REFINEMENT OF THE CRYSTAL STRUCTURE OF INSULIN AT 1.2 RESOLUTION

The crystal structure of 2 Zn porcine insulin has been refined at 1.2 resolution. The reciprocal space refinement was restrained by the incorporation of extensive chemical observations into the least squares equations. In addition to the non-hydrogen atoms, hydrogen atoms of protein, water molecules and the bulk solvent have been determined and refined. After two cycles of anisotropic refinement of non-hydrogen atoms of insulin, the final agreement factor was 0.128 for 20,005 reflexions (F_o>1σ(F_o)) in a spacing 1.2 and the root mean squares deviation from ideal covalent bond lengths was 0.021. On the electron density maps, the appearances of weight and shape of non-hydrogen atoms were very clear and reasonable. The anisotropic appearances of sulphur atoms could be seen clearly. After anisotropic refinement, the situation fit to the electron density was improved distinctly.     

X-RAY STUDIES ON THE STRUCTURE OF DES-PENTAPEPTIDE INSULIN AT 2.4 RESOLUTION——THE REFINEMENT OF THE STRUCTURE

The determination of an initial model for the crystal structure of des-pentapeptide in-sulin, using only the phase information obtained from the scattering of cadmium ions inthe native crystal, has been described. This paper describes the refinement of this modelagainst both the experimental X-ray observations and the a priori stereochemical observationsusing the method of restrained parameter least squares. The corrected and extended modelincluded not only all the non-hydrogen atoms of the protein and one cadmium ion, but alsosome 49 water molecules. Fourier syntheses using amplitudes of 2F_o-F_c, phase angles prob-abilistically combined from the anomalous scattering and model phase information, witheach term weighted according to its reliability gave clear results without detectable bias to-wards the current model. The final model has acceptable stereochemistry (root mean squaredeviation from ideal bond lengths 0.027 A), and predicts the observed X-ray scattering sat-isfactorily (R = 0.182 for all dat     

THE CRYSTAL STRUCTURE OF BAYLEYITE

The bayleyite crystallizes in monoclinic space group C_2~5h-P2_1/c with a=6.499(1), b=15.235(5), c=26.513(6), β= 92.92(2)°, Z=4. Intensities of 3430 independent reflections are collected with diffractometer using MoKα radiation. The crystal structure has been solved by the Patterson method and refined by block least square refinement for positional parameters and isotropic temperature factor of non-hydrogen atoms. The final R factor is 0.038.The result of crystal structure analysis shows that the structure consists of discrete [UO_2(CO_3)_3]~(4-) ions and Mg~(2 ) cations are between slab-like units, but they are not in a slablike unit. Its crystal struture is different from that of liebigite which was determined by Appleman. Complexes and cations between slab-like units and in a slab-like unit are connected by hydrogen bonds formed by water molecules.     

REFINED CRYSTAL STRUCTURE OF INSULIN AT 1.8A RESOLUTION——CRYST

The structure of insulin has been refined by difference Fourier method at 1.8A resolu-tion. A set of computer programs calculating the mF_o-nF_c Fourier synthesis and the cor-rections of parameters automatically has been set up. With the programs to refine theinsulin model obtained from MIR map at 1.8A resolution for 11 cycles, the R index(R=∑|KF_o- F_c|/∑KF_o) is reduced to 0.210 from the initial value of 0.388. Duringthe refinement the stereochemistry of the insulin molecules is constantly detected andadjusted to fit the reasonable geometry. The refinement has greatly improved the structuremodel of insulin and provided more detailed structure information. On the basis of this thesystems of hydrogen bond in an insulin dimer are determined and the interaction betweenwater and insulin molecules in the crystal is investigated.     

STRUCTURE OF (Trp)~(B1)-INSULIN AT 2RESOLUTION

The rhombohedral crystal structure of [Trp]~(B1)-insulin has been refined, using data to 2 and atomic coordinates of 2-zinc porcine insulin as starting model, and through the use of the restrained least-squares method, to an R value of 0.24. The result of refinement shows that in comparison with the 2-zinc insulin structure, some changes in local conformation occur, and are asymmetric for the two independent molecules related by a local two-fold axis. The obvious conformational changes are found to be in molecule 1, at its B-chain N-terminus and A13-residue region.     

STUDY OF THE CRYSTAL STRUCTURE OF BIS(2,4-DIMETHYL-PENTADIENYL) MONOCARBONYL-VANADIUM USING A LOW TEMPERATURE X-RAY DIFFRACTION TECHNIQUE

<正> The single crystal X-ray diffraction data of (2,4-(CH3)2C5H5]2VCO have been collected under low temperature (-60℃) and the crystal structure has been solved by heavy atom method. It belongs to orthorhombic system, space group P212121, a =9.921(6), b =9.899(6), c=14.491(8) A, Z=4. Several cycles of block matrix least-squares refinement gave the final R=0.087.     

STUDIES ON RESPONSE CHARACTERISTICS OF DRUG ISE''''S (Ⅶ)——PERFORMANCE AND THEORETICAL TREATMENT OF MICROCELLS CONNECTED IN SERIES

A new type of MCCS (microcells connected in series) has been constructed and its performances investigated. It has been applied to the determination of streptomycin. The sensitivity and accuracy have been increased significantly. A theoretical model for the error of determination using the MCCS has been suggested and proved experimentally using the Monte Carlo method, and the error model proposed in Ref. [1] revised.     

CRYSTAL AND MOLECULAR STRUCTURE OF DEHYDROCRYDALINE CHLORIDE

The crystals of alkaloid Dehydrocrydaline chloride (C_(22)H_(24)NO_4·HCl) belong to the orthorhombic system. The space group is D_(2k)~(14)-Pbcn with the unit cell parameters of a=8.528,b=23.317 and c=24.798, and eight molecules per unit cell. The coordinates for all the non-hydrogen atoms were found by using direct methods and Fourier syntheses. During the course of refinement of this structure (using least squares and difference Fouriers), it was discovered that there are 4.5 water molecules with different occupancies in one asymmetric volume of the unit cell. The anisotropic refinement of non-hydrogen atoms and the isotropic refinement of non-aqueous hydrogen atoms led to a final R-factor of 0.053. Water molecules formed a relatively complex network around chloride ion.In this paper the small molecule structure and the network of water molecules are described.     

STUDIES ON THE CRYSTAL STRUCTURE OF Al-(L-TRYPTOPHAN) INSULIN AT 2.1RESOLUTION

In order to study the biological effect of alterations to the N-terminus of the insulin A-chain, we have determined the crystal structure of Al-(L-Trp) insulin and discovered that it belongs to the trigohal system with space group R3. The parameters oof the unit cell are a=b=80.3A, c=37.5A. The model was adjusted and refined by using a stereochemically-restrained least squares program, assisted by manual revision of the model based on the difference Fourier map, to a final R-factor of 0.195. The main and side chains of both Al-(L-Trp) residues in the asymmetric unit are well ordered. It was found that the Al-Trp residue of molecule I occupied two distinct positions. We have proposed from the results of the three-dimensional structure that the 4-zinc insulin hexameric form is a stored state of insulin molecules in a conformation of low activity. The structural details of the insulin molecule and its structure and function relationship have also been discussed.     

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.     

A MARKOV-TYPE ANALOG MODEL FOR PREDICTION OF TYPHOON MOTION IN NORTHWESTERN PACIFIC

In this paper, a Markov-type analog model for the prediction of the tropical cyclone motion is developed for the Northwestern Pacific. The probabilities are studied by using the United States National Hurricane Center HURRAN model as a guide. In order to approach and suit to the new circumstance continuously, a Markov process has been used to describe the probability forecast for typhoon movement. The model is different from the traditional analog method both in searching probability solutions and in renewing initial data.A transplantation model (Model 1) has also been developed by using the traditional analog methods. Both Model 1 and Markov-type analog model (Model 2) have been tested for 95 simultaneous cases, which are independent data for the years 1981 and 1982. It has been shown from this examination that the Markov-type model appears to give smaller forecast errors.     

THE CRYSTALLOGRAPHIC STRUCTURE OF THE PHOTOOXIDIZED PRODUCT OF HYPOCRELLIN A AND THE STUDY OF THE PHOTODYNAMIC ACTION MECHANISM

In attempting to study the phototherapeutic action and the photosensitized oxygenation mechanism, we have determined the crystal structure of the main oxidized product of hypocrellin A (HA). It was crystallized in monoclinic system with space group P2_1. The cell data are: a=10.030(3), b=8.877(3), c=15.764(5), β=104.50(2)°, Z=2. The crystal structure has been determined by direct method and refined to a final R of 0.055 based on the 1408 observed reflections with l>2.5σ(Ⅰ). The photooxidized product is composed of a heptacyclic aliphatic hydrocarbon connecting with two α-naphthoquinone derivatives as its skeletal molecule. No peroxidic linkage has been found. On the basis of the crystal structure determined, we have deduced part of the process of formation of the oxide, ⅰ. e. firstly, the peroxide was formed by photocycloaddition of oxygen molecule to Hypocrellin A, then thermodissociation took place to form a stable oxide.     

STUDY ON THE SWELLING BEHAVIOUR OF COPOLYMER HYDROGEL

The states of water in poly (N-vinylpyrrolidone-methylmethacrylate) and poly (N-vinylpyrroli-done-2-hydroxyethyl methacrylate) hydrogels have been studied by means of DSC. The effect ofpolmer structure on equilibrium swelling extent of water has been examined. It was found that thestate of water and the water content in different hydrogels were dependent on the kind of monomer used,the component of copolymer, the sequence distribution of the monomer unit and the degree of cross-linking (including chemical and physical) to a great extent. The equilibrium water content of thehydrogel may be regarded as the sum of the different state of swollen water contents of the hydrogel.Based on these, a semiempirical formula used to estimate the equilibrium water content of the copolymerhydrogels was presented.     

EFFECT OF THE COMPOSITION OF m-CRESOL/H2O SOLVENT ON HYDRODYNAMIC PROPERTIES OF NYLON 6

The intrinsic viscosity [ η], Huggins constant (KH), [ η]0, α3 and flow activation energy values of nylon 6 have been measured in water/m-cresol (0/100-20/80) systems at different temperatures (20-60℃). It has been found that the intrinsic viscosity, [η]0 and α3 increase with the increase in water contents in m-cresol up to 15% and then decrease. They increase with the increase in temperature irrespective of solvent composition. It has been noted that the percent increase of α3 is the highest at 60℃ and the lowest at 20℃ for a particular solvent system. The intrinsic viscosity data obey Arrhenius equation over the considered conditions. The activation energy and the KH values decrease very sharply with the addition of water,giving a minimum value at 15% of water and then increase slowly. The variation of all the parameters has been explained in terms of variation in thermodynamic quality of solvent with the addition of water to m-cresol and change in temperature,resulting in the change of conformational and orientational properties of polymer molecules. This change of solvent quality also results in variation of selective sorption of solvent over the polymer, such as hydrogen bonding, etc.     

CRYSTAL AND MOLECULAR STRUCTURE OF 1.3-DI-ISO-PROPYL-2-PHENYL-4-METHOXY-4,5-DIOXO-2-THIO-1,3,2,4-DIAZADTPHOSPHOLANE

<正> The structure of the title compound has been determined by X-ray analysis. The crystals of this coiapound are monoclinic, space group P21/c with a=8.432(1),b=11.735(3),c=18.254(4)A,β=93.25(2)°,Z=4, and Dx=1.33 g/cm3. The final refinement converged with R=0.031 and Rw=0.031 for 1788 observed independent reflections.     

MOLECULAR STRUCTURE AND ABSOLUTE CONFIGURATION OF SUBEROGORGIN

In the present paper it is reported that the molecular structure and absolute configuration of poisonous suberogorgin are determined by using X-ray diffraction method. The crystal of suberogorgin belongs to orthogonal system with space group D_2~4-P2_12_12_1. The crystallographic parameters are: a=16.135, b=13.189, c=12.901, Z=8. The initial model of the crystal structure was solved by the direct method. The refinement of the strueture parameters was carried out by using the least square method and led to a final R-factor of 0.056. In accordance with the molecular structure of suberogorgin mentioned above, the solvent effect of NMR has been further discussed and the relationship between the molecular structure of suberogorgin and its toxicity has also been preliminarily investigated.     

Reaction mechanism and chemoselectivity of gold(Ⅰ)-catalyzed cycloaddition of 1-(1-alkynyl) cyclopropyl ketones with nucleophiles to yield substituted furans

The mechanisms of gold(Ⅰ)-catalyzed cycloaddition of 1-(1-alkynyl) cyclopropyl ketones with nucleophiles have been investigated using density functional theory calculations at the B3LYP/6-31G(d,p) level of theory.A polarizable continuum model(PCM) has been established in order to evaluate the effects of solvents on the reactions.The results of the calculations indicate that the first step of the catalytic cycle is the cyclization of the carbonyl oxygen onto the triple bond which forms a new and stable resonance structure of an oxonium ion and a carbocation intermediate.The subsequent ring expansion step results in the formation of the final product and regeneration of the catalyst.Furthermore,the regioselectivity and effect of substituents has been discussed,including an analysis of energy,bond length,and natural bond orbital(NBO) charge distributions in the rate-determining step.Our computational results are consistent with earlier experimental observations.     

Fabrication of Poly(dimethylsiloxane)-Based Capillary Electrophoresis Microchips Using Epoxy Templates

A novel method for the fabrication of poly(dimethylsiloxane) (PDMS)-based capillary electrophoresis (CE) microchips using epoxy templates is described. A PDMS plate containing the channel structure was replicated from a hard master with the positive relief of negative photoresist on a silicon wafer by replica molding. It was used as a soft mold to produce the positive relief of a hard epoxy template for molding of the final soft PDMS micro devices. The present hard-to-soft, soft-to-hard, and hard-to-soft micro fabrication method offers a promising way for the mass production of PDMS microchips, epoxy and other hard polymer templates. The epoxy templates are durable for molding PDMS electrophoresis microchips because of its higher mechanical strength. High chip-to-chip reproducibility has been found with relative standard deviations (n = 30) of 3.7 and 4.1% for the widths (49.2 μm) and depths (41.5 μm) of the replicated channels in the final PDMS substrates, respectively. The feasibility and performance of the PDMS microchips fabricated by the new method have been demonstrated by separating and detecting dopamine and catechol in connection to end-column amperometric detection. Factors influencing the analytical performance of the microsystem for the separation of the two analytes have been characterized and optimized.