable improvement in the performance of the biofilter combined with a photocatalytic reactor was observed, and the elimination capacity of the biological process increased by more than 12 g C h^?1 m^?3 at the inlet loads studied of 50–100 g C h^?1 m^?3. No positive effect on toluene removal was observed for the combination of UV photoreactor and biofilter. CONCLUSIONS: Biofilter pre‐treatment based on UV_{254 nm} photocatalysis showed promising results for the removal of hydrophobic and recalcitrant air pollutants, providing synergistic improvement in the removal of toluene. Copyright © 2011 Society of Chemical Industry     

Incorporation of chloramphenicol and captopril into poly(GL)‐b‐poly(GL‐co‐TMC‐co‐CL)‐b‐poly(GL) monofilar surgical sutures

Incorporation of chloramphenicol and captopril into coated and uncoated monofilament sutures was evaluated, as well as the derived bactericide and wound healing effects. To this end, a commercially available suture and an amorphous random copolymer constituted by trimethylene carbonate and lactide units were considered. The suture had a segmented architecture based on polyglycolide hard blocks and a soft block constituted by glycolide, trimethylene carbonate and ε‐caprolactone units. Chloramphenicol was better loaded when the coating copolymer was employed due to its protective effect whereas captopril showed an opposite behavior due to partial solubilization during immersion in the coating bath. Interestingly, the release behavior was very different for the two studied drugs since a significant retention of chloramphenicol was always detected, suggesting the establishment of interactions between drug and copolymers. On the other hand, delivery of captopril showed a typical dose dependent behavior. A low in vitro toxicity of the two drugs was determined considering both epithelial‐like and fibroblast‐like cells. Bactericide effect of chloramphenicol against Gram‐negative and Gram‐positive bacteria was demonstrated at a dose that was non‐toxic for all assayed cells. An accelerating wound healing effect of captopril was also demonstrated for early events. In this case, the use of a coating copolymer was fundamental to avoid cytotoxic effects on highly loaded sutures. © 2017 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2017 , 134, 44762.     

Improved thermal stability of oxide-supported naked gold nanoparticles by ligand-assisted pinning

We report a method to improve the thermal stability, up to 900 °C, of bare-metal (naked) gold nanoparticles supported on top of SiO(2) and SrTiO(3) substrates via ligand-assisted pinning. This approach leads to monodisperse naked gold nanoparticles without significant sintering after thermal annealing in air at 900 °C. The ligand-assisted pinning mechanism is described.     

Multiarm star poly(glycidol)-block-poly(styrene) as modifier of anionically cured diglycidylether of bisphenol A thermosetting coatings

Well-defined multiarm star copolymer poly(glycidol)-b-poly(styrene) (PGOH-b-PS) with an average number of PS arms per molecule of 85 has been prepared. The core first approach has been selected as the methodology using atom transfer radical polymerization (ATRP) of styrene to grow the arms from an activated hyperbranched poly(glycidol) as core. This activated hyperbranched macroinitiator was prepared by esterification of hyperbranched poly(glycidol) (PGOH) with 2-bromoisobutyryl bromide.PGOH-b-PS was used to modify diglycidylether of bisphenol A coatings cured by anionic ring-opening mechanism using 1-methyl imidazole as the initiator. The kinetics of the curing process, studied by dynamic scanning calorimetry (DSC), was not much affected when PGOH-b-PS was added to the formulation. By rheometry the effect of this new polymer topology on the complex viscosity (η^*) of the reactive mixture was analyzed. The phase-separation of the modified coatings was proved by dynamic thermomechanical analysis (DMTA) and electronic microscopy (SEM and TEM) showing nano- or microphase separation as a function of the modifier content. The addition of this star polymer led to increase in the rigidity in terms of Young's modulus and in the microhardness in comparison to neat DGEBA.     

Electrospun nanofibers of a degradable poly(ester amide). Scaffolds loaded with antimicrobial agents

Electrospinning conditions were evaluated to prepare micro/nanofibers of a biodegradable poly(ester amide) constituted by L-alanine, 1,12-dodecanediol and sebacic acid. 1,1,1,3,3,3-Hexafluroroisopropanol appeared as the most appropriate solvent to obtain fibers in a wide range of electrospinning conditions that allowed tuning the final diameter size. Fiber diameter increased with the flow, distance between the needle tip and the collector and decreasing voltage, which made it possible to obtain homogeneous fibers in the 1700–320 nm range. Fibers were loaded with antimicrobial agents like silver and chlorohexidine, and the influence of agent concentration in the electrospinning solutions on the fiber diameter size was determined. The polymer was able to crystallize during the electrospinning process, giving rise to a structure slightly different from that obtained by solution crystallization and related to that attained after crystallization from the melt state. Addition of antimicrobial agents had little effect on the degree of crystallinity, although it decreased slightly when chlorhexidine was employed. Scaffolds prepared from the silver and chlorhexidine loaded samples supported cell adhesion and proliferation. Furthermore, a clear and well differentiated antimicrobial effect against both Gram-positive (e.g. M. luteus) and Gram-negative (e.g. E. coli) bacteria was demonstrated.     

Preparation of random poly(butylene alkylate-co-terephthalate)s with different methylene group contents: crystallization and degradation kinetics

Random copolyesters having 1,4-butanediol units were synthesized from a transesterification process between homopolymers constituted by aliphatic dicarboxylates (i.e. succinate, adipate or sebacate) and the aromatic therephthalate derivative, as verified by NMR spectroscopy. Biodegradability of resulting copolyesters was studied via enzymatic hydrolysis using Pseudomonas cepacia lipase at pH = 7.2 and 37 °C. Kinetics of degradation showed that in all cases the degradation rate decreased after 19 days of exposure. The observed glass transition temperatures, T _g, of the random copolyesters showed a non-linear dependence on composition, a feature that was explained in terms of the internal stiffening effect of butylene terephthalate units. Copolymers with higher aliphatic (i.e. 50 and 70 mol-%) and methylene (i.e. adipate and sebacate units) contents showed double melting peaks in DSC thermograms. These copolyesters resulted in two different crystalline rich phases after melt-crystallization and subsequent cooling. The ratio between these phases logically depended on the predominant aliphatic or aromatic dicarboxylate content. The copolymers initially crystallized via the aromatic units through a heterogeneous nucleation and a spherulitic growth. The presence of aliphatic dicarboxylate units hindered the beginning of the crystallization process, but the overall growth kinetic constant was similar for all samples. The secondary nucleation constants were determined and showed higher values for samples with higher adipate and sebacate contents.     

Discovery of novel non-cyclam polynitrogenated CXCR4 coreceptor inhibitors

HIV cell fusion and entry have been validated as targets for therapeutic intervention against infection. Bicyclams were the first low-molecular-weight compounds to show specific interaction with CXCR4. The most potent bicyclam was AMD3100, in which the two cyclam moieties are tethered by a 1,4-phenylenebis(methylene) bridge. It was withdrawn from clinical trials owing to its lack of oral bioavailability and cardiotoxicity. We have designed a combinatorial library of non-cyclam polynitrogenated compounds by preserving the main features of AMD3100. At least two nitrogen atoms on each side of the p-phenylene moiety, one in the benzylic position and the other(s) in the heterocyclic system were maintained, and the distances between them were similar to the nitrogen atom distances in cyclam. A selection of diverse compounds from this library were prepared, and their in vitro activity was tested in cell cultures against HIV strains. This led to the identification of novel potent CXCR4 coreceptor inhibitors without cytotoxicity at the tested concentrations.     

Effluent content from albedo degradation and kinetics at different temperatures in the enzymatic peeling of grapefruits

This work studies the variation in the effluent content from the reactor in enzymatic peeling of grapefruits, to determine the loss of soluble solids, reducing sugars and galacturonic acid, the main component from the albedo of the skin to model the solid–liquid transfer in this process. Experiments to study the efficiency of the enzymatic reaction include the effect of the temperature on the kinetics of albedo degradation to find an equation relating both variables and also the activation energy of this process, its value being 36.9 kJ/mol.