Novel catalytic effects of Mn3O4 for all vanadium redox flow batteries

A new approach for enhancing the electrochemical performance of carbon felt electrodes by employing non-precious metal oxides is designed. The outstanding electro-catalytic activity and mechanical stability of Mn(3)O(4) are advantageous in facilitating the redox reaction of vanadium ions, leading to efficient operation of a vanadium redox flow battery.     

Surface-dependent, ligand-mediated photochemical etching of CdSe nanoplatelets

Photochemical etching of CdSe nanoplatelets was studied to establish a relationship between the nanocrystal surface and the photochemical activity of an exciton. Nanoplatelets were synthesized in a mixture of octylamine and oleylamine for the wurtzite (W) lattice or in octadecene containing oleic acid for the zinc-blende (ZB) lattice. For photochemical etching, nanoplatelets were dispersed in chloroform containing oleylamine and tributylphosphine in the absence or presence of oleic acid and then irradiated with light at the band-edge absorption maxima. Etching phenomena were characterized using UV-vis absorption spectroscopy and transmission electron microscopy. The absorption spectra of both W and ZB CdSe nanoplatelets showed that the exciton was confined in one dimension along the thickness. However, the two nanoplatelets presented different etching kinetics and erosion patterns. The rate of etching for W CdSe nanoplatelets was much faster than that for ZB nanoplatelets. Small holes were uniformly perforated on the planar surface of W nanoplatelets, whereas the corners and edges of ZB nanoplatelets were massively eroded without a significant perforation on the planar surface. This suggests that the amine-passivated surface of trivalent cadmium atoms on CdSe nanoplatelets is photochemically active, but the carboxylate-passivated surface of divalent cadmium atoms is not. Hence, the ligand, which induces the growth of W or ZB CdSe nanoplatelets, mediates the surface-dependent photochemical etching. This result implies that an electron-hole pair can be extracted from the planar surface of amine-passivated W nanoplatelets but from the corners and edges of carboxylate-passivated ZB nanoplatelets.     

Magnetic structure variation in manganese-oxide clusters

Negative-ion photoelectron spectroscopy and ab initio simulations are used to study the variation in magnetic structure in Mn(x)O(y) (x = 3, 4[semicolon] y = 1, 2) clusters. The ferrimagnetic and antiferromagnetic ground-state structures of Mn(x)O(y) are 0.16-1.20 eV lower in energy than their ferromagnetic isomers. The presence of oxygen thus stabilizes low-spin isomers relative to the preferred high-spin ordering of bare Mn(3) and Mn(4). Each cluster has a preferred overall magnetic moment, and no evidence is seen of competing states with different spin multiplicities. However, non-degenerate isomags, which possess the same spin multiplicity but different arrangements of local moments, do contribute additional features and peak broadening in the photoelectron spectra. Proper accounting for all possible isomags is shown to be critical for accurate computational prediction of the spectra.     

A novel and efficient route to diarylmethanes catalyzed by nickel(II) ion on nanoporous carbon

Much improved catalytic carbon-carbon bond-forming reactions between aryl chlorides and Grignard reagents has been achieved using nickel(II) ion on nanoporous carbon.     

Catalytic carbonylation for the synthesis of chemical intermediates

Chemistry related to three catalytic carbonylation reactions is discussed. Synthesis of diphenylurea from nitrobenzene, aniline, and CO gives isolated yields above 98% at 100–120 °C and 15–60 bar of CO in the presence of a palladium (II) complex, PPh₃ and NEt₄Cl. Experimental evidence was provided to prove a new reaction stoichiometry and involvement of a carbamoyl intermediate. In carbonylation of HCHO over ion exchange resin catalysts, reaction temperature, time, pressure, and solvent were important variables to obtain high yields of methyl glycolate. Carbonylation of isobutylphenylethanol at 120°C and 40 bar of CO in the presence of PdCl₂−PPh₃−HCl gives 98% yield of α-(4-isobutylphenyl) propionic acid (ibuprofen). Each catalyst component had a definite role that is indispensable for an efficient overall reaction.     

Simultaneous,real-time measurement of nitric oxide and oxygen dynamics during cardiac ischemia-reperfusion of the rat utilizing sol-gel-derived electrochemical microsensors

In this study, we simultaneously measured nitric oxide (NO) and oxygen (O₂) dynamics in the myocardium during myocardial ischemia-reperfusion (IR) utilizing sol-gel modified electrochemical NO and O₂ microsensors. In addition, we attempted to clarify the correlation between NO release in the ischemic period and O₂ restoration in the myocardium after reperfusion, comparing a control heart with a remote ischemic preconditioning (RIPC)-treated heart as an attractive strategy for myocardial protection. Rat hearts were randomly divided into two groups: a control group (n = 5) and an RIPC group (n = 5, with RIPC treatment). Myocardia that underwent RIPC treatment (182 ± 70 nM, p < 0.05) released more NO during the ischemic period than those of the control group (63 ± 41 nM). The restoration value of oxygen tension (pO₂) in the RIPC group significantly increased and was restored to pre-ischemic levels (92.6 ± 36.8%); however, the pO₂ of the control group did not increase throughout the reperfusion period (5.7 ± 7.5%, p = 0.001). Myocardial infarct size measurements revealed a significant decrease in cell death in the myocardium region of the RIPC group (41.44 ± 6.42%, p = 0.001) compared with the control group (60.05 ± 10.91%). As a result, we showed that the cardioprotective effect of RIPC could be attributed to endogenous NO production during the ischemic period, which subsequently promoted reoxygenation in post-ischemic myocardia during early reperfusion. Our results suggest that the promotion of endogenous formation during an ischemic episode might be helpful as a therapeutic strategy for protecting the myocardium from IR injury. Additionally, our NO and O₂ perm-selective microsensors could be utilized to evaluate the effect of drug or treatment.     

Self-Assembly Behavior and Application of Terphenyl-Cored Trimaltosides for Membrane-Protein Studies: Impact of Detergent Hydrophobic Group Geometry on Protein Stability

Amphipathic agents are widely used in various fields including biomedical sciences. Micelle-forming detergents are particularly useful for in vitro membrane-protein characterization. As many conventional detergents are limited in their ability to stabilize membrane proteins, it is necessary to develop novel detergents to facilitate membrane-protein research. In the current study, we developed novel trimaltoside detergents with an alkyl pendant-bearing terphenyl unit as a hydrophobic group, designated terphenyl-cored maltosides (TPMs). We found that the geometry of the detergent hydrophobic group substantially impacts detergent self-assembly behavior, as well as detergent efficacy for membrane-protein stabilization. TPM-Vs, with a bent terphenyl group, were superior to the linear counterparts (TPM-Ls) at stabilizing multiple membrane proteins. The favorable protein stabilization efficacy of these bent TPMs is likely associated with a binding mode with membrane proteins distinct from conventional detergents and facial amphiphiles. When compared to n-dodecyl-β-d -maltoside (DDM), most TPMs were superior or comparable to this gold standard detergent at stabilizing membrane proteins. Notably, TPM-L3 was particularly effective at stabilizing the human β₂ adrenergic receptor (β₂AR), a G-protein coupled receptor, and its complex with G_s protein. Thus, the current study not only provides novel detergent tools that are useful for membrane-protein study, but also suggests a critical role for detergent hydrophobic group geometry in governing detergent efficacy.     

Recent Advances in Aerosol‐Assisted Spray Processes for the Design and Fabrication of Nanostructured Metal Chalcogenides for Sodium‐Ion Batteries

Increasing demand for sodium‐ion batteries (SIBs), one of the most feasible alternatives to lithium ion batteries (LIBs), has resulted because of their high energy density, low cost, and excellent cycling stability. Consequently, the design and fabrication of suitable electrode materials that govern the overall performance of SIBs are important. Aerosol‐assisted spray processes have gained recent prominence as feasible, scalable, and cost‐effective methods for preparing electrode materials. Herein, recent advances in aerosol‐assisted spray processes for the fabrication of nanostructured metal chalcogenides (e.g., metal sulfides, selenides, and tellurides) for SIBs, with a focus on improving the electrochemical performance of metal chalcogenides, are summarized. Finally, the improvements, limitations, and direction of future research into aerosol‐assisted spray processes for the fabrication of various electrode materials are presented.     

Synthesis of trisubstituted thiazoles by ligand-free palladium-catalyzed direct 5-arylation of 2,4-disubstituted thiazoles under conventional and microwave-assisted heating

Trisubstituted thiazoles were synthesized with excellent yields using ligand-free, palladium-catalyzed, direct 5-arylation of 2,4-disubstituted thiazole and conventional or microwave-assisted heating. The palladium-catalyzed reaction yields were significantly influenced by LiCl additive, solvent, and heating method. The reaction times were reduced dramatically by employing microwave radiation instead of conventional heating. The synthetic methods can be applied to diverse 2,4,5-trisubstituted thiazoles by varying the aryl bromide and disubstituted thiazole reactants.