2 + 2] photocycloadditions in the synthesis of chiral molecules

A strategy for the synthesis of chiral molecules that receives growing popularity among organic chemists employs the photochemically mediated [2 + 2] cycloaddition reaction. These reactions can be performed on a multigram scale and often proceed with high yield and with stereocontrol. These features, in combination with the useful properties of the four-membered ring photoproducts in subsequent chemical transformations, make them attractive options in the early stage of a synthesis design. Various combinations of unsaturated functional groups can participate in this reaction process. Accordingly, these chemical reactions can be economical solutions to problems relating to the synthesis of a variety of target molecules.     

核-壳介孔SiO2的合成

利用不同的三烷氧基硅在胶体介孔SiO2（CMS）的内部和外部表面烷选择性地修饰不同的官能团,这是利用了延迟共沉淀得到双功能化CMS的新方法。此种方法制得的CMS纳米粒子修饰有两种不同的官能团,它们分别位于核和壳上或同时位于核上。我们的合成方法提供了一种新颖的多步共沉淀策略,可将不同的官能团定位修饰在介孔纳米粒子的核或壳上。     

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).     

薄荷蔗糖酶的化学修饰

采用NBS、PMSF、IAc、BrAc、SUAN、TNBS、PCMB、DTT以及金属离子和相关试剂在一定条件下选择性修饰蔗糖酶．结果表明：0．5mmol／L的PMSF使酶活性丧失95％,10／μmol／L的NBS使酶活性丧失93％0．5mmol／LNPCMB使酶活性降至12％,酶修饰呈一级反应,推测Trp、Ser的残基可能是薄荷叶片蔗糖酶的活啦必需基团,而His、Lys的残基不在薄荷蔗糖酶的活性中心．     

Antibody active sites and immunoglobulin molecules

In order to obtain detailed information about the relationship between structure and function in antibody molecules, a method called affinity labeling has been devised to attach chemical labels specifically to amino acid residues in the active sites of antibody molecules. With antibodies to three different haptens, highly specific labeling of the active sites has been achieved. Tyrosine residues on both heavy and light polypeptide chains have been labeled in a molar ratio close to 2:1, and labels on the two chains are equally specific to the active sites. Peptide fragmentation studies of the labeled chains of one antibody system have shown that: (i) within 25 amino acid residues of the labeled tyrosine on either chain, substantial chemical heterogeneity exists among different antibody molecules of the same specificity; and (ii) the labeled peptide fragments from both chains are very similar in physicochemical characteristics, including average size, heterogeneity, and unusual hydrophobicity. These experimental results have led us to the view that a particular region of the heavy chain and a particular region of the light chain are utilized to construct the active sites of the three different antibodies, differences in specificity arising from chemical perturbations in these two regions. Correlated structural studies of affinity-labeled antibodies and of the homogeneous light chains (Bence Jones proteins) and heavy chains produced in multiple myeloma may permit the identification of these special active-site regions. The view that active sites of different specificity are chemical perturbations of a particular region of the antibody molecule has a possible close analogue in enzyme systems, particularly among the esterases. The marked chemical similarities we have observed between the active site regions of heavy and light chains indicate to us that chemical homologies, but not identities, exist between the chains. This is reinforced by recently obtained amino acid sequence data which reveal homologies between the two chains near their carboxyl-terminals. These results indicate that the structural genes which code for the synthesis of heavy and light chains are related, presumably having arisen from some common ancestral gene during evolution. This conclusion strongly suggests that both heavy and light chains determine antibody specificity, and has important implications for the still-unknow mechanisms of antibody biosynthesis.     

硬球链流体在硬球粒子表面的密度分布和剩余吸附研究

在密度泛函的理论(Density Functional Theory,DFT)框架下,应用Yu等改进的基本度量理论(Modified Fundamental Measure Theory,MFMT)和Wertheim等发展的微扰理论分别表达剩余自由能的硬球作用和链连接作用,对硬球链流体体系进行了研究,建立了适用于均匀和非均匀流体的状态方程和化学势,得到了硬球链流体在硬球粒子表面的密度分布表达式,计算了在硬球粒子表面的链节密度分布,并将理论计算数据与叶等进行的Monte Carlo计算机模拟所得数据进行比较,结果吻合较好。此外,还进一步探讨了硬球粒子尺度和硬球链链节数对体系剩余吸附的影响。     

HPLC study of the physicochemical characteristics of chitosan preparations during their manufacture and storage

A change in the physicochemical characteristics of chitosan preparations as a consequence of the occurrence of chemical reactions of carbonyl and hydroxyl groups of chitosan polymer molecules with amino groups of chitosan-chitin polymer molecules and chitosan-protein complex during long storage of chitosan preparations was established by high performance liquid chromatography.     

Reversing the inactivation of peroxiredoxins caused by cysteine sulfinic acid formation

The active-site cysteine of peroxiredoxins is selectively oxidized to cysteine sulfinic acid during catalysis, which leads to inactivation of peroxidase activity. This oxidation was thought to be irreversible. However, by metabolic labeling of mammalian cells with 35S, we show that the sulfinic form of peroxiredoxin I, produced during the exposure of cells to H2O2, is rapidly reduced to the catalytically active thiol form. The mammalian cells' ability to reduce protein sulfinic acid might serve as a mechanism to repair oxidatively damaged proteins or represent a new type of cyclic modification by which the function of various proteins is regulated.     

生物质炭可溶性有机物化学组成及生物活性意义

生物质热解炭化过程中,有机可挥发组分从固相逸出,冷凝后重新吸附于生物质炭,成为其中的可溶性有机物。生物质炭可溶性有机物化学组成复杂,主要含小分子有机物与芳香类化合物且含有丰富的官能团,具有较高的化学反应活性和生物活性,可显著地改变土壤中养分元素和污染物的形态与有效性,影响土壤微生物组成与丰度,调控作物的生长与健康。依生物质原料和热解条件的差异,生物质炭可溶性有机物的化学结构与生物活性功能也不尽相同。生物质炭可溶性有机物的生物活性意义主要表现为对生物的刺激作用,但部分生物质炭可溶性有机物可能具有一定的潜在毒性风险。通过提取生物质炭可溶性有机物可生产具有生物刺激作用的商品液体有机肥,从而实现生物质炭的分值利用。未来需要进一步加强生物质炭可溶性组分的生物活性或毒性物质的鉴定及其形成机制的研究,这对于生物质炭产品的优化是十分必要的,也是应用生物质炭尽量避免环境风险的要求。     

Surface trapping of atoms and molecules with dipole rings

The trapping of single molecules on surfaces without the formation of strong covalent bonds is a prerequisite for molecular recognition and the exploitation of molecular function. On nanopatterned surfaces, molecules may be selectively trapped and addressed. In a boron nitride nanomesh formed on Rh(111), the pattern consisted of holes 2 nanometers in diameter on a hexagonal superlattice, separated by about 3 nanometers. The trapping was further investigated with density functional theory and the photoemission of adsorbed xenon, where the holes were identified as regions of low work function. The analysis showed that the trapping potential was localized at the rims of the holes.     

A small gold-conjugated antibody label: improved resolution for electron microscopy

A general method has been developed to make the smallest gold-conjugated antibody label yet developed for electron microscopy. It should have wide application in domainal mapping of single molecules or in pinpointing specific molecules, sites, or sequences in supramolecular complexes. It permits electron microscopic visualization of single antigen-binding antibody fragments (Fab') by covalently linking an 11-atom gold cluster to a specific residue on each Fab' such that the antigenic specificity and capacity are preserved. The distance of the gold cluster from the antigen is a maximum of 5.0 nanometers when the undecagold-Fab' probe is used as an immunolabel.     

Antigen binding to cells: determination by enzymic fluorogenic group hydrolysis

A sensitive method for detecting cells containing antibody to beta-galactosidase has been devised. The enzyme attached to the cells containing antibody can hydrolyze a fluorogenic substrate and yield fluorescent products which are measured microphotofluorometrically. This method of detecting a few molecules of antibody is applicable to other enzyme antigen systems.     

The fluid mosaic model of the structure of cell membranes

A fluid mosaic model is presented for the gross organization and structure of the proteins and lipids of biological membranes. The model is consistent with the restrictions imposed by thermodynamics. In this model, the proteins that are integral to the membrane are a heterogeneous set of globular molecules, each arranged in an amphipathic structure, that is, with the ionic and highly polar groups protruding from the membrane into the aqueous phase, and the nonpolar groups largely buried in the hydrophobic interior of the membrane. These globular molecules are partially embedded in a matrix of phospholipid. The bulk of the phospholipid is organized as a discontinuous, fluid bilayer, although a small fraction of the lipid may interact specifically with the membrane proteins. The fluid mosaic structure is therefore formally analogous to a two-dimensional oriented solution of integral proteins (or lipoproteins) in the viscous phospholipid bilayer solvent. Recent experiments with a wide variety of techniqes and several different membrane systems are described, all of which abet consistent with, and add much detail to, the fluid mosaic model. It therefore seems appropriate to suggest possible mechanisms for various membrane functions and membrane-mediated phenomena in the light of the model. As examples, experimentally testable mechanisms are suggested for cell surface changes in malignant transformation, and for cooperative effects exhibited in the interactions of membranes with some specific ligands. Note added in proof: Since this article was written, we have obtained electron microscopic evidence (69) that the concanavalin A binding sites on the membranes of SV40 virus-transformed mouse fibroblasts (3T3 cells) are more clustered than the sites on the membranes of normal cells, as predicted by the hypothesis represented in Fig. 7B. T-here has also appeared a study by Taylor et al. (70) showing the remarkable effects produced on lymphocytes by the addition of antibodies directed to their surface immunoglobulin molecules. The antibodies induce a redistribution and pinocytosis of these surface immunoglobulins, so that within about 30 minutes at 37 degrees C the surface immunoglobulins are completely swept out of the membrane. These effects do not occur, however, if the bivalent antibodies are replaced by their univalent Fab fragments or if the antibody experiments are carried out at 0 degrees C instead of 37 degrees C. These and related results strongly indicate that the bivalent antibodies produce an aggregation of the surface immunoglobulin molecules in the plane of the membrane, which can occur only if the immunoglobulin molecules are free to diffuse in the membrane. This aggregation then appears to trigger off the pinocytosis of the membrane components by some unknown mechanism. Such membrane transformations may be of crucial importance in the induction of an antibody response to an antigen, as well as iv other processes of cell differentiation.     

Generation of a catalytic antibody by site-directed mutagenesis

A hybrid Fv fragment of the dinitrophenyl-binding immunoglobulin A (IgA), MPOC315, has been generated by reconstituting a recombinant variable light chain (VL) produced in Escherichia coli with a variable heavy chain (VH) derived from the antibody. The Tyr34 residue of VL was substituted by His in order to introduce a catalytic imidazole into the combining site for the ester hydrolysis. The His mutant Fv accelerated the hydrolysis of the 7-hydroxycoumarin ester of 5-(2,4-dinitrophenyl)-aminopentanoic acid 90,000-fold compared to the reaction with 4-methyl imidazole at pH 6.8 and had an initial rate that was 45 times as great as that for the wild-type Fv. The hydrolyses of aminopropanoic and aminohexanoic homologs were not significantly accelerated. Thus a single deliberate amino acid change can introduce significant catalytic activity into an antibody-combining site, and chemical modification data can be used to locate potential sites for the introduction of catalytic residues.     

甜玉米遗传距离与特殊配合力的关系

按照Griffing守全双列杂交遗传交配设计方法Ⅰ配制组合，对甜玉米产量性状的特殊配合力进行了测定并根据70个甜玉米自交系数量性状的表现计算了它们之间的遗传距离。回归分析结果表明：F1代产量的特殊配合力与双亲之间的遗传距离呈三次曲线关系，而F1代含糖量性状的特殊配合力与双亲之间的遗传距离无确定关系。同时，对遗传距离预测F1产量的特殊配合力的可能性进行了探讨。     

Antibody-based bio-nanotube membranes for enantiomeric drug separations

Synthetic bio-nanotube membranes were developed and used to separate two enantiomers of a chiral drug. These membranes are based on alumina films that have cylindrical pores with monodisperse nanoscopic diameters (for example, 20 nanometers). Silica nanotubes were chemically synthesized within the pores of these films, and an antibody that selectively binds one of the enantiomers of the drug was attached to the inner walls of the silica nanotubes. These membranes selectively transport the enantiomer that specifically binds to the antibody, relative to the enantiomer that has lower affinity for the antibody. The solvent dimethyl sulfoxide was used to tune the antibody binding affinity. The enantiomeric selectivity coefficient increases as the inside diameter of the silica nanotubes decreases.     

Antireceptor antiserum causes specific inhibition of reactivity to rat histocompatibility antigens

The antigen receptor of lymphocytes destined to form antibody appears to have the characteristics of the immunoglobulin produced. Antibody directed against the combining region of this immunoglobulin should interact with the combining region of the cell receptor for the antigen. Purified Lewis rat alloantibody prepared against Brown Norway (BN) rat histocompatibility antigens was used to immunize L x BN F(1) hybrids. The resultant antiserum has anti-receptor activity because (i) it yields precipitin lines in gel diffusion when reacted against the immunizing alloantibody; (ii) it inhibits the hemagglutinin antibody response of Lewis rats to BN histocompatibility antigens; and (iii) it inhibits the local graft-versus-host response of Lewis lymphoid cells against BN antigens. This suggests that antireceptor antibody may inhibit cell-mediated responses as well as antibody responses to histocompatibility antigens and may play a role in the regulation of immune responses to such antigens.     

Forces and bond dynamics in cell adhesion

Adhesion of a biological cell to another cell or the extracellular matrix involves complex couplings between cell biochemistry, structural mechanics, and surface bonding. The interactions are dynamic and act through association and dissociation of bonds between very large molecules at rates that change considerably under stress. Combining molecular cell biology with single-molecule force spectroscopy provides a powerful tool for exploring the complexity of cell adhesion, that is, how cell signaling processes strengthen adhesion bonds and how forces applied to cell-surface bonds act on intracellular sites to catalyze chemical processes or switch molecular interactions on and off. Probing adhesion receptors on strategically engineered cells with force during functional stimulation can reveal key nodes of communication between the mechanical and chemical circuitry of a cell.     

现代化鸡场的计算机网络管理

本文结合一个实际的鸡场计算机网络管理信息系统,就其实现过程中的设计问题,特别是系统的处理模型、工作流程、数据关系、功能设计等进行详细的论述,作为国内同类鸡场和类似企业进行开发的参考。     

Linear alkane polymerization on a gold surface

In contrast to the many methods of selectively coupling olefins, few protocols catenate saturated hydrocarbons in a predictable manner. We report here the highly selective carbon-hydrogen (C-H) activation and subsequent dehydrogenative C-C coupling reaction of long-chain (>C(20)) linear alkanes on an anisotropic gold(110) surface, which undergoes an appropriate reconstruction by adsorption of the molecules and subsequent mild annealing, resulting in nanometer-sized channels (1.22 nanometers in width). Owing to the orientational constraint of the reactant molecules in these one-dimensional channels, the reaction takes place exclusively at specific sites (terminal CH(3) or penultimate CH(2) groups) in the chains at intermediate temperatures (420 to 470 kelvin) and selects for aliphatic over aromatic C-H activation.