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41.
The electronic structure of adenosylcobalamin (B12 coenzyme, AdoCbl) has been calculated by a density functional method, using the orthogonalized linear combination of the atomic orbital method (OLCAO). Since a fixed accurately determined geometry was needed in such calculations, the crystal structure of adenosylcobalamin has been redone and refined to R = 0.065, using synchrotron diffraction data. Comparison with the recently reported electronic structures of cyano- (CNCbl) and methylcobalamin (MeCbl) shows that the net charges and bond orders vary only on the axial donors. The values in the three cobalamins suggest that the Co-C bond in MeCbl has a strength similar to that in AdoCbl, but it is significantly weaker that that in CNCbl. Present results are compared with those previously reported for the analogous corrin derivatives; i.e., simplified cobalamins with the side chains a-f replaced by H atoms. Despite a qualitative agreement, a discrepancy in the calculated HOMO-LUMO gap is found. 相似文献
42.
With the rapid development of human society, clean energy forms are imperative to sustain the normal operations of various mechanical and electrical facilities under a cozy environment. Hydrogen is considered among the most promising clean energy sources for the future. Recently, electrochemical water splitting has been considered as one of the most efficient approaches to harvest hydrogen energy, which generates only non-pollutant water on combustion. However, the sluggish anodic oxygen evolution reaction significantly restricts the efficiency of water splitting and requires a relatively high cell voltage to drive the electrolysis. Therefore, seeking a thermodynamically favorable anodic reaction to replace the sluggish oxygen evolution reaction by utilizing highly active bifunctional electrocatalysts for the anodic reaction and hydrogen evolution are crucial for achieving energy-efficient hydrogen production for industrial applications. Nevertheless, it is known that the oxygen evolution reaction can be replaced with other useful and thermodynamically favorable reactions to reduce the electrolysis voltage for realizing energy-efficient hydrogen production. Therefore, in this study, we present a bifunctional nickel nanoparticle-embedded carbon (Ni@C) prism-like microrod electrocatalyst synthesized via a two-step method involving the synthesis of a precursor metal-organic framework-74 and subsequent carbonization treatment for methanol oxidation and hydrogen evolution. The interfacial structure consisting of a nickel and carbon skeleton was realized via in situ carbonization. However, the dispersed nickel nanoparticles do not easily aggregate owing to the partition by the surrounding carbon as it would sufficiently expose the active Ni sites to the electrolytes, ensuring fast charge transfer between the catalyst and electrolytes by accelerating the electrochemical kinetics. In the anodic methanol oxidation, the products were detected as carbon dioxide and formate with faradaic efficiencies of 36.2% and 62.5%, respectively, at an applied potential of 1.55 V. Meanwhile, the Ni@C microrod catalyst demonstrated high activity and durability (2.7% current decay after 12 h of continuous operation) toward methanol oxidation, which demonstrates that methanol oxidation precedes oxidation under voltage forces. Notably, the bifunctional catalyst not only exhibits excellent performance toward methanol oxidation but also yields a low overpotential of 155 mV to drive 10 mA∙cm−2 toward hydrogen evolution in 1.0 mol∙L−1 KOH aqueous solution with 0.5 mol∙L−1 methanol at room temperature, which guarantees the hydrogen production efficiency. More importantly, the constructed two-electrode electrolyzer produced a current density of 10 mA∙cm−2 at a low cell voltage of 1.6 V, which decreased by 240 mV after replacing the oxygen evolution reaction with methanol oxidation. 相似文献
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不同种类羧酸钠对草酸钙结晶过程中晶相的影响 总被引:2,自引:0,他引:2
采用X射线衍射法研究了水溶液中不同种类羧酸钠对尿结石主要成份草酸钙结晶的影响,这些羧酸钠分别为含有一、二、三和四个羧基的羟基乙酸钠(NaGly)、酒石酸钠(Na2Tart)、柠檬酸钠(Na3Cit)和EDTA二钠盐(Na2EDTA).结果表明,随着羧酸钠浓度的增加,草酸钙的晶相均发生规律性的变化:从最稳定的一水草酸钙(COM),到不稳定的二水草酸钙(COD),最后转化为次稳定的三水草酸钙(COT).不同结构羧酸钠抑制COM生长、促进COD生成的顺序为:Na3Cit >Na2Tart >Na2EDTA >NaGly.该结果将为临床上选择防结石药物提供新的思路. 相似文献
45.
Effects of temperature and sodium carboxylate additives on mineralization of calcium oxalate in silica gel systems 总被引:5,自引:0,他引:5
Bernd Tieke 《中国科学B辑(英文版)》2004,47(4):311-319
Urolithiasis remains a major medical problem in China, especially in Guangdong Province in the southest of China[1]. A survey in Shenzhen city, the most southern city in China, showed the incidence of renal calculus was 4.87%, being 6.12% in the males and 4.07% in the females[2]. The prevalence of renal calculus has been more as the age advances and in the male population and so was in the less-educated population. The recurrence rate is more than 80%, with a moderate improvement by conventi… 相似文献
46.
Yizhao Ouyang Miao Zhan Jing Zhou Jiao Jiao Hao Hu Yoichi M. A. Yamada Pengfei Li 《中国化学》2019,37(8):807-810
A rigid C2‐symmetric chiral bipyridine ligand Z‐bpy with a triptycene‐like backbone was designed and synthesized from simple chemicals in a scalable route. Using this new ligand, copper(I) catalyzed cyclopropanation of styrenes with commercial ethyl diazoacetate produced various corresponding cyclopropanes in high yields, diastereoselectivity and enantioselectivity up to 97% ee. 相似文献
47.
Shangqing Li Jinglong Ma Xiaojun Wu Baolong Zhang Chen Ouyang Tianze Wang Dan Wang Xuan Wang Yutong Li 《中国光学快报(英文版)》2021,(5):60-64
We propose a spatial diffraction diagnostic method via inserting a millimeter-gap double slit into the collimated terahertz beam to monitor the minute variation of the terahertz beam in strong-field terahertz sources, which is difficult to be resolved in conventional terahertz imaging systems. To verify the method, we intentionally fabricate tiny variations of the terahertz beam through tuning the iris for the infrared pumping beam before the tilted-pulse-front pumping setups.The phenomena can be well explained by the theory based on the tilted-pulse-front technique and terahertz diffraction. 相似文献
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淡水瓣鳃类鳃的扫描电镜观察 总被引:7,自引:0,他引:7
运用扫描电镜观察了圆顶珠蚌,褶纹冠蚌,背角无齿蚌,卵形尖嵴蚌及河蚬的鳃表面纤毛的分布,排列方式及细微形态结构,结果表明:这5种蚌的鳃表面都有前纤毛,侧纤毛和前侧纤毛。此餐,仅在河蚬鳃表面前纤毛和前侧纤毛之间,观察到一种新的纤毛结构-前触毛。这一结构可能在河蚬取食时起作用。 相似文献
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