A simple, multidimensional approach to high-throughput discovery of catalytic reactions

Transition metal complexes catalyze many important reactions that are employed in medicine, materials science, and energy production. Although high-throughput methods for the discovery of catalysts that would mirror related approaches for the discovery of medicinally active compounds have been the focus of much attention, these methods have not been sufficiently general or accessible to typical synthetic laboratories to be adopted widely. We report a method to evaluate a broad range of catalysts for potential coupling reactions with the use of simple laboratory equipment. Specifically, we screen an array of catalysts and ligands with a diverse mixture of substrates and then use mass spectrometry to identify reaction products that, by design, exceed the mass of any single substrate. With this method, we discovered a copper-catalyzed alkyne hydroamination and two nickel-catalyzed hydroarylation reactions, each of which displays excellent functional-group tolerance.     

Analysis of phenotype array data from Biolog MicroPlatesTM

Biolog MicroPlates TM. are employed to characterize Trichoderma isolates based on differential assimilation of test substrates and redox reactions in a 96-well test plate. The Biolog method is potentially advantageous in being relatively simple, fast and economical, and data acquisition can be automated using a microplate reader and applicable software. Several research applications of the Biolog system are presented: i) “monophenetic groups” from cluster analyses of phenotype array da…     

西安城市整体水环境的构建研究(英文)

[目的]对西安城市整体水环境的构建进行研究。[方法]从城市规划层面对"长安八水"整体恢复和构建的必要性及其基本原则进行讨论,并对从长期规划策略和逐步建设实施 2 个层面来实现目标的方法和途径进行探讨。[结果]提出在恢复"长安八水"城市景观基底时,必须从构筑城市整体水环境角度进行统筹规划,改变线性代谢模式,建设城市水系循环网络;结合现有城市水环境的状况,尝试就地解决城市雨、污水的自循环净化;整体考虑城市集水、存水、引水等工程的联系和贯通,由点及面逐步恢复城市作为生态节点的基本"新陈代谢功能",改善城市人居环境。[结论]主动把握古城西安创建国际化大都市的独特机会,统筹规划设计、实施和保护城市水环境系统,将有助于重塑古城水系,重建宜居城市环境;更有助于彰显"长安八水"的城市生态和文脉特征,为城市的未来发展带来无限机遇和可能。     

西安城市整体水环境的构建研究

[目的]对西安城市整体水环境的构建进行研究。[方法]从城市规划层面对"长安八水"整体恢复和构建的必要性及其基本原则进行讨论,并对从长期规划策略和逐步建设实施2个层面来实现目标的方法和途径进行探讨。[结果]提出在恢复"长安八水"城市景观基底时,必须从构筑城市整体水环境角度进行统筹规划,改变线性代谢模式,建设城市水系循环网络;结合现有城市水环境的状况,尝试就地解决城市雨、污水的自循环净化;整体考虑城市集水、存水、引水等工程的联系和贯通,由点及面逐步恢复城市作为生态节点的基本"新陈代谢功能",改善城市人居环境。[结论]主动把握古城西安创建国际化大都市的独特机会,统筹规划设计、实施和保护城市水环境系统,将有助于重塑古城水系,重建宜居城市环境;更有助于彰显"长安八水"的城市生态和文脉特征,为城市的未来发展带来无限机遇和可能。     

Diels-alder in aqueous molecular hosts: unusual regioselectivity and efficient catalysis

Self-assembled, hollow molecular structures are appealing as synthetic hosts for mediating chemical reactions. However, product binding has inhibited catalytic turnover in such systems, and selectivity has rarely approached the levels observed in more structurally elaborate natural enzymes. We found that an aqueous organopalladium cage induces highly unusual regioselectivity in the Diels-Alder coupling of anthracene and phthalimide guests, promoting reaction at a terminal rather than central anthracene ring. Moreover, a similar bowl-shaped host attains efficient catalytic turnover in coupling the same substrates (although with the conventional regiochemistry), most likely because the product geometry inhibits the aromatic stacking interactions that attract the planar reagents to the host.     

Shape changes of supported Rh nanoparticles during oxidation and reduction cycles

The microscopic insight into how and why catalytically active nanoparticles change their shape during oxidation and reduction reactions is a pivotal challenge in the fundamental understanding of heterogeneous catalysis. We report an oxygen-induced shape transformation of rhodium nanoparticles on magnesium oxide (001) substrates that is lifted upon carbon monoxide exposure at 600 kelvin. A Wulff analysis of high-resolution in situ x-ray diffraction, combined with transmission electron microscopy, shows that this phenomenon is driven by the formation of a oxygen-rhodium-oxygen surface oxide at the rhodium nanofacets. This experimental access into the behavior of such nanoparticles during a catalytic cycle is useful for the development of improved heterogeneous catalysts.     

Capture of a single molecule in a nanocavity

We describe a heptameric protein pore that has been engineered to accommodate two different cyclodextrin adapters simultaneously within the lumen of a transmembrane beta barrel. The volume between the adapters is a cavity of approximately 4400 cubic angstroms. Analysis of single-channel recordings reveals that individual charged organic molecules can be pulled into the cavity by an electrical potential. Once trapped, an organic molecule shuttles back and forth between the adapters for hundreds of milliseconds. Such self-assembling nanostructures are of interest for the fabrication of multianalyte sensors and could provide a means to control chemical reactions.     

Female access to fertile land and other inputs in Zambia: why women get lower yields

Throughout the developing world, it is a well-documented fact that women farmers tend to get lower yields than their male counterparts. Typically this is attributed to disproportionate access to high-quality inputs and labor, with some even arguing there could be a skills-gap stemming from unbalanced access to training and education. This article examines the gender-based yield gap in the context of Zambian maize producers. In addition to the usual drivers, we argue that Zambia’s patriarchal and multi-tiered land distribution system could disfavor women with respect to accessing quality soils. We are uniquely able to control for soil characteristics using farm data from a sample of 1573 fields with accompanying soil analysis. We find an expected difference in yields, but no evidence of a gap in unobserved characteristics, like skill, after controlling for access to inputs, especially quality soil, suggesting women are indeed disproportionately disadvantaged. We discuss how our findings could be used to develop self-targeting policy interventions that could empower women and would be consistent with the government’s stated equity goals.     

基质渗透系数分析及其应用研究

[目的]比较不同基质的渗透系数及其在人工湿地中的适用范围。[方法]采用达西定律分析不同基质的渗透系数,结合中试分析人工湿地的净化能力。[结果]不同基质的渗透系数存在比较大的差异,砂子和炉渣的渗透系数比较高,且与其大颗粒粒径(>0.5 mm)呈显著正相关(P<0.05);而黄筋泥的渗透系数比较抵,不同比例的砂子和黄筋泥混合可以提高黄筋泥的渗透系数。以炉渣和砂子作为基质建立人工湿地工程时,人工湿地运行稳定,在水力负荷0.13 m/d的条件下,总氮、总磷、BOD5和高锰酸钾指数的去除率分别为43.52%3、0.26%、79.33%和63.96%。[结论]室内-中试试验结果说明达西定律可以作为一种简便的筛选人工湿地基质的方法。     

西伯利亚百合的鳞片扦插繁殖试验

[目的]对西伯利亚百合的鳞片扦插繁殖体系进行研究.[方法]以西伯利亚百合的鳞片为材料,研究不同基质、不同酚类物质和植物激素对百合鳞片扦插再生小鳞茎的影响.[结果]用细沙为基质有利于百合鳞片生根及小鳞茎的膨大;酚类物质水杨酸(SA)能促进母鳞片产生小鳞茎,并增加繁殖系数和小鳞茎的直径,同时还可提高母鳞片内可溶性糖和可溶性蛋白质的含量,为小鳞茎的形成及膨大提供营养物质和能量;植物激素中NAA能促进百合鳞片根的形成,但对小鳞茎的形成无明显促进作用.[结论]该研究为百合鳞片的快速繁育提供了参考.     

大豆SSR-PCR反应体系优化

应用单因素试验和L16(45)正交设计对影响大豆SSR-PCR的主要参数进行优化,建立适合大豆SSR-PCR反应的最佳体系。各因素不同水平对PCR反应结果均有影响,优化后的大豆SSR反应体系为:2.0 mmol/L Mg2+、1.00μmol/L引物、0.150 mmol/L dNTP、0.5 UTaq酶、50ngDNA模板。运用优化后的反应体系对大豆进行多态性引物的筛选,从140对引物中筛选出扩增条带清晰、多态性丰富的SSR引物45对。     

不同基质黄瓜育苗试验研究

为了筛选出适宜黄瓜育苗的最佳基质类型,选择在宁夏应用范围较广的5种基质开展黄瓜育苗对比试验研究。结果表明,5种基质都够为黄瓜苗期的生长提供充足的营养,其中以中青瓜类专用型基质和嘉禾一型基质在黄瓜幼苗的株高、茎粗、主根长、壮苗指数等综合性状表现较好,适合在宁夏大面积推广应用。     

溶液中无机化学反应的平衡常数统一为一种类型

 根据广义氧化还原理论,溶液中所有的无机反应都是氧化还原反应,因此,这些反应的平衡都是氧化还原平衡。归根到底,溶液中的无机反应的平衡常数就是一种类型：广义氧化还原平衡常数,这样就可能使无机化学实现进一步的系统化。     

Hot hydrogen atoms: initiators of reactions of interest in interstellar chemistry and evolution

Photochemically generated hot hydrogen atoms initiate reactions with simple molecular substrates including methane to produce organic alcohols, amines, acids, amino acids, and other compounds. The typical quantum yields for the formation of amino acids are 2 x 10(-5) to 4 x 10(-5). Hot hydrogen atoms may be important initiators of reactions in interstellar space and in planetary atmospheres.     

Reactive and nonreactive scattering of H2 from a metal surface is electronically adiabatic

The Born-Oppenheimer approximation of uncoupled electronic and nuclear motion is a standard tool of the computational chemist. However, its validity for molecule-metal surface reactions, which are important to heterogeneous catalysis, has been questioned because of the possibility of electron-hole pair excitations. We have performed experiments and calculations on the scattering of molecular hydrogen from a catalytically relevant metal surface, obtaining absolute probabilities for changes in the molecule's velocity parallel to the representative Pt(111) surface. The comparison for in-plane and out-of-plane scattering and results for dissociative chemisorption in the same system show that for hydrogen-metal systems, reaction and diffractive scattering can be accurately described using the Born-Oppenheimer approximation.     

人工湿地的基质及其深度对生活污水中氮磷去除效果的影响

目前人工湿地常用的基质一般为土壤、河砂和砾石,这类基质净化效率低,容易吸附饱和,且除磷脱氮的能力不高,致使出水中氮、磷浓度较高.针对于此,本试验研究选择了沸石、草炭、蛭石、页岩、砂子5种基质,利用两组模拟土柱系统模拟人工湿地对生活污水的处理,主要研究基质种类及其深度对生活污水处理效果的影响,并根据各基质对生活污水中总氮(TN)、总磷(TP)的去除率进行方差分析及基质对污水处理能力的显著差异性分析.实验结果表明:(1)各基质去除TN的能力差别不明显,沸石、蛭石、页岩的处理效果稍好.对TP的去除能力依次为草炭>页岩>砂子>沸石>蛭石.(2)基质深度的增加对2个指标处理效果的影响不同.对TN来说,深度对各基质的处理效果无明显影响.对TP来说,当深度在100 cm以内时,5种基质对11P的去除率均随深度的增加而明显增大,当深度超过100 cm后.各基质的这种增大趋势都不太明显.因此,对这2个指标而言,基质的填充深度应为100 cm.     

Experimental and theoretical differential cross sections for a four-atom reaction: HD + OH → H₂O + D

Quantum dynamical theories have progressed to the stage in which state-to-state differential cross sections can now be routinely computed with high accuracy for three-atom systems since the first such calculation was carried out more than 30 years ago for the H + H(2) system. For reactions beyond three atoms, however, highly accurate quantum dynamical calculations of differential cross sections have not been feasible. We have recently developed a quantum wave packet method to compute full-dimensional differential cross sections for four-atom reactions. Here, we report benchmark calculations carried out for the prototypical HD + OH → H(2)O + D reaction on an accurate potential energy surface that yield differential cross sections in excellent agreement with those from a high-resolution, crossed-molecular beam experiment.     

Enantioselective organocatalysis using SOMO activation

The asymmetric alpha-addition of relatively nonpolar hydrocarbon substrates, such as allyl and aryl groups, to aldehydes and ketones remains a largely unsolved problem in organic synthesis, despite the wide potential utility of direct routes to such products. We reasoned that well-established chiral amine catalysis, which activates aldehydes toward electrophile addition by enamine formation, could be expanded to this important reaction class by applying a single-electron oxidant to create a transient radical species from the enamine. We demonstrated the concept of singly occupied molecular orbital (SOMO) activation with a highly selective alpha-allylation of aldehydes, and we here present preliminary results for enantioselective heteroarylations and cyclization/halogenation cascades.     

Hydrocarbons in hydrothermal vent fluids: the role of chromium-bearing catalysts

Fischer-Tropsch type (FTT) synthesis has long been proposed to account for the existence of hydrocarbons in hydrothermal fluids. We show that iron- and chromium-bearing minerals catalyze the abiotic formation of hydrocarbons. In addition to production of methane (CH4aq), we report abiotic generation of ethane (C2H6aq) and propane (C3H8aq) by mineral-catalyzed hydrothermal reactions at 390 degrees C and 400 bars. Results suggest that the chromium component in ultramafic rocks could be an important factor for FTT synthesis during water-rock interaction in mid-ocean ridge hydrothermal systems. This in turn could help to support microbial communities now recognized in the subsurface at deep-sea vents.     

Supramolecular chemistry: receptors, catalysts, and carriers

Supramolecular chemistry is the study of the structures and functions of the supermolecules that result from binding substrates to molecular receptors. Macropolycyclic receptors and coreceptors have been designed that form cryptate inclusion complexes and display molecular recognition towards spherical, tetrahedral, and linear substrates of various kinds (metal cations, inorganic anions, and organic or biological cations or anions). Anion binding has led to the development of anion coordination chemistry. Metalloreceptors simultaneously bind organic molecules and metal ions; speleands combine polar and nonpolar binding subunits. Receptors bearing reactive functional groups may act as molecular reagents or catalysts, performing a chemical transformation on the bound substrates (by such reactions as hydrogen transfer, ester cleavage, and protoadenosinetriphosphatase and protokinase activities). Receptors fitted with lipophilic groups can operate as molecular carriers, translocating bound species through a membrane; this transport can be coupled to chemical potentials (proton and redox gradients).