Hydrodesulfurization of thiophene on carbon nanofiber supported Co/Ni/Mo catalysts

Co, Mo, NiMo and CoMo catalysts supported on alumina, fishbone and platelet carbon nanofibers (CNFs) have been prepared. The dispersion of the oxide phases was qualitatively studied and compared using X-ray diffraction (XRD) and transmission electron microscopy (TEM). The reducibility of the catalysts was studied by temperature programmed reduction (TPR). Hydrodesulfurization (HDS) of thiophene was used as a model reaction to compare the activity of different catalysts. The activity tests showed that the alumina supported catalysts exhibited higher activity compared to the corresponding CNF supported catalysts, and the NiMo catalysts were more active than the corresponding CoMo catalysts. The thiophene HDS activity was correlated with the dispersion of the molybdenum species and the reducibility of different catalysts. Interestingly, the CNF supported Co catalysts have higher thiophene HDS activity than the CNF supported Co(Ni)Mo catalysts.     

The role of the conserved threonine in P450 BM3 oxygen activation: substrate-determined hydroxylation activity of the Thr268Ala mutant

The hydroxylation activity of the Thr268Ala mutant of P450(BM3) has been shown to occur to varying degrees with small alterations in the structure of a fatty-acid substrate. Ten substrates were investigated, including straight chain, branched chain and cis-cyclopropyl substituted fatty acids with a straight-chain length that varied between 12 and 16 carbon atoms. The efficacy of the hydroxylation activity appeared to be governed by the chain length of the substrate. Substrates possessing 14 to 15 carbons afforded the highest levels of activity, which were comparable with the wild-type enzyme. Outside of this window, straight-chain fatty acids showed reduced activity over the other substrate types. These results provide a cautionary tale concerning the loss of ferryl activity in such cytochrome P450 threonine to alanine mutants, as the nature of the substrate can determine the extent to which hydroxylation chemistry is abolished.     

Oxygen reduction reaction properties of carbon nanofibers: Effect of metal purification

Carbon nanofibers (CNFs) are grown on metal catalysts and electrochemical treatment is used to remove the metal catalyst residuals from the as-grown CNFs. For comparison, the CNFs are also purified by a chemical method and a thermal method. The oxygen reduction reaction (ORR) properties of CNFs purified by these three methods are examined by cyclic voltammetry. CNFs treated by the electrochemical method have a more positive ORR onset reduction potential and peak potential compared with those treated by chemical and thermal methods, and this is because the microstructures of CNFs are less changed by electrochemical method. However, they have a lower electrochemical capacity and ORR peak current than those treated by the chemical method. Cyclic voltammetric measurements at different scan rates confirm that the oxygen reductions on CNFs treated by electrochemical and chemical methods are controlled by diffusion, while on CNFs treated by thermal method is partially influenced by diffusion.     

钽等离子体渗氮的表面过程分析

对钽表面渗氮的固－气界面反应过程进行了热力学和动力学分析,从到理论预测了各种参数（压力、气体、组成、温度、电参数等）对表面过程的影响,并借助于等离子体,在较你廿获得由层与Ｎ在ＴＡ中的固溶体组成的表面硬化层,层为六方晶系的Ｔａ６Ｎ２,５７和／或非昌态。通过调整工艺参数有效地抑制了钽表面氧的渗入和Ｔａ２Ｏ５的形成,使得离子渗氮后,仍保持较低的表面粗糙度。     

Surface roughness of a hot-dipped galvanized sheet steel as a function of deformation mode

A hot-dipped galvanized zinc-coated sheet steel was deformed with three different laboratory test systems: a Marciniak punch system, a flat-die friction test system, and a cupping system. These systems were able to impose various combinations of deformation modes to the sheet. The deformation modes include: (1) strain without die contact, (2) sliding, (3) pressing, and (4) bending. Strain measurements from the electrolitically gridded specimens were made at the same locations as surface profilometry measurements, allowing a direct correspondence of surface roughness with strain. Quantification of the roughening as a function of strain, sliding and bending was determined. The roughening rate depends upon the strain level as well as the strain path. Increased strain without die contact causes an increase in the surface roughness with strain paths close to plane strain exhibiting the highest roughening rate. The deformation modes of sliding, pressing, and bending cause a decrease in the surface roughness (i.e. smoothing) to occur. A first-order model is proposed to account for the surface roughness as a function of these deformation modes.     

Gold nanoclusters as colloidal catalysts for oxidation of long chain aliphatic 1,2-diols in alcohol solvents

Long chain aliphatic 1,2-diols like 1,2-hexanediol and 1,2-octanediol can be converted to the corresponding α-hydroxy-alkanoates with total chemoselectivity, in an oxidation catalyzed by an aqueous gold sol under O₂ atmosphere. The sol is stabilized with poly(vinylalcohol), and the reaction is performed in alcohol solvents. Two methods are proposed for the efficient recycling of the colloidal Au catalyst. Firstly a solvent-resistant membrane filtration can be applied. As the membrane material, poly(dimethylsiloxane) is chosen. Secondly, in appropriate conditions, the reaction proceeds in the liquid biphasic mode, and the aqueous Au sol can be recycled by phase separation. Using either of both approaches, the colloidal stability and catalytic activity can be preserved over several recycles.     

Pulsed Electromagnetic Field Stimulation in Osteogenesis and Chondrogenesis: Signaling Pathways and Therapeutic Implications

Mesenchymal stem cells (MSCs) are the main cell players in tissue repair and thanks to their self-renewal and multi-lineage differentiation capabilities, they gained significant attention as cell source for tissue engineering (TE) approaches aimed at restoring bone and cartilage defects. Despite significant progress, their therapeutic application remains debated: the TE construct often fails to completely restore the biomechanical properties of the native tissue, leading to poor clinical outcomes in the long term. Pulsed electromagnetic fields (PEMFs) are currently used as a safe and non-invasive treatment to enhance bone healing and to provide joint protection. PEMFs enhance both osteogenic and chondrogenic differentiation of MSCs. Here, we provide extensive review of the signaling pathways modulated by PEMFs during MSCs osteogenic and chondrogenic differentiation. Particular attention has been given to the PEMF-mediated activation of the adenosine signaling and their regulation of the inflammatory response as key player in TE approaches. Overall, the application of PEMFs in tissue repair is foreseen: (1) in vitro: to improve the functional and mechanical properties of the engineered construct; (2) in vivo: (i) to favor graft integration, (ii) to control the local inflammatory response, and (iii) to foster tissue repair from both implanted and resident MSCs cells.     

Evaluation of 4-(4-Fluorobenzyl)piperazin-1-yl]-Based Compounds as Competitive Tyrosinase Inhibitors Endowed with Antimelanogenic Effects

There is a considerable attention for the development of inhibitors of tyrosinase (TYR) as therapeutic strategy for the treatment of hyperpigmentation disorders in humans. Continuing in our efforts to identify TYR inhibitors, we describe the design, synthesis and pharmacophore exploration of new small molecules structurally characterized by the presence of the 4-fluorobenzylpiperazine moiety as key pharmacophoric feature for the inhibition of TYR from Agaricus bisporus (AbTYR). Our investigations resulted in the discovery of the competitive inhibitor [4-(4-fluorobenzyl)piperazin-1-yl]-(3-chloro-2-nitro-phenyl)methanone 26 (IC₅₀=0.18 μM) that proved to be ∼100-fold more active than reference compound kojic acid (IC₅₀=17.76 μM). Notably, compound 26 exerted antimelanogenic effect on B16F10 cells in absence of cytotoxicity. Docking analysis suggested its binding mode into AbTYR and into modelled human TYR.     

A Dual Physical Cross-Linking Strategy to Construct Tough Hydrogels with High Strength,Excellent Fatigue Resistance,and Stretching-Induced Strengthening Effect

Hydrogels with excellent stiffness, toughness, anti-fatigue, and self-recovery properties are regarded as promising water-containing materials. In this work, a dual physically cross-linked (DPC) sodium alginate (SA)/poly[acrylamide (AAm)-acrylic acid (AAc)-octadecyl methacrylate (OMA)]-Fe³⁺ hydrogel is reported, which is constructed by hydrophobic association (HA) and ionic coordination (IC). The optimal DPC hydrogel demonstrates excellent mechanical performance: tensile modulus of 0.65 MPa, tensile strength of 3.31 MPa, elongation at break of 1547%, and toughness of 27.8 MJ m^–3. SA/P(AAm-AAc-OMA)-Fe³⁺ DPC hydrogels also exhibit prominent anti-fatigue and self-recovery performance (99.1–109.7% modulus recovery and 90.4–108.9% dissipated energy recovery after resting for 5 min without additional stimuli at ambient temperature) through the reconstruction of reversible physical cross-linking. Some of the SA/P(AAm-AAc-OMA)-Fe³⁺ DPC hydrogels even exhibit a stretching-induced strengthening effect, which is similar to the performance of muscle—“the more training, the more strength.” Hence, the combination of HA and IC will provide an effective approach to design DPC hydrogels with desirable mechanical performances and a longer service life for wider applications of soft materials.