General acid-base catalysis in the mechanism of a hepatitis delta virus ribozyme

Many protein enzymes use general acid-base catalysis as a way to increase reaction rates. The amino acid histidine is optimized for this function because it has a pK(a) (where K(a) is the acid dissociation constant) near physiological pH. The RNA enzyme (ribozyme) from hepatitis delta virus catalyzes self-cleavage of a phosphodiester bond. Reactivity-pH profiles in monovalent or divalent cations, as well as distance to the leaving-group oxygen, implicate cytosine 75 (C75) of the ribozyme as the general acid and ribozyme-bound hydrated metal hydroxide as the general base in the self-cleavage reaction. Moreover, C75 has a pK(a) perturbed to neutrality, making it "histidine-like." Anticooperative interaction is observed between protonated C75 and a metal ion, which serves to modulate the pK(a) of C75. General acid-base catalysis expands the catalytic repertoire of RNA and may provide improved rate acceleration.     

酸碱对改性豆胶耐水胶合强度的影响

采用酸、碱和酸碱联合3种方式处理脱脂豆粉,制备改性豆胶,并用于压制三层胶合板,以Ⅱ类胶合板的标准检测其耐水胶合强度。结果表明,酸碱处理均能提高改性豆胶的耐水性能,当酸用量为11.9份时,改性豆胶压制的胶合板最高耐水胶合强度为0.48MPa;碱的用量为22.6份时,耐水胶合强度为0.43MPa;酸碱联合改性豆胶的效果优于单独用酸或碱改性,当酸、碱的用量分别为11.9和39.9份时,改性豆胶压制的胶合板最优耐水胶合强度为0.61MPa。红外光谱分析表明,酸碱联合改性豆胶能综合酸、碱单独使大豆蛋白变性的优点,更有利于提高改性豆胶的耐水性。     

Imaging nucleophilic substitution dynamics

Anion-molecule nucleophilic substitution (S(N)2) reactions are known for their rich reaction dynamics, caused by a complex potential energy surface with a submerged barrier and by weak coupling of the relevant rotational-vibrational quantum states. The dynamics of the S(N)2 reaction of Cl- + CH3I were uncovered in detail by using crossed molecular beam imaging. As a function of the collision energy, the transition from a complex-mediated reaction mechanism to direct backward scattering of the I- product was observed experimentally. Chemical dynamics calculations were performed that explain the observed energy transfer and reveal an indirect roundabout reaction mechanism involving CH3 rotation.     

Medium effects in antibody-catalyzed reactions

Catalytic antibody technology has been used to explore the contribution of medium effects to the overall rate of an enzyme-catalyzed reaction. An antibody generated against a derivative of 2-acetamido-1,5-napthalenedisulfonate efficiently catalyzes the decarboxylation of 5-nitro-3-carboxybenzisoxazole. This unimolecular reaction is not susceptible to general acid-base catalysis but is highly sensitive to microenvironment; thus, it provides a simple chemical model for biologically important decarboxylations. The 10(4)-fold rate acceleration observed for the antibody reflects the kinetic advantage of the low-dielectric environment of the binding pocket acting to destabilize the substrate by desolvation and to stabilize the charge-delocalized transition state through dispersion interactions. These results are pertinent to an understanding of solvent effects in enzymic reactions in general and suggest approaches for developing antibody catalysts for numerous other reactions that involve large changes in charge distribution as the reaction coordinate is traversed.     

土壤化学中的广义氧化还原反应

 土壤化学中的酸碱反应、沉淀溶解反应、配位反应和氧化还原反应都属于广义氧化还原反应。土壤化学反应中的某些性质可用广义氧化还原理论给出新的解释。     

Autoionization in liquid water

The dissociation of a water molecule in liquid water is the fundamental event in acid-base chemistry, determining the pH of water. Because of the short time scales and microscopic length scales involved, the dynamics of this autoionization have not been directly probed by experiment. Here, the autoionization mechanism is revealed by sampling and analyzing ab initio molecular dynamics trajectories. We identify the rare fluctuations in solvation energies that destabilize an oxygen-hydrogen bond. Through the transfer of protons along a hydrogen bond "wire," the nascent ions separate by three or more neighbors. If the hydrogen bond wire connecting the two ions is subsequently broken, a metastable charge-separated state is visited. The ions may then diffuse to large separations. If, however, the hydrogen bond wire remains unbroken, the ions recombine rapidly. Because of their concomitant large electric fields, the transient ionic species produced in this case may provide an experimentally detectable signal of the dynamics we report.     

褐飞虱治理计算机决策支持系统

本文描述了褐飞虱治理的决策过程、决策所需信息及计算机系统的结构和功能。该系统由数据库、模型库、决策分析和使用说明四部份组成。数据库可用于贮存和查询有关褐飞虱迁入量、气温、发生期和发生量、种群动态、临近地区历年发生情况、生态学特性及农药方面的资料。模型库包括可用于预测发生期、发生量、为害程度和种群动态的四个模型,决策分析学系统包括决策分析模型和专家系统。系统综合了数据库、模拟模型和专家系统的特点,为支持和改善褐飞虱治理的决策提供了一种实用工具。     

化学改性提高木质素水溶性及其对Zn2+的络合能力

以生物炼制并通过酸沉淀获得的玉米芯工业碱木质素(L)为原料,经过酚化(PL)及酚化+羟甲基化(HPL)两种前处理,增加反应活性位点,再分别对前处理产物PL和HPL进行羧甲基化改性得到CMPL和CMHPL。以期通过化学改性增强木质素水溶性和对Zn~(2+)的络合能力,从而使改性木质素具有作为水溶性螯合微肥施用的价值,进一步运用红外、热重、荧光显微镜、元素、电位滴定分析方法对木质素和改性木质素的结构及化学性质进行了探究,结果表明:通过酚化和羟甲基化两步前处理再经羧甲基化改性可以显著提高木质素的水溶性和对Zn~(2+)的络合能力。     

外源镁对强酸性紫色土壤阳离子交换效应的研究

[目的]为研究外源镁对强酸性紫色土壤阳离子交换效应。[方法]选择重庆地区强酸性紫色土壤为对象,采用1：5的土水比,用10emol（＋）／LMgSO4溶液对土壤进行多次交换处理。[结果]在实验条件下,外源镁能快速取代土壤胶体上吸附的各种盐基离子,但对致酸离子（H＋、A1＋）则难以达到快速、完全取代,经5次交换后,盐基饱和度由46．6％上升至72．4％,土壤pH仅上升0．7个单位;Mg2＋与Ca＋、Na＋的交换分别可以用指数方程Y=14．998e-1．4849x（R2=0．9938）、二次方程Y=0．011 1x2-0．1005x＋0．233（R‘=0．986）进行很好地拟合;Mg“与K’的交换后期明显表现出有部分土壤次生黏土矿物层间固定的K’会被交换出来,导致被交换出的K’总量增加。[结论]在无酸碱中和的条件下,外源钱可以改变土壤胶体盐基离子的构成,但对于改良强酸性土壤并无实际意义,反之,过量的外源镁还可能造成土壤其他盐基离子的损失。     

蓝莓的功能、用途及有机栽培研究进展

概述了对蓝莓食用和营养价值、保健和药用功能以及加工性能和开发方面的研究进展,重点评述了蓝莓的育种成就和有机栽培尤其是蓝莓对土壤酸碱反应的特殊需求,展望了蓝莓的发展前景.     

DNA conformation, dynamics, and interactions in solution

The conformation and dynamics of the d(CGCGAATTCGCG) duplex, its analogs containing mismatched base pairs and helix interruptions, and its complexes with actinomycin and Netropsin, bound separately and simultaneously, have been investigated by nuclear magnetic resonance spectroscopy in aqueous solution. Structural information has been deduced from chemical shift and nuclear Overhauser effect parameters, while the kinetics have been probed from line width and saturation recovery experiments on proton and phosphorus markers at the individual base pair level. These studies lead to an improved understanding of the role of nucleic acid sequence on the structure, flexibility, and conformational interconversions in the duplex state. The nuclear magnetic resonance measurements readily identify helix modification and antibiotic binding sites on the nucleic acid and estimate the extent to which the observed conformational and dynamic perturbations are transmitted to adjacent base pair regions.     

Pattern formation and shape changes in self-oscillating polymer gels

We developed an efficient model for responsive gels that captures large-scale, two-dimensional (2D) deformations and chemical reactions within a swollen polymer network. The 2D calculations allowed us to probe not only volume changes but also changes in sample shape. By focusing on gels undergoing the oscillatory Belousov-Zhabotinsky reaction, we observed traveling waves of local swelling that form a rich variety of dynamic patterns and give rise to distinctive oscillations in the gel's shape. The observed patterns depend critically on the gel's dimensions. The approach provides a useful computational tool for probing the dynamics of chemomechanical processes and uncovering morphological transformations in responsive gels.     

链霉菌702所产抑真菌物质理化性质的初步研究

用链霉菌702所产的抑真菌物质纯品进行了极性试验和官能团反应。极性试验表明该物质属于中性的非水溶性Ⅰ型抗生素;在官能团反应中,Molisch反应和Hopkins—Col反应呈阳性,表明该物质含有糖基和色氨酸,为进一步对该抑菌物质进行结构鉴定,提供了有益的实验依据。     

Facile splitting of hydrogen and ammonia by nucleophilic activation at a single carbon center

In possessing a lone pair of electrons and an accessible vacant orbital, singlet carbenes resemble transition metal centers and thus could potentially mimic their chemical behavior. Although singlet di(amino)carbenes are inert toward dihydrogen, it is shown that more nucleophilic and electrophilic (alkyl)(amino)carbenes can activate H2 under mild conditions, a reaction that has long been known for transition metals. However, in contrast to transition metals that act as electrophiles toward dihydrogen, these carbenes primarily behave as nucleophiles, creating a hydride-like hydrogen, which then attacks the positively polarized carbon center. This nucleophilic behavior allows these carbenes to activate NH3 as well, a difficult task for transition metals because of the formation of Lewis acid-base adducts.     

Rectification of STM Current to Graphite Covered with Phthalocyanine Molecules

The scanning tunneling microscope (STM) can be used to measure current-voltage characteristics on an atomic scale. The attachment of copper phthalocyanine molecules, in contrast to a variety of other molecules, to graphite changes the electrical characteristics of the STM from relatively symmetric to highly asymmetric or rectifying. Evidence is presented to show that the asymmetry arises because of the electronic energy levels of the copper phthalocyanine. The organic molecules were bonded to the graphite by an acid-base reaction that may have wide applicability.     

Mode-specific energy disposal in the four-atom reaction OH + D2 --> HOD + D

Experiments, employing crossed molecular beams, with vibrational state resolution have been performed on the simplest four-atom reaction, OH + D2 --> HOD + D. In good agreement with the most recent quantum scattering predictions, mode-specific reaction dynamics is observed, with vibration in the newly formed oxygen-deuterium bond preferentially excited to v = 2. This demonstrates that quantum theoretical calculations, which in the past decade have achieved remarkable accuracy for three-atom reactions involving three dimensions, have progressed to the point where it is now possible to accurately predict energy disposal in four-atom reactions involving six dimensions.     

应用氧化值法判断一些有机化学反应规则

本文应用简单的氧化值法，介绍一种判断亲电加成反应和亲核加成反应规则，判断对苯环亲电取代反应起定位作用的定位基属哪类定位基的方法。     

Electrons in finite-sized water cavities: hydration dynamics observed in real time

We directly observed the hydration dynamics of an excess electron in the finite-sized water clusters of (H2O)n- with n = 15, 20, 25, 30, and 35. We initiated the solvent motion by exciting the hydrated electron in the cluster. By resolving the binding energy of the excess electron in real time with femtosecond resolution, we captured the ultrafast dynamics of the electron in the presolvated ("wet") and hydrated states and obtained, as a function of cluster size, the subsequent relaxation times. The solvation time (300 femtoseconds) after the internal conversion [140 femtoseconds for (H2O)35-] was similar to that of bulk water, indicating the dominant role of the local water structure in the dynamics of hydration. In contrast, the relaxation in other nuclear coordinates was on a much longer time scale (2 to 10 picoseconds) and depended critically on cluster size.     

Chemical transformations in individual ultrasmall biomimetic containers

Individual phospholipid vesicles, 1 to 5 micrometers in diameter, containing a single reagent or a complete reaction system, were immobilized with an infrared laser optical trap or by adhesion to modified borosilicate glass surfaces. Chemical transformations were initiated either by electroporation or by electrofusion, in each case through application of a short (10-microsecond), intense (20 to 50 kilovolts per centimeter) electric pulse delivered across ultramicroelectrodes. Product formation was monitored by far-field laser fluorescence microscopy. The ultrasmall characteristic of this reaction volume led to rapid diffusional mixing that permits the study of fast chemical kinetics. This technique is also well suited for the study of reaction dynamics of biological molecules within lipid-enclosed nanoenvironments that mimic cell membranes.     

氰氟草酯(XDE-537)在土壤中的降解

在杭州市富阳郊区水稻田，研究了除草剂千金（有效成分为氰氮草酯，代号XDE-537）在土壤中的降解动态，测定了土壤样品中的XDE-537及其降解产物。结果表明，氰氟草酯在土壤中迅速降解至检测限以下，分解首先生成氰氟草酯的丙酸同系物（ACID），进一步形成的降解产物为无除草活性的二酸同系物（DIACID）。ACID的降解较缓慢，DIACID的形成与ACID的降解成负相关。由于氰氟草酯、ACID和DIACID在土壤环境中均分解较快，可以认为千金在环境中属非滞留性除草剂。