手性胶束中不对称诱导的结构效应

为了探讨手性胶束中的不对称诱导机理，研究了手性表面活性剂及受物的结构对反应的对映体选择性影响．结果表明，表面活性剂适当位置（如铵基的α－位）有羟基存在，可得到较高的光学产率，增长表面活性剂或硫醚中烷基的链长，一般有利于手性胶束的不对称诱导．     

不同改良剂对苏打草甸碱土渗透性的影响

针对苏打碱土碱性强、渗透性弱的特点,本文研究了不同用量MM改良剂和JD改良剂对大安市不同土层苏打草甸碱土渗透性的影响。结果表明,MM改良剂效果高于JD改良剂;MM改良剂对表层土(0～20 cm)的影响最大。土壤渗透系数随着改良剂施入量增加有明显增加。     

Metals and DNA: molecular left-handed complements

Chiral metal complexes provide unique molecular probes for DNA. Chiral reagents that "recognize" different local structures along the DNA strand have been designed by a process in which the asymmetry in shape and size of the complex is matched to that of the DNA helical groove. As a result, the chiral metal complexes provide very sensitive probes for local helical structure, both left- and right-handed. Direct coordination of chiral complexes to the DNA bases adds an element of sequence selectivity to the probe design. With a suitable reactive metal center, reagents that target chemically specific sites along the strand may be developed. One such chiral reagent, which cleaves left-handed DNA sites with photoactivation, has been useful in mapping this distinct conformation and examining its biological role. The conformation-specific molecular cleaver, much like a DNA-binding enzyme, recognizes and reacts at discrete sites along the DNA strand. These site-specific chiral metal complexes provide exciting new tools for probing the local variations in DNA structure and its role in the regulation of gene expression.     

Identification of active edge sites for electrochemical H2 evolution from MoS2 nanocatalysts

The identification of the active sites in heterogeneous catalysis requires a combination of surface sensitive methods and reactivity studies. We determined the active site for hydrogen evolution, a reaction catalyzed by precious metals, on nanoparticulate molybdenum disulfide (MoS2) by atomically resolving the surface of this catalyst before measuring electrochemical activity in solution. By preparing MoS2 nanoparticles of different sizes, we systematically varied the distribution of surface sites on MoS2 nanoparticles on Au(111), which we quantified with scanning tunneling microscopy. Electrocatalytic activity measurements for hydrogen evolution correlate linearly with the number of edge sites on the MoS2 catalyst.     

土地利用方式对土壤活性有机碳分布的影响

对福建省建瓯市山地红壤的园地(茶园、桔园)、林地(杉木、木荷、封育)不同土层(0-10 cm、10-20 cm)土壤活性有机碳(轻组有机碳、可溶性有机碳、微生物量碳)含量进行研究。结果表明,林地转变园地后,在0-10 cm土层土壤轻组有机碳(LFC)、可溶性有机碳(DOC)和微生物量碳(MBC)含量平均分别下降了65.97%、64.60%和54.78%,在10-20 cm则平均分别下降了57.39%、21.88%和43.71%;土壤微生物商在不同利用方式下没有明显分异规律。土壤活性有机碳含量随土层加深而递减(桔园除外),但不一定有显著差异。因此,亚热带山地红壤内林地转变为园地会导致土壤活性有机碳含量大幅度下降,活性有机碳比土壤总有机碳对土地利用变化更为敏感。     

四种手性农药在CHIRALPAK AS-H柱上的直接拆分

采用高效液相色谱手性固定相在CHIRALPAK AS-H柱上对三唑醇、戊唑醇、烯唑醇和顺式高效氯氟氰菊酯4种手性农药进行了直接拆分,同时考察了流动相中极性改性剂醇的种类及含量对手性拆分的影响.结果表明:在室温及0.5mL·min-1流速下,4个手性农药样品均获得基线分离,其中三唑醇的最佳拆分条件为V正己烷:V乙醇=95:5,Rs=2.00;戊唑醇、烯唑醇和顺式高效氯氟氰菊酯的最佳拆分条件均为V正己烷:V异丙醇=90:10,Rs分别为1.40、2.76和1.80.     

Dynamic aggregation of chiral spinners

An object spinning at the surface of a liquid creates a chiral vortex. If the spinning object is itself chiral, its shape modifies the characteristics of the vortex; interactions between that vortex and other vortices then depend on the chirality of the objects that produce them. This paper describes the aggregation of millimeter-sized, chiral magnetized plates floating at a liquid-air interface and rotating under the influence of a rotating external magnetic field. This external field confines all the plates at densities that cause the vortices they generate to interact strongly. For one set of plates investigated, plates of one chirality attract one another, and plates of the other chirality repel other plates of both chiralities.     

谱拆分研究O,O-二甲基-1-(4-甲氧基苯氧乙酰氧基)乙基膦酸酯对映体的高效液相色

采用手性固定相高效液相色谱法研究了不同固定相类型、流动相中不同醇改性剂和不同异丙醇含量以及温度对O,O-二甲基-1-(4-甲氧基苯氧乙酰氧基)乙基膦酸酯拆分效果的影响,并初步讨论了它的热力学机理。结果表明:在25℃的直链淀粉-三(-3,5-二甲基氨基甲酸酯)(Chiralpak AD-H)手性柱中,以正已烷∶异丙醇体积90∶10为流动相,流速为1.0 ml/min,检测波长220 nm时,对映体可得到基线分离。     

三聚氰胺–尿素–葡萄糖（MUG）生物质树脂/硅酸钠复合改性杨木的性能与机理研究

  目的  研究改性材的微观形貌、化学结构和元素成分等变化,探讨三聚氰胺–尿素–葡萄糖（MUG）生物质树脂复合改性剂对杨木的改性作用机理,旨在为MUG复合改性剂的应用提供依据,促进木材的绿色改性。  方法  通过将有机硅烷等疏水基团,引入MUG生物质树脂与硅酸钠的复配溶液中,制备硅烷杂化MUG树脂/硅酸钠复合改性剂（GS_T）,对杨木进行真空加压浸渍处理,测试改性杨木的物理力学性能,采用扫描电镜–X射线能谱仪（SEM-EDX）、傅里叶变换红外光谱仪（FTIR）、X射线光电子能谱仪（XPS）和X射线衍射仪（XRD）等,表征改性材的微观形貌、化学结构、元素成分和结晶度,利用微型量热仪（MCC）测试其燃烧性能和热解特性。  结果  SEM-EDX分析表明:GS_T改性剂渗透性好,能有效渗入木材细胞腔和细胞壁中;改性材的C、O、Si元素无规分布于木材细胞腔、细胞壁、细胞间隙等处,导管沉积最为明显;改性剂对木材孔隙的填充以及对纤维素非结晶区的充胀,有效提高了木材的尺寸稳定性和力学性能。FTIR分析表明:GS_T改性材中半纤维素等多糖与改性剂发生了交联反应,减少了C=O、—OH等吸水性基团。XPS分析表明:GS_T改性材的C1最多,C3最少,木材的多糖类物质、木质素醇羟基、酚羟基以及羰基等活性基团与改性剂发生反应,减少了羰基等活性基团,增加了C—H、C—C结构含量。XRD分析表明:GS_T改性材衍射峰无明显变化,相对结晶度增大,说明改性剂进入纤维素非结晶区使其分子排列更加有序。MCC分析表明:GS_T改性材的热释放能力、热释放速率峰值和总热释放量分别下降了65.7%、66.2%和6.2%,800 ℃残炭率提高了122.6%,热释放强度大大降低,火灾危险性减小。  结论  GS_T复合改性剂可有效渗入杨木内部,与木材中半纤维素等多糖发生交联反应,减少糖基等活性基团,使非结晶区排列更为有序,从而提升改性杨木的物理力学性能。      

Synthesis of two-dimensional polymers

A synthetic pathway is described to construct "in bulk" two-dimensional (2D) polymers shaped as molecular sheets. A chiral oligomeric precursor is used that contains two reactive sites, a polymerizable group at one terminus and a reactive stereogenic center near the middle of the molecule. The bulk reaction yields bilayer 2D polymers of molecular weight in the order of millions and a monodisperse thickness of 50.2 angstroms. The 2D molecular objects form through molecular recognition by the oligomers, which self-organize into layers that place the reactive groups within specific planes. The oligomers become catenated by two different stitching reactions involving the reactive sites. At room temperature, stacks of these molecular objects can organize as single crystals and at higher temperatures melt into smectic liquid crystals. Nonlinear optical experiments reveal that solid films containing the 2D polymers form structures that are thermally and temporally more stable than those containing analogous 1D polymers. This observation suggests that the transformation of common polymers from a 1D to a 2D architecture may produce generations of organic materials with improved properties.     

芝麻核桃面包的研制

以面粉为主要原料,加入芝麻和核桃,研制具有保健功能的芝麻核桃面包。通过正交试验确定芝麻核桃面包的配方和工艺参数。结果表明,芝麻核桃面包的配方是:芝麻30g.kg-1,核桃50g.kg-1、改良剂为8g.kg-1面粉、活性干酵母为10g.kg-1面粉、白砂糖为40g.kg-1面粉。优化工艺参数:焙烤时间为15min,其中烘焙13min,上色2min;焙烤温度180℃,上色温度210℃。     

鲁宁管道添加CE—S原油改性剂工业性试验

为了提高管道输油效益,从１９９４年起,开始对鲁宁线原油进行添加改性剂的研究,并于１９９５年７月在鲁宁线做了加剂输送的工业性试验,经过一年多时间的加剂运行,取得了明显的社会效益和良好的经济效益。重点介绍了鲁宁线加改性剂的目的,改性剂的研制和室内试验、加剂试验过程,各阶段的运行情况,加剂后的能耗及加剂试验所得出的结果。     

Improved oxygen reduction activity on Pt3Ni(111) via increased surface site availability

The slow rate of the oxygen reduction reaction (ORR) in the polymer electrolyte membrane fuel cell (PEMFC) is the main limitation for automotive applications. We demonstrated that the Pt3Ni(111) surface is 10-fold more active for the ORR than the corresponding Pt(111) surface and 90-fold more active than the current state-of-the-art Pt/C catalysts for PEMFC. The Pt3Ni(111) surface has an unusual electronic structure (d-band center position) and arrangement of surface atoms in the near-surface region. Under operating conditions relevant to fuel cells, its near-surface layer exhibits a highly structured compositional oscillation in the outermost and third layers, which are Pt-rich, and in the second atomic layer, which is Ni-rich. The weak interaction between the Pt surface atoms and nonreactive oxygenated species increases the number of active sites for O2 adsorption.     

Scanning Single-Electron Transistor Microscopy: Imaging Individual Charges

A single-electron transistor scanning electrometer (SETSE)-a scanned probe microscope capable of mapping static electric fields and charges with 100-nanometer spatial resolution and a charge sensitivity of a small fraction of an electron-has been developed. The active sensing element of the SETSE, a single-electron transistor fabricated at the end of a sharp glass tip, is scanned in close proximity across the sample surface. Images of the surface electric fields of a GaAs/AlxGa1-xAs heterostructure sample show individual photo-ionized charge sites and fluctuations in the dopant and surface-charge distribution on a length scale of 100 nanometers. The SETSE has been used to image and measure depleted regions, local capacitance, band bending, and contact potentials at submicrometer length scales on the surface of this semiconductor sample.     

Geothermal convection through oceanic crust and sediments in the Indian ocean

Closely spaced heat flow surveys at four sites on the flanks of the Central Indian Ridge and the Southeast Indian Ridge delineate a pattern of oscillatory heat flow which can only result from cellular convection of oceanic bottom water through the oceanic crust and overlying sediment. These cells have a wavelength of 5 to 10 kilometers and are presently active in sea floor 18 x 10(6), 25 x 10(6), and 45 x 10(6) years old of the Crozet Basin and in sea floor 55 x 10(6) years old of the Madagascar Basin. The precise measurement of nonlinear temperature profiles makes it possible to calculate the conductive and convective heat transfer components through the sea floor. Even in the oldest sites, geothermal convection is still a major component of heat transfer through both the crust and sedimentary layers. These observations coupled with the results of earlier oceanwide geothermal studies indicate that more than one-third of the entire surface area of the world's ocean floor contains presently active geothermal convection that is cellular in plan form.     

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.     

热带雨林林缘不同热力作用面热力特征初探

片断化森林林缘不仅具有水平空间特征,同时也具有立体空间特征.为探讨立体林缘壁面的热力效应是否存在,该热力效应与林内外地面、林冠的差异,该文利用西双版纳热带雨林南向边缘的表温观测资料,采用同期资料对比方法,分析了片断化热带雨林林缘不同热力作用面表面温度的水平、垂直分布特征及其差异. 指出在片断化热带雨林林缘,林缘壁面的热力效应是不可忽视的.在林缘区域,除了公认的林外地表面、林冠面和林内地表面3个热力作用面之外,林缘壁面构成了一个新的第4热力作用面. 对其进行深入细致的研究,将有助于解释森林边缘的小气候效应和生物效应.     

热带雨林林缘不同热力作用面热力特征初探

片断化森林林缘不仅具有水平空间特征 ,同时也具有立体空间特征 .为探讨立体林缘壁面的热力效应是否存在 ,该热力效应与林内外地面、林冠的差异 ,该文利用西双版纳热带雨林南向边缘的表温观测资料 ,采用同期资料对比方法 ,分析了片断化热带雨林林缘不同热力作用面表面温度的水平、垂直分布特征及其差异 .指出在片断化热带雨林林缘 ,林缘壁面的热力效应是不可忽视的 .在林缘区域 ,除了公认的林外地表面、林冠面和林内地表面 3个热力作用面之外 ,林缘壁面构成了一个新的第 4热力作用面 .对其进行深入细致的研究 ,将有助于解释森林边缘的小气候效应和生物效应     

Morphology of nascent ziegler-natta polymers

In the polymerization of alpha-olefins with heterogeneous Ziegler-Natta catalysts, the polymer is formed directly as long fibrillar units with folder chains. It is proposed that the fibrils are formed by the crystallization of polymer chains growing from the active sites on the catalyst surface, a process which is likened to root growth in whiskers.     

Privileged chiral catalysts

One of the most active current areas of chemical research is centered on how to synthesize handed (chiral) compounds in a selective manner, rather than as mixtures of mirror-image forms (enantiomers) with different three-dimensional structures (stereochemistries). Nature points the way in this endeavor: different enantiomers of a given biomolecule can exhibit dramatically different biological activities, and enzymes have therefore evolved to catalyze reactions with exquisite selectivity for the formation of one enantiomeric form over the other. Drawing inspiration from these natural catalysts, chemists have developed a variety of synthetic small-molecule catalysts that can achieve levels of selectivity approaching, and in some cases matching, those observed in enzymatic reactions.