Antibody catalysis of the oxidation of water

Recently we reported that antibodies can generate hydrogen peroxide (H2O2) from singlet molecular oxygen (1O2*). We now show that this process is catalytic, and we identify the electron source for a quasi-unlimited generation of H2O2. Antibodies produce up to 500 mole equivalents of H2O2 from 1O2*, without a reduction in rate, and we have excluded metals or Cl- as the electron source. On the basis of isotope incorporation experiments and kinetic data, we propose that antibodies use H2O as an electron source, facilitating its addition to 1O2* to form H2O3 as the first intermediate in a reaction cascade that eventually leads to H2O2. X-ray crystallographic studies with xenon point to putative conserved oxygen binding sites within the antibody fold where this chemistry could be initiated. Our findings suggest a protective function of immunoglobulins against 1O2* and raise the question of whether the need to detoxify 1O2* has played a decisive role in the evolution of the immunoglobulin fold.     

The promotional effect of gold in catalysis by palladium-gold

Acetoxylation of ethylene to vinyl acetate (VA) was used to investigate the mechanism of the promotional effect of gold (Au) in a palladium (Pd)-Au alloy catalyst. The enhanced rates of VA formation for low Pd coverages relative to high Pd coverages on Au single-crystal surfaces demonstrate that the critical reaction site for VA synthesis consists of two noncontiguous, suitably spaced, Pd monomers. The role of Au is to isolate single Pd sites that facilitate the coupling of critical surface species to product, while inhibiting the formation of undesirable reaction by-products.     

光纤技术在盐穴储气库油水界面监测中的应用

盐穴储气库腔体形态控制是制约储气库库容和实现储气库稳定运行的重要因素,控制阻溶剂界面位置是控制腔体形态的关键。为了改进现有控制方法监控成本高、不能实时测量等缺点,提出光纤式界面监测方法:使用新型光纤界面测试仪进行测量,利用分布式光纤测试技术,通过光缆中的电缆加热,由于卤水和垫层介质(一般用柴油、氮气)的比热容不同,光缆与周围介质进行热交换发生温度变化,根据温差即可判断介质界面位置。基于光纤式界面监测方法,研制了新型的分布式光纤界面测试仪,其具有操作简单、探测范围广、监测成本低、实时测量井下介质界面的优点。利用该技术可实现盐穴储气库的大规模反循环造腔,加快造腔速度,保障腔体安全。(图5,表1,参24)     

氧化钛/活性炭纳米光催化剂氧化苯酚的研究

以活性炭(AC)为载体,利用溶胶-凝胶工艺制备氧化钛(TiO2)溶胶,通过浸渍法制备负载型 TiO2／AC纳米光催化剂以及掺杂Fe3+和Cu2+的M-TiO2／AC纳米复合光催化剂。以紫外灯做光源,用制得的 TiO2／AC纳米光催化剂对苯酚溶液进行光催化氧化降解试验,并研究了掺杂Fe3+和Cu2+的M-TiO2／AC纳米复合光催化剂对苯酚的催化活性。结果表明,在紫外光条件下,TiO2／AC纳米光催化剂对苯酚的降解率达99％,较日光条件下高;掺杂Fe3+能提高M-TiO2／AC纳米复合光催化剂对苯酚的催化活性。     

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%。     

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.     

超临界水氧化法去除偏二甲肼条件的研究

在压力24-30 MPa和温度400-500℃条件下,以Cu2为催化剂、H2O2为氧化剂、在连续流管式 反应器中进行了催化超临界水氧化偏二甲肼试验,研究温度、压力、停留时间和Cu2质量浓度对偏二甲肼氧化降解 的影响结。结果表明,在超临界水中偏二甲肼能被有效去除。偏二甲肼的去除率随反心温度和压力的升高、停留时间 的延长和Cu4质量浓度的增大而提高。当压力为30MPa、温度为450℃、停留时间为3．9 s、Cu-质量浓度为15 mg/L时,COD去除率可达97．8%。     

Identification of active gold nanoclusters on iron oxide supports for CO oxidation

Gold nanocrystals absorbed on metal oxides have exceptional properties in oxidation catalysis, including the oxidation of carbon monoxide at ambient temperatures, but the identification of the active catalytic gold species among the many present on real catalysts is challenging. We have used aberration-corrected scanning transmission electron microscopy to analyze several iron oxide-supported catalyst samples, ranging from those with little or no activity to others with high activities. High catalytic activity for carbon monoxide oxidation is correlated with the presence of bilayer clusters that are approximately 0.5 nanometer in diameter and contain only approximately 10 gold atoms. The activity of these bilayer clusters is consistent with that demonstrated previously with the use of model catalyst systems.     

Reactivity of organic compounds in hot water: geochemical and technological implications

Understanding of the reactivity of organic molecules in hot water is developing from studies aimed at explaining how organic matter (kerogen) forms in natural environments and then breaks down into energy source materials. In natural systems where kerogens are depolymerized, hot water is ubiquitous and usually contains salt and minerals. Reactions such as ionic condensation, cleavage, and hydrolysis are facilitated by changes in the chemical and physical properties of water as temperature increases. These changes make the solvent properties of water at high temperature similar to those of polar organic solvents at room temperature, thus facilitating reactions with organic compounds. An understanding of aqueous organic chemistry may lead to potential applications in areas as diverse as the recycling of plastics, the synthesis of chemicals, and coal liquefaction.     

Green, catalytic oxidation of alcohols in water

Alcohol oxidations are typically performed with stoichiometric reagents that generate heavy-metal waste and are usually run in chlorinated solvents. A water-soluble palladium(II) bathophenanthroline complex is a stable recyclable catalyst for the selective aerobic oxidation of a wide range of alcohols to aldehydes, ketones, and carboxylic acids in a biphasic water-alcohol system. The use of water as a solvent and air as the oxidant makes the reaction interesting from both an economic and environmental point of view.     

高级氧化法在水处理领域中的应用研究

阐述了Fenton法、O3氧化法、光化学氧化法、电化学氧化法、湿式氧化法、超临界水氧化法、超声波氧化法等不同高级氧化技术的反应原理及在水处理领域中的研究现状,并探讨了不同高级氧化技术在应用过程中存在的问题及今后的研究方向.     

4种饵料对选育中间养成阶段的凡纳滨对虾投喂效果分析

为了解凡纳滨对虾（Litopenaeus vannamei）在选育保种中间养成阶段（约10 ~40g/尾）的营养需求,以同一全同胞家系的凡纳滨对虾为对象,体质量为（10.30±1.61）g,选择配合饲料、软颗粒饲料、虎斑乌贼（Sepia pharaonis）和双齿围沙蚕（Perineresis aibuhitensis）这4种饵料进行60d的投喂试验,在对4种饵料进行营养评价的基础上,研究其对对虾生长、成活,以及消化、生长相关基因表达的影响。结果显示：（1）4种饵料投喂下对虾的特定生长率和成活率从高到低依次为双齿围沙蚕、配合饲料、软颗粒饲料和虎斑乌贼;（2）人工饲料组对虾肝胰腺中消化相关的α-淀粉酶d4基因表达水平显著高于生物饵料组（P<0.05）,蛋白酶基因表达趋势同α-淀粉酶d4基因相似,双齿围沙蚕组和软颗粒饲料组的胰脂肪酶基因表达显著高于配合饲料组（P<0.05）。虎斑乌贼组小核核糖核蛋白多肽基因表达显著低于其他饵料组（P<0.05）,生物饵料组y+L氨基酸转运载体-2基因表达显著高于人工饲料组（P<0.05）;（3）虎斑乌贼和双齿围沙蚕的氨基酸营养评价相对较高,而配合饲料和双齿围沙蚕的脂肪组成和含量相对更优。研究发现：双齿围沙蚕的营养价值最高,软颗粒饲料最低;4种试验饵料的投喂效果依次为双齿围沙蚕、配合饲料、软颗粒饲料和虎斑乌贼;除蛋白酶基因外,其他基因表达同试验饵料的营养组成和投喂效果一致。     

选择性氧化棉纤维的力学性能研究

采用高碘酸钠溶液对棉纤维进行选择性氧化处理,通过控制氧化反应条件,研究了高碘酸钠浓度、氧化反应时间、处理温度等因素对棉纤维力学性能的影响.结果表明,棉纤维经高碘酸钠氧化后产生重量损失,轻度氧化的棉纤维断裂强度基本不变,而深度氧化的棉纤维断裂强度下降,且这一趋势随着棉纤维氧化度的提高更加明显.     

中国民族特色药材艾纳香研究进展

\t\t\t\t\t目的\t\t\t\t\t了解特色药用植物艾纳香(Blumea balsamifera L. DC.)幼苗期在不同水分胁迫下不同取样时期的苗高、地径、生物量及叶结构变化,寻找最佳栽培条件。\t\t\t\t\t\t\t\t\t\t\t\t\t\t\t\t\t\t方法\t\t\t\t\t2014年5—9月,以一年生艾纳香幼苗为试验材料,进行不同程度(土壤田间持水量：CK为80%,轻度胁迫LD为60%,中度胁迫MD为40%,重度胁迫SD为30%)的干旱胁迫盆栽试验,测定艾纳香生物量和显微镜下的叶结构指标,分析不同程度干旱对艾纳香生物量和叶片结构的影响。\t\t\t\t\t\t\t\t\t\t\t\t\t结果\t\t\t\t\t不同干旱程度下,艾纳香的生物量、叶片厚度、栅栏组织与细胞结构紧密度(CTR)均随土壤水分的减少而减少,而根冠比、细胞结构疏松度(SR)与海绵组织随水分的减少而增大。\t\t\t\t\t\t\t\t\t\t\t\t\t结论\t\t\t\t\t中度胁迫是艾纳香生长可承受的最大范围,人工种植在土壤含水量40%下能维持叶片与地径的生长,从而获得药用材料。\t\t\t\t     

风鹅加工过程中脂肪氧化作用的研究

通过硫代巴比妥酸值（TBARS）、羰基值和双烯值、过氧化值等氧化指标的测定,研究了风鹅生产过程中各工艺点样品的肌间脂肪和皮下脂肪氧化状况。结果显示,肌间脂肪TBARS峰值出现较早,但风干后期的上升变化远落后于皮下脂肪;肌间脂肪过氧化值检出也早于皮下脂肪且变化较强;肌间脂肪羰基值和双烯值的总体趋势不断升高;风干3d时,风鹅的腊香味已经相当强烈。     

Scanning tunneling microscopy of galena (100) surface oxidation and sorption of aqueous gold

Scanning tunneling microscopy was used to characterize the growth of oxidized areas on galena (100) surfaces and the formation of gold islands by the reductive adsorption of AuCl(4)(-) from aqueous solution. The gold islands and galena substrate were distinguished by atomic resolution imaging and tunneling spectroscopy. Oxidized areas on galena have [110]-trending boundaries; gold islands elongate along [110] directions. However, there are no obvious structural registry considerations that would lead to elongation of gold islands in a [110] direction. Instead, it is probable that a direct coupling of gold reduction and sulfide surface oxidation controls the initial formation of gold islands. Gold islands grow less quickly on preoxidized galena surfaces and show no preferred direction of growth.     

水分胁迫对山黧豆萌发中蛋白质和游离氨基酸的影响

对山黧豆 (L athyrus sativus)进行不同浓度 PEG胁迫处理 ,研究水分胁迫对山黧豆种子萌发过程中蛋白质和游离氨基酸的影响。结果表明 ,水分胁迫能导致山黧豆根芽和子叶可溶性蛋白质含量增加 ,非可溶性蛋白质分解受到抑制 ;子叶游离氨基酸含量降低 ,而根芽游离氨基酸含量增高 ,尤其是丙氨酸、异亮氨酸、脯氨酸和精氨酸。随着种子萌发时间的延长 ,根芽 β- ODAP含量逐渐增加 ,而子叶 β- ODAP却降低 ;在水分胁迫下子叶和根芽 β-ODAP含量均增加     

Asymmetric catalysis of the transannular Diels-Alder reaction

Transannular chemical reactions are unparalleled in their ability to generate high degrees of stereochemical and architectural complexity in a single transformation. However, the successful application of this approach in synthesis depends on the ability to predict and control the outcome of the transannular reaction. Use of a chiral catalyst in this context represents an attractive, yet unused, strategy. This report describes a catalytic, asymmetric transannnular Diels-Alder (TADA) reaction that affords polycyclic products in high enantiomeric excess. This catalyst system can also alter the inherent diastereoselectivity of cyclizations with substrates containing chiral centers. Additionally, the catalytic enantioselective TADA has been used as the key step in a total synthesis of the sesquiterpene 11,12-diacetoxydrimane; this route may provide a general approach to the polycyclic carbon framework shared by many terpene natural products.