Design of a calcium-binding protein with desired structure in a cell adhesion molecule

Ca2+, "a signal of life and death", controls numerous cellular processes through interactions with proteins. An effective approach to understanding the role of Ca2+ is the design of a Ca2+-binding protein with predicted structural and functional properties. To design de novo Ca2+-binding sites in proteins is challenging due to the high coordination numbers and the incorporation of charged ligand residues, in addition to Ca2+-induced conformational change. Here, we demonstrate the successful design of a Ca2+-binding site in the non-Ca2+-binding cell adhesion protein CD2. This designed protein, Ca.CD2, exhibits selectivity for Ca2+ versus other di- and monovalent cations. In addition, La3+ (Kd 5.0 microM) and Tb3+ (Kd 6.6 microM) bind to the designed protein somewhat more tightly than does Ca2+ (Kd 1.4 mM). More interestingly, Ca.CD2 retains the native ability to associate with the natural target molecule. The solution structure reveals that Ca.CD2 binds Ca2+ at the intended site with the designed arrangement, which validates our general strategy for designing de novo Ca2+-binding proteins. The structural information also provides a close view of structural determinants that are necessary for a functional protein to accommodate the metal-binding site. This first success in designing Ca2+-binding proteins with desired structural and functional properties opens a new avenue in unveiling key determinants to Ca2+ binding, the mechanism of Ca2+ signaling, and Ca2+-dependent cell adhesion, while avoiding the complexities of the global conformational changes and cooperativity in natural Ca2+-binding proteins. It also represents a major achievement toward designing functional proteins controlled by Ca2+ binding.     

Mössbauer and electric conductivity studies of bidentate base adducts of acetylacetonatoiron(II)

Summary Bidentate bridging base polymer complexes of acetylacetonatoiron(II) [Fe(acac)₂L]_n, where L=pyrazine(pyz), 4,4-bipyridine(bpy),trans-1,2-bis(4-pyridyl)ethylene(bpe), 1,2-bis(4-pyridyl)ethane(bpa) and 4,4-trimethylene bipyridine(tmbpy), have been prepared, characterized and oxidized by iodine to give a range of iron(III) and iron(II) complexes [Fe(acac)₂L · I_x]_n] in which the Fe^III/Fe^II ratios were established by Mössbauer spectroscopy. The electric conductivities of compressed pellets of the polysalts were obtained. The conductivities and Mössbauer parameters (I.S. and Q.S.) both change with respect to the kind of bidentate bridging bases.The conjugation of bridged ligand markedly affects the conductivity of the complexes.     

添加剂对SiO电性能的影响及其机理分析

SiO_x/CoO and SiO/Li₂CO₃ composite materials were prepared by mechanical ball-milling. The structures of the obtained materials were characterized by X-ray diffraction (XRD). And scanning electron microscopes (SEM) of three samples after 20 cycles were also given. In addition， the electrochemical performances of three materials with galvanostatic charge-discharge cycling were investigated. The results show that the composite samples have larger initial reversible capacities and better cycle performance than pure SiO. Also，a schematic diagram showing the buffer effects of Li₂CO₃ addition and the mechanism of improving electrochemical performance by adding Li₂CO₃ are suggested.     

Ag/ZrO2催化剂上的1,2-丙二醇选择性气相氧化反应

采用浸渍法制备了一系列Ag/ZrO₂催化剂, 考察了Ag/ZrO₂催化剂对1,2-丙二醇选择性氧化合成丙酮醛反应的催化性能. 实验结果表明: 在原料气配比为V(N₂)∶V(O₂)＝300∶19, n(O₂)/n(alcohol)＝1.2, 反应物液时空速为3.2 g/(g•h), 反应温度为673 K时, 1,2-丙二醇选择性氧化合成丙酮醛反应的转化率为95.7%, 选择性为55.3%, 高于传统电解银催化剂. UV-Vis DRS和XPS的研究结果表明: 在Ag/ZrO₂催化剂上存在大量的Ag^＋和Ag_n^δ＋有利于促进催化活性的提高.     

Tuning the oxidation properties of vanadium(V) through ligand stoichiometry

Vanadium(V) (5 mol %) and hydroxamic acid ligand (45 mol %) were found to promote the selective tert-butyl hydroperoxide-mediated oxidation of allylic and propargylic alcohols to the corresponding aldehydes and ketones.     

Valence bond theoretical study for chemical reactivity

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芦荟中多糖的光度测定新方法

利用正交试验考察了芦荟多糖与刚果红显色反应的最佳条件；研究了麦芽糖糊精等多糖、蔗糖等低聚糖和葡萄糖等单糖对显色反应的影响；建立了简便快速、常见糖类基本无干扰的测定芦荟多糖含量的吸光光度法。对芦荟鲜叶和芦荟制品中的多糖进行分析，加标回收率在92％～96％范围内，相对标准偏差≤5％。     

饱和锌的粘土矿物吸附半胱氨酸的机理

用红外光谱、X射线衍射（XRD）和热分析研究了饱和过渡金属锌的粘土矿物吸附半胱氨酸的机理；XRD结果显示吸附了半胱氨酸后的粘土矿物的d(001)方向的距离明显增大，说明被吸附的半胱氨酸进入了粘土的层状结构之中；饱和了锌的粘土矿物吸附半胱氨酸有两种方式，其一为弱相互作用，另一种强相互作用；后一种方式吸附的半胱氨酸与粘土的过渡金属之间形成了配合结构，结合力比较强，在热作用下，它们一直到395℃左右才分解；强相互作用吸附的半胱氨酸主要是以去质子的两性离子和阴离子形式存在于粘土矿物上，与过渡金属形成螯合的六元环结构。