X-RAY STUDIES ON THE STRUCTURE OF DES-PENTAPEPTIDE INSULIN AT 2.4  RESOLUTION——SOLUTION OF THE PHASE PROBLEM USING THE ANOMALOUS SCATTERING OF CADMIUM AND THE DERIVATION OF A MODEL STRUCTURE

The three dimensional structure of des-pentaptide insulin has been solved at a resolu-tion of 2.4A. The structure determination was achieved without the use of heavy atom de-rivatives, by using only the phase information obtained from the seattering (both real andimaginary) of X-rays by cadmium ions present in the native crystal. Using this phase in-formation, a map, with figure of merit 0.56, was produced which enabled an initial modelof the protein to be constructed. Because of the novelty of this approach to the solutionof the phase problem the procedures used are explained in some detail.     

6-对硝基苯基-2-环己烯酸和6-对甲氧苯基-2-环己烯酸的合成和晶体结构

X射线衍射法测定了6-对硝基苯基-2-环己烯酸(1)和6-对甲氧苯基-2-环已烯酸(2)的晶体结构。晶体(1)属三斜晶系,空间群为P1,晶胞参数a=10.300,b=8.062,c=7.804A,α=71.39,β=80.40,γ=74.77°,Z=2,偏离因子R=0.073。晶体(2)属单斜晶系,空间群为P2_1/c,晶胞参数a=16.550,b=5.583,c=14.600A,β=116.0°Z=4,偏离因子R=0.048。根据实验结果对成环加成反应的活性和区域选择性进行了讨论。     

2.4分辨率去五肽胰岛素结构的X射线研究——DPI分子及其同胰岛素的关系

本文描述了单体胰岛素类似物去五肽(B26—B30)胰岛素的结构。同三方二锌胰岛素结构的详细比较说明,DPI虽然在结构上有一些大的改变,但是基本的二级结构单位仍然完整地保持着。像胰岛素的其他晶形那样,DPI结构比较接近于二锌胰岛素结构中的分子Ⅰ。除了结构表面的改变之外,在分子中心还有一些微妙和广泛的改变。分子在晶体中紧密地堆积,有着许多不同的接触,包括蛋白质-镉相互作用的复合网及大量以水为媒介的接触。分子表面大批疏水基团绕蛋白质群集而成一厚带。晶体结构具有良好的有序性,某些侧链的清晰度和水分子的确定性优于在更具活动性的三方二锌胰岛素六体晶体所得的结果。     

2.4分辨率去五肽胰岛素结构的X射线研究——结构的修正

本文报道起始模型对于X射线实验观测量和已知立体化学观测量作约束参数最小二乘修正的结果.经修正和扩展的模型,不仅包括DPI分子的全部非氢原子和一个镉原子,而且还加进49个水分子.由反常散射和模型信息概率相联合得到相角,各项系数按相角可靠性加权,其2F_o-F_c Fourier综合给出清晰的结果,无明显的对试用模型的偏向.最后得到的模型有合理的立体化学,同理想键长的均方根偏离是0.027A;同观测X射线散射相当吻合,对 10—2.4A分辨率的全部数据其偏离因子R=0.182.     

STUDIES ON THE CRYSTAL STRUCTURE OF Al-(D-TRYPTOPHAN) INSULIN

We have determined the crystal structure of Al-(D-Trp) insulin and discovered that it belongs to the trigonal system with space group R3. The parameters of the unit cell are a=b=78.6, c=50.0. A set of data for half a sphere reciprocal space to a spacing of 2.2 were collected. The model was adjusted and refined by using a step-by-step approach and a stereochemically-restrained least squares program, assisted by manual revision based on the difference Fourier maps, to a final R-factor of 0.218. The main and side chains of both Al-D-Trp residues in the asymmetric unit are well ordered. The packing of Al-(D-Trp) insulin in the unit cell, the conformational differences with other insulin structures and its structure and function relationship bave also been discussed.     

MOLECULAR CLOSE-PACKING METHOD AND ITS APPLICATION TO CRYSTAL STRUCTURE DETERMINATION OF DESHEXAPEPTIDE (B25--B30) INSULIN

Based on the molecule-packing theory, we defined a molecule-packing function express-ing the compatibility of packing among the symmetry-related molecules in a unit cell. Acomputer program imitating the close-packing of molecules in the objective crystal latticeand giving the function value of each rotation and translation of the molecule in the unitcell was performed, and it therefore made the close-packing of molecules expressquantitatively. This method not only could judge a correct solution from several peaks ofthe rotation or translation function but it may also independently, quantitatively and quicklysolve some specific problems of rotation and translation. Using known structure of despenta-peptide (B26--B30) insulin as an example, the effectiveness of this method and its programwas inspected, and this method was successfully applied to solving the translation problem ofthe unknown structure of deshexapeptide (B25--B30) insulin. The molecular close-packingmethod proved by the results of R--search     

SYNTHESES AND PROPERTIES OF ELEVEN-COORDINATED COMPLEXES FORMED FROM LANTHANIDE NITRATES AND 1,8-NAPHTHO-16-CROWN-5

Complexs formed from lanthanide nitrates Ln (NO_3)_3 (Ln=La, Ce, Pr, Nd) and 1, 8-naph-tho-161crown-5 with a 1:1 stoichiometry have been synthesized and characterized by elementalanalyses; IR spectra, X-ray powder diagrams as well as thermogravimetric and differentialthermal analyses. A single crystal X-ray structural analysis indicates that the coordination num-ber of these complexes is eleven.     

胺三乙酸银晶体和分子结构的测定

(CH₂COOH)₂NCH₂COOAg属于单斜晶系,单位晶胞中包含有四个分子,晶胞周期为α=7.61₁?,b=4.98₄?,c=23.25?,β=104°52′。空间羣为P2₁/c(C_2h⁵)。用柏特森及电子密度函数方法获得了原子坐标。键长C—C=1.51?,N—C=1.48?,C—O=1.28?及Ag—O=2.23—2.73?。指出了在分子之间具有较强的氢键O…O=2.54?。     

柳珊瑚酸的分子结构和绝对构型

本文首次应用X射线单晶衍射法证实了一种新的倍半萜骨架,并测定了柳珊瑚酸的分子结构和绝对构型。柳珊瑚酸的晶体属于正交晶系,空间群:D_2~ -P2_12_12_1,晶胞参数:a=16.135,b=13.189,c=12.901,α=β=γ=90°。单胞中分子数为8,不对称单位含两个分子,用直接法导出全部非氢原子位置,经最小二乘法修正后,最终偏离因子R=0.056。文中还对柳珊瑚酸分子的结构进行了讨论,并对核磁共振溶剂效应有关理论进行了较深入的讨论,初步探讨了分子结构与其毒性之间的关系。     

MOLECULAR STRUCTURE AND ABSOLUTE CONFIGURATION OF THE DITERPENE LACTONE, PRAELOLIDE

Praelolide is a new compound which was isolated out from the gorgonian, Menella praelonga (Ridley), collected from the South Sea of China at Zhanjiang, Guangdong. The molecular formula is C_(28) H_(35) O_(12)C1. The research result by X-ray diffraction method on the crystal structure is presented. The compound is orthorhombic with space group P2_12_12, cell dimensions α=16.936, b=16.709, c=10.333, and Z=4. The structure has been solved by direct method and refined to R=0.055 for 2257 unique observable reflexions by least-squares. The molecule is composed of the major conformational isomer in which the three main rings(a six-membered ring, an eight-membered ring, a six-membered ring) take separately the form of chair-chairboat-chair, a five-membered actone ring, a C1 substitution, 4 acetate groups, and a three-membered epoxide ring. The absolute configuration of the molecule has also been determined by statistics (R factor ratio =1.012) and Bijvoet pairs observation. For 30 pairs of the greatest anomalo