A perovskite oxide optimized for oxygen evolution catalysis from molecular orbital principles

The efficiency of many energy storage technologies, such as rechargeable metal-air batteries and hydrogen production from water splitting, is limited by the slow kinetics of the oxygen evolution reaction (OER). We found that Ba(0.5)Sr(0.5)Co(0.8)Fe(0.2)O(3-δ) (BSCF) catalyzes the OER with intrinsic activity that is at least an order of magnitude higher than that of the state-of-the-art iridium oxide catalyst in alkaline media. The high activity of BSCF was predicted from a design principle established by systematic examination of more than 10 transition metal oxides, which showed that the intrinsic OER activity exhibits a volcano-shaped dependence on the occupancy of the 3d electron with an e(g) symmetry of surface transition metal cations in an oxide. The peak OER activity was predicted to be at an e(g) occupancy close to unity, with high covalency of transition metal-oxygen bonds.     

Visualization of dioxygen bound to copper during enzyme catalysis

X-ray crystal structures of three species related to the oxidative half of the reaction of the copper-containing quinoprotein amine oxidase from Escherichia coli have been determined. Crystals were freeze-trapped either anaerobically or aerobically after exposure to substrate, and structures were determined to resolutions between 2.1 and 2.4 angstroms. The oxidation state of the quinone cofactor was investigated by single-crystal spectrophotometry. The structures reveal the site of bound dioxygen and the proton transfer pathways involved in oxygen reduction. The quinone cofactor is regenerated from the iminoquinone intermediate by hydrolysis involving Asp383, the catalytic base in the reductive half-reaction. Product aldehyde inhibits the hydrolysis, making release of product the rate-determining step of the reaction in the crystal.     

A powerful chiral counterion strategy for asymmetric transition metal catalysis

Traditionally, transition metal-catalyzed enantioselective transformations rely on chiral ligands tightly bound to the metal to induce asymmetric product distributions. Here we report high enantioselectivities conferred by a chiral counterion in a metal-catalyzed reaction. Two different transformations catalyzed by cationic gold(I) complexes generated products in 90 to 99% enantiomeric excess with the use of chiral binaphthol-derived phosphate anions. Furthermore, we show that the chiral counterion can be combined additively with chiral ligands to enable an asymmetric transformation that cannot be achieved by either method alone. This concept of relaying chiral information via an ion pair should be applicable to a vast number of metal-mediated processes.     

The proteasome of Mycobacterium tuberculosis is required for resistance to nitric oxide

The production of nitric oxide and other reactive nitrogen intermediates (RNI) by macrophages helps to control infection by Mycobacterium tuberculosis (Mtb). However, the protection is imperfect and infection persists. To identify genes that Mtb requires to resist RNI, we screened 10,100 Mtb transposon mutants for hypersusceptibility to acidified nitrite. We found 12 mutants with insertions in seven genes representing six pathways, including the repair of DNA (uvrB) and the synthesis of a flavin cofactor (fbiC). Five mutants had insertions in proteasome-associated genes. An Mtb mutant deficient in a presumptive proteasomal adenosine triphosphatase was attenuated in mice, and exposure to proteasomal protease inhibitors markedly sensitized wild-type Mtb to RNI. Thus, the mycobacterial proteasome serves as a defense against oxidative or nitrosative stress.     

Carbon compounds in interplanetary dust: evidence for formation by heterogeneous catalysis

Associations of carbonaceous material with iron-nickel alloy, carbides, and oxides were identified by analytical electron microscopy in ten unmelted chondritic porous micrometeorites from the earth's stratosphere. These associations, which may be interpreted in terms of reactions between a carbon-containing gas and catalytically active dust grains, suggest that some of the carbon in the chondritic porous subset of interplanetary dust was emplaced through heterogeneous catalysis.     

一种具有对映选择性催化萘普生乙酯水解的多克隆抗体

研究了一种具有对映选择性催化萘普生乙酯水解的多克隆抗体。先设计并合成消旋膦酸酯Ｐ１，与载体蛋白偶联得到适于动物免疫的抗原体系Ｐ２和Ｐ３，通过适当的分离和离子交换色谱处理，得到一种新的免疫球蛋白（ＩｇＧ）－多克隆抗体。它能加速Ｒ－构型萘普生乙酯水解成为Ｓ－构型，且具有高度专一性，此多克隆抗体为超分子识别。     

Carbon dioxide exchange between air and seawater: no evidence for rate catalysis

It has been suggested that enzymatic catalysis plays a major role in regulating the mass transport of carbon dioxide from the atmosphere into the oceans. Evidence for this mechanism was not found in a series of gas exchange experiments in which the gas transfer rate coefficients for samples obtained from various natural seawaters, with and without the addition of carbonic anhydrase, were compared with those from artificial seawater. Wind-induced turbulence appears to be the major factor controlling the ocean's response to anthropogenic increases in atmospheric carbon dioxide.     

植物体内一氧化氮的合成及其对非生物胁迫响应的研究进展

一氧化氮在植物的生长发育和对胁迫的反应过程中参与了多种生理活动。植物通过NO合成酶、硝酸还原酶、非酶促途径3种途径合成NO;大多数非生物胁迫都能诱导NO的产生。植物细胞中的NO具有双重作用:低浓度的NO能够促进植物的生长与发育,提高植物的抗逆性;而高浓度的NO则对植物细胞有毒害作用。在对非生物胁迫的反应中,NO能够减轻活性氧对植物细胞的伤害,并和其他的信号分子结合,共同调节胁迫响应基因的表达。     

氧化亚氮超浅麻醉在人工流产术中的应用与护理

人工流产作为避孕失败后常用的补救措施之一,无痛性操作越来越多地成为人们的要求.我院自2003年12月起将氧化亚氮超浅吸入麻醉应用于人工流产术,取得了较好的疗效,现将观察和护理结果报道如下.     

水温骤降后凡纳滨对虾血清中NO、NOS水平及对副溶血弧菌的敏感性

测定了水温骤降后(A组(25→22℃)、B组(25→19℃)、C组(25→16℃)、对照组(25℃))6、24 h凡纳滨对虾Penaeus vannam ei血清中一氧化氮(NO)的浓度、一氧化氮合成酶(n i-tric oxide synthase,NOS)的活性以及溶菌酶活力的变化,并在水温变化后24 h用副溶血弧菌Vibrioparahaem olyticus对对虾进行人工感染,以评价凡纳滨对虾对副溶血弧菌的敏感性。结果表明,水温骤降后6 h,各试验组对虾血清中NO浓度、NOS活性、溶菌酶活力均与对照组差异不显著(P>0.05)。水温骤降后24 h,B组对虾血清中NO浓度显著高于对照组(P<0.05),A、C两组与对照组差异不显著(P>0.05);B组对虾血清中NOS的活性显著高于对照组(P<0.05),C组显著低于对照组(P<0.05),A组与对照组差异不显著(P>0.05);各试验组对虾血清中的溶菌酶活力与对照组差异不显著(P>0.05);用副溶血弧菌人工感染对虾的死亡率C组为58.3%,与对照组(33.3%)存在显著差异(P<0.05)。这说明水温大幅度急剧下降后,凡纳滨对虾血清中的NOS活性、溶菌酶活力下降,因而导致凡纳滨对虾对副溶血弧菌的敏感性升高。     

农田氧化亚氮减排的关键是合理施氮

农业源氧化亚氮(N2O)排放量占全球人为源总排放量的2/3,是最大的人为排放源,氮肥和有机肥的施用是其主要贡献者。合理施氮是获得较高目标产量、维持土壤氮肥力和降低因施氮引起环境污染风险的关键,在减少农田土壤N2O排放、缓解温室效应中起重要作用。本文基于合理施肥的“4R”(Right amount,Right type,Right time,Right place)理念和技术,论述了施氮量与N2O排放量之间的数量关系,肥料品种、施肥时期和方法对N2O减排的影响。强调了氮素投入超过作物需氮量后,N2O排放量会呈现指数型增长;将施氮量控制在合理范围对N2O减排的重要性。建议在不同土壤-气候-作物体系下,同时开展产量、品质,氨挥发、硝酸盐淋洗、N2O排放和土壤肥力的长期系统研究,不能顾此失彼;形成同类地区能够机械操作的规范化种植模式与合理施肥措施,包括与其他农艺措施的配合,如轮作与耕作、灌溉、有机肥和秸秆还田、磷钾肥和中微量元素管理等,以实现产量、品质、效益与环境效应相协调的可持续集约化作物生产目标。     

一氧化氮合成酶(NOS)研究方法及其在植物中的应用

一氧化氮(NO)在动植物生命活动中具有重要作用。近年来,其合成途径已成为研究焦点。文章综述了近10年来一氧化氮合成酶(NOS)研究方法及其在植物中的应用,包括生物化学方法、免疫学方法和分子生物学方法,并对其研究前景进行展望。     

Epitaxial cubic gadolinium oxide as a dielectric for gallium arsenide passivation

Epitaxial growth of single-crystal gadolinium oxide dielectric thin films on gallium arsenide is reported. The gadolinium oxide film has a cubic structure isomorphic to manganese oxide and is (110)-oriented in single domain on the (100) gallium arsenide surface. The gadolinium oxide film has a dielectric constant of approximately 10, with low leakage current densities of about 10(-9) to 10(-10) amperes per square centimeter at zero bias. Typical breakdown field is 4 megavolts per centimeter for an oxide film 185 angstroms thick and 10 megavolts per centimeter for an oxide 45 angstroms thick. Both accumulation and inversion layers were observed in the gadolinium oxide-gallium arsenide metal oxide semiconductor diodes, using capacitance-voltage measurements. The ability to grow thin single-crystal oxide films on gallium arsenide with a low interfacial density of states has great potential impact on the electronic industry of compound semiconductors.     

一氧化氮参与疣粒野生稻对水稻白叶枯病的抗性

疣粒野生稻高抗水稻白叶枯病,但是其具体的抗性机制目前仍不清楚。一氧化氮（nitric oxide,NO）是一种重要的信号分子,在植物的抗病反应中起到了重要的作用,然而对于NO是否参与疣粒野生稻对水稻白叶枯病的抗性目前仍缺乏研究。以抗病的疣粒野生稻和感病的水稻品种日本晴为材料,研究了接种白叶枯病菌对叶片病斑、NO含量、NO亚细胞定位和木质部超微结构的影响。结果表明,病菌侵染导致了日本晴叶片呈现枯黄色的干枯斑,疣粒野生稻叶片呈现褐色的凋亡斑,而且野生稻的病斑长度要明显短于日本晴的病斑长度。接种白叶枯病菌后日本晴叶片内NO含量未见明显的变化,而野生稻叶片内NO含量则显著升高,并且大部分的NO定位于导管细胞壁内。进一步通过电镜观察,发现病菌侵染诱导了野生稻叶片导管细胞壁厚度的明显增加。基于这些结果,推测NO参与了疣粒野生稻对白叶枯病的抗性,其功能可能包括诱导导管细胞壁增厚,从而抑制病菌的进一步侵染。     

氧化铁/水界面Cd吸附研究:CD-MUSIC模型模拟

以针铁矿和赤铁矿为研究对象,研究p H、Cd浓度等对不同类型氧化铁Cd吸附行为的影响,构建氧化铁Cd吸附的CD-MUSIC模型,并分析氧化铁表面Cd的形态分布特征。结果表明:氧化铁表面Cd吸附量和吸附密度均随p H升高、Cd浓度增大而增大。针铁矿对Cd的吸附量和吸附密度显著高于赤铁矿。CD-MUSIC模型能准确模拟Cd在氧化铁/水界面的吸附特征,拟合结果表明Cd主要以(Fe OH)2Cd+1、(Fe OH)2Cd OH0两种形态吸附在氧化铁表面,其在针铁矿和赤铁矿表面亲和常数(lg KCd)分别是7.3、12.8和6.1、11.0。Cd的形态分布受p H的影响显著,但几乎不受Cd浓度的影响。p H 5.0和7.0时,针铁矿的Cd形态分布与赤铁矿相似,(Fe OH)2Cd+1是主要吸附形态。p H 9.0时,针铁矿上超过80%的Cd以(Fe OH)2Cd OH0形态存在。赤铁矿上,Cd浓度较低时,(Fe OH)2Cd+1是主要吸附形态;随Cd浓度增大,(Fe OH)2Cd+1和(Fe OH)2Cd OH0所占比例均逐渐接近50%。