Electrode Kinetics and Activation Energy of Uranyl-Ferron Chelate by Polarography

The uranyl chelate of ferron was investigated polarographically over the pH range 1.98–10.00 and ligand concentration 0.005–0.060.M. A reversible and diffusion controlled reduction wave was obtained, however, when ferron concentration below 0.02M and pH below 5.0, it became irreversible. The chelate species identified were UO₂(HA) ₂ at pH range 2.5–7.1 and UO₂(OH) (A) ₂^?3 over pH 7.1. The electron-transfer coefficient, rate constant, diffusion coefficient and activation energy of the reduction process were determined.     

Carbonylchromium derivatives of bismuth: new syntheses and relevance to cbond;o activation

We have discovered a series of novel pentacarbonylchromium derivatives of bismuth from the reactions of NaBiO(3) with [Cr(CO)(6)] in KOH/MeOH solutions. When the reaction was carried out at room temperature, the highly charged [Bi[Cr(CO)(5)](4)](3-) (1) was obtained, whose structure was shown by X-ray analysis to possess a central bismuth atom tetrahedrally coordinated to four [Cr(CO)(5)] groups. As the reaction was heated at 80 degrees C, the methyl-substituted complex [MeBi[Cr(CO)(5)](3)](2-)(2) was obtained, presumably via the CbondO activation of MeOH. Further reactions of 1 with CH(2)Cl(2) or CHtbondCCH(2)Br form the halo-substituted complexes [XBi[Cr(CO)(5)](3)](2-)(X=Cl, 3; Br, 4), respectively. On the other hand, the reactions of 1 with RI (R=Me, Et) led to the formation of the alkyl-substituted complexes [RBi[Cr(CO)(5)](3)](2-)(R=Me, 2; Et). The formation of complexes 1-4 is discussed, presumably via the intermediate bismuthinidene [Bi[Cr(CO)(5)](3)](-) or the trianion [Bi[Cr(CO)(5)](3)](3-).     

发光反应型有机铵分子与CdSe纳米晶的组装

用巯基乙酸做稳定剂制备了水溶性CdSe纳米颗粒, 用十六烷基三甲基溴化铵(HTAB)、发光性(4-甲氧基均二苯乙烯基)二甲基乙基溴化铵 (MODAB)及末端含有双键的(4-甲基丙烯酰氧基均二苯乙烯基)二甲基乙基溴化铵(MSDAB)对该CdSe纳米颗粒进行了混合组装.通过改变三种有机分子的比例可以调控所得组装体的溶解性、聚合性及其发光性质.实验结果表明,当HTAB:MODAB:MSDAB=1:5.98～5.90:0.02～0.10(摩尔比)时,所得组装体具有较好的聚合性、溶解性和荧光性质.     

Syntheses of chromium pentacarbonyl derivatives of arsenic(V) and antimony(V). contrasting chemical reactivity with organic halogen derivatives

We have synthesized a new series of chromium-group 15 dihydride and hydride complexes [H(2)As(Cr(CO)(5))(2)](-) (1) and [HE(Cr(CO)(5))(3)](2)(-) (E = As, 2a; E = Sb, 2b), which represent the first examples of group 6 complexes containing E-H fragments. The contrasting chemical reactivity of 2a and 2b with organic halogen derivatives is demonstrated. The reaction of 2a with RBr (R = PhCH(2), HC triple bond CCH(2)) produces the RX addition products [(R)(Br)As(Cr(CO)(5))(2)](-) (R = PhCH(2), 3; R = C(3)H(3), 4), while the treatment of 2b with RX (RX = PhCH(2)Br or HC triple bond CCH(2)Br, CH(3)(CH(2))(5)C(O)Cl) forms the halo-substituted complexes [XSb(Cr(CO)(5))(3)](2-) (X = Br, 5; X = Cl, 6). Moreover, the dihaloantimony complexes [XX'Sb(Cr(CO)(5))(2)](-) can be obtained from the reaction of 2b with the appropriate organic halides. In this study, a series of organoarsenic and antimony chromium carbonyl complexes have been synthesized and structurally characterized and the role of the main group on the formation of the resultant complexes is also discussed.     

CO在铜基催化剂上活化及助催剂作用本质的量子化学研究

提出了CO在助促和非助促的铜基催化剂上吸附活化的两种活性中心原子族模型Cu_5和Cu_4M~(n+)O。应用电荷自洽离散变分X_a近似计算方法对CO在这两种模型上活化本质,并对过渡金属助催剂离子M~(n+)(从ⅣA—ⅧA族中各选一个V~(3+),Ti~(3+),Fe~(3+),Mn~(2+),Mo~(4+))与合成甲醇铜基催化剂上金属铜原子相互作用的本质及其对CO活化的效应进行量子化学研究。计算表明CO是以碳端吸附在活性中心模型Cu_4M~(n+)O中的Cu(1)原子上,并向助催剂M~(n+)离子倾斜45°。从吸附态CO—Cu_5和CO—Cu_4M~(n+)O的原子簇轨道,态密度以及C—O间重选集居数的计算结果指出,CO分子受到活化。助催剂与催化剂中铜原子间相互作用影响了铜原子的价态,改变体系E_f能级,改善了前线轨道HOMO与CO 2π~*轨道的匹配,从而增加d电子的反馈,降低CO间的重选集居数,促进了CO的活化。     

Phenolic Constituents,Antioxidant and Cytoprotective Activities,Enzyme Inhibition Abilities of Five Fractions from Vaccinium dunalianum Wight

The bud of Vaccinium dunalianum Wight has been traditionally consumed as health herbal tea by “Yi” people in Yunnan Province, China, which was locally named “Que Zui tea”. This paper studied the chemical constituents of five fractions from Vaccinium dunalianum, and their enzyme inhibitory effects of α-glucosidase and pancreatic lipase, antioxidant activity, and cytoprotective effects on H₂O₂-induced oxidative damage in HepG2 cells. The methanol extract of V. dunalianum was successively partitioned with petroleum ether (PF), chloroform (CF), ethyl acetate (EF), n-butanol (BF), and aqueous (WF) to obtain five fractions. The chemical profiling of the five fractions was analyzed by ultra-high-performance liquid chromatography coupled with a tandem mass spectrometry (UHPLC-MS/MS), and 18 compounds were tentatively identified. Compared to PF, CF, BF and WF, the EF revealed the highest total phenols (TPC) and total flavonoids (TFC), and displayed the strongest enzyme inhibition ability (α-glucosidase and pancreatic lipase) and antioxidant capacity (DPPH, ABTS and FRAP). Furthermore, these five fractions, especially EF, could effectively inhibit reactive oxygen species (ROS) production and cell apoptosis on H₂O₂-induced oxidative damage protection in HepG2 cells. This inhibitory effect might be caused by the up-regulation of intracellular antioxidant enzyme activity (CAT, SOD, and GSH). The flavonoids and phenolic acids of V. dunalianum might be the bioactive substances responsible for enzyme inhibitory, antioxidant, and cytoprotective activities.     

Effects of SiNx on two-dimensional electron gas and current collapse of AlGaN/GaN high electron mobility transistors

SiN_x is commonly used as a passivation material for AlGaN/GaN high electron mobility transistors (HEMTs). In this paper, the effects of SiN_x passivation film on both two-dimensional electron gas characteristics and current collapse of AlGaN/GaN HEMTs are investigated. The SiN_x films are deposited by high- and low-frequency plasma-enhanced chemical vapour deposition, and they display different strains on the AlGaN/GaN heterostructure, which can explain the experiment results.     

Controlled decoherence of three-level rf-SQUID qubit with asymmetric potential

A scheme is proposed to controll the decoherence of three-level rf-SQUID qubit with asymmetric potential by designing an external electric circuit for superconductive flux qubit. The results show that it may not only raise the gate speed but also extend decoherence time for a three-level structure.     

Antiinflammation Derived Suzuki-Coupled Fenbufens as COX-2 Inhibitors: Minilibrary Construction and Bioassay

A small fenbufen library comprising 18 compounds was prepared via Suzuki Miyara coupling. The five-step preparations deliver 9–17% biphenyl compounds in total yield. These fenbufen analogs exert insignificant activity against the IL-1 release as well as inhibiting cyclooxygenase 2 considerably. Both the para-amino and para-hydroxy mono substituents display the most substantial COX-2 inhibition, particularly the latter one showing a comparable activity as celecoxib. The most COX-2 selective and bioactive disubstituted compound encompasses one electron-withdrawing methyl and one electron-donating fluoro groups in one arene. COX-2 is selective but not COX-2 to bioactive compounds that contain both two electron-withdrawing groups; disubstituted analogs with both resonance-formable electron-donating dihydroxy groups display high COX-2 activity but inferior COX-2 selectivity. In silico simulation and modeling for three COX-2 active—p-fluoro, p-hydroxy and p-amino—fenbufens show a preferable docking to COX-2 than COX-1. The most stabilization by the p-hydroxy fenbufen with COX-2 predicted by theoretical simulation is consistent with its prominent COX-2 inhibition resulting from experiments.     

Influence of the tangential velocity on the compressible Kelvin−Helmholtz instability with nonequilibrium effects

Kelvin−Helmholtz (KH) instability is a fundamental fluid instability that widely exists in nature and engineering. To better understand the dynamic process of the KH instability, the influence of the tangential velocity on the compressible KH instability is investigated by using the discrete Boltzmann method based on the nonequilibrium statistical physics. Both hydrodynamic and thermodynamic nonequilibrium (TNE) effects are probed and analyzed. It is found that, on the whole, the global density gradients, the TNE strength and area firstly increase and decrease afterwards. Both the global density gradient and heat flux intensity in the vertical direction are almost constant in the initial stage before a vortex forms. Moreover, with the increase of the tangential velocity, the KH instability evolves faster, hence the global density gradients, the TNE strength and area increase in the initial stage and achieve their peak earlier, and their maxima are higher for a larger tangential velocity. Physically, there are several competitive mechanisms in the evolution of the KH instability. (i) The physical gradients increase and the TNE effects are strengthened as the interface is elongated. The local physical gradients decrease and the local TNE intensity is weakened on account of the dissipation and/or diffusion. (ii) The global heat flux intensity is promoted when the physical gradients increase. As the contact area expands, the heat exchange is enhanced and the global heat flux intensity increases. (iii) The global TNE intensity reduces with the decreasing of physical gradients and increase with the increasing of TNE area. (iv) The nonequilibrium area increases as the fluid interface is elongated and is widened because of the dissipation and/or diffusion.