非还原脲变性蛋白溶菌酶稀释复性过程中集聚现象的研究

用十二烷基硫酸钠-聚丙烯酰胺凝胶电泳、阴极聚丙烯酰胺凝胶电泳和高效凝胶排阻色谱法, 研究了非还原脲变性蛋白溶菌酶在稀释复性过程中的集聚现象. 实验发现, 在整个稀释复性过程中, 没有蛋白溶菌酶集聚体沉淀产生. 当最终复性液中蛋白溶菌酶浓度小于4.0 mg/mL时, 复性过程中不会形成蛋白溶菌酶分子集聚体; 当最终复性液中蛋白溶菌酶浓度介于4.0～8.0 mg/mL时, 复性过程中会形成由非共价相互作用所引起的蛋白溶菌酶二分子和三分子集聚体; 而当最终复性液中蛋白溶菌酶浓度大于8.0 mg/mL时, 复性过程中除了会形成二分子和三分子蛋白溶菌酶集聚体外, 还会形成四分子蛋白溶菌酶集聚体. 在此基础上, 结合文献, 对非还原脲变性蛋白溶菌酶的稀释复性过程进行了描述.     

Dielectric studies of binary mixtures of n -propyl alcohol and ethylenediamine

Dielectric constant (ε’) and dielectric loss (ε") of n-propyl alcohol (PA), ethylenediamine (EDA) and their binary mixtures, for different mole fractions of ethylenediamine have been experimentally measured at 11.15 GHz microwave frequency. Values of density (ρ), viscosity (η) and square refractive index (n _D ² ) of binary mixtures as well as those of pure liquids are reported. Excess square refractive index, viscosity and activation energy of viscous flow have also been estimated. These parameters have been used to explain the formation of complexes in the system.     

Influence of SMA content on the electro-optical properties of polymer-dispersed liquid crystal prepared by monodisperse poly(MMA-co-SMA)/LC microcapsules

Monodisperse poly(methyl methacrylate) (PMMA) particles containing various concentrations of stearyl methacrylate (SMA) were prepared, and a liquid crystal (LC) was swollen into the particles using a solute co-diffusion method (SCM). Phase separation behaviors between the polymer and LC were monitored by utilizing an optical and a polarized microscope (OM/POM). The monodisperse LC microcapsules were then applied to a polymer-dispersed liquid crystal (PDLC), and the electro-optical properties were investigated. As a result, the threshold and driving voltages were improved when the SMA content increased. The long alkyl chains of SMA in the capsules should exist at the interface of the LC and polymer resulting in an enhancement of phase separation between the polymer and LC, which largely influences the electro-optical properties of PDLC.     

Microgels and ionic associations in solutions of cellulose diacetate

Solutions of cellulose diacetate (CDA) from two sources (cotton linters and wood pulp Floranier) were analysed in various solvents by size exclusion chromatography (SEC). Without special precautions, the SEC chromatograms presented three peaks — or prehumps — before the main polymer peak. The first prehump which could be eliminated by ultracentrifugation corresponded to microgels whose sugar composition was determined. These microgels were also investigated by electron microscopy, X-ray and electron diffraction analysis. They corresponded mainly to cellulose triacetate (CTA-II) in the case of CDA from cotton linters and a mixture of CTA-II and xylan diacetate (XDA) in the case of CDA from the wood pulp Floranier. The second and third prehumps could be attributed to ionic effects corresponding to the association of remaining sulfate groups on the CDA molecules with residual calcium. It was found that these ionic effects could be eliminated by the addition of LiBr or LiCl to the elution solvents. This led to chromatograms devoid of prehumps.Presented in part at the Cellulose '91 meeting in New Orleans.     

Dansyl-Modified γ-Cyclodextrin as a fluorescent sensor for molecular recognition

The crystal structure of thiamine iodide sesquihydrate has been determined by X-ray diffraction methods as a host-guest model for coenzyme-substrate interactions. The asymmetric unit contains two chemical units. Both the thiamine molecules A and B, which are crystallographically independent, assume the usualF conformation and have a disordered hydroxyethyl side chain. An iodide anion (or a water molecule) bridges the pyrimidine and thiazolium rings of molecule A (or B) by forming a hydrogen bond with the amino group and an electrostatic contact with the thiazolium ring to stabilize the molecular conformation. In the crystal the thiamine molecules self-associate to form a pipe-like polymeric structure, in which four thiamine hosts surround an iodide guest and hold it through C(2)-H...I hydrogen bonds and thiazolium...I electrostatic interactions. Crystal data: C₁₂H₁₇N₄OS⁺·I^– · 1.5 H₂O, monoclinic,P2₁/c, a=12.585(2), b=25.303(5), c=12.030(2) Å, =115.15(1)°,V=3468(1) ų,Z=8,D _c=1.606 g cm^–3,R=0.045 for 3328 observed reflections. Supplementary Data relating to this article are deposited with the British Library as Supplementary Publication No. SUP. 82156 (13 pages).     

Synthesis of new titanatranes containing organic substituents in the atrane fragment

Titanatrane CpTi(OCH(CH₃)CH₂)₃N (3) was prepared by the reaction of CpTiCl₃ with N(CH₂CH(CH₃)OH)₃ in the presence of triethylamine. The reaction of CpTi(OMe)₃ (8) with N(CH₂CH₂OH)₂(CH₂CHPhOH), erythro-N(CH₂CH₂OH)₂(CHPhCHPhOH), and N(CH₂CH₂OH)₂(CH₂CPh₂OH) gave cyclopentadienyltitanatranes 12–14. Compound 8 reacts with threo-N(CH₂CH₂OH)₂(CHPhCHPhOH) to give a mixture of threo-CpTi(OCH₂CH₂)₂(OCHPhCHPh)N and threo-MeOTi(OCH₂CH₂)₂(OCHPhCHPh)N. Slow hydrolysis of the latter product gave threo-[Ti₃O(OMe){(OCH₂CH₂)₂₋ (OCHPhCHPh)N} ₃]₂, which was studied by X-ray diffraction analysis. The crystal structures of 3 and 12 were also determined by X-ray diffraction analysis. The titanium coordination polyhedron in these complexes is a distorted trigonal bipyramid in which the equatorial positions are occupied by three oxygen atoms and the axial positions contain the N atom and the Cp group. The titanium—nitrogen distances (2.313(2), 2.291(2) Å in two independent molecules of 3 and 2.271(2) Å in compound 12) confirm the presence of Ti←N transannular interaction. Published in Russian in Izvestiya Akademii Nauk. Seriya Khimicheskaya, No. 12, pp. 2736–2744, December, 2005.     

Model dipeptides incorporating the trans cyclohexane analogues of phenylalanine: further evidence of the relationship between side-chain orientation and β-turn type

In order to study the influence of the side-chain orientation on the peptide backbone conformation we have synthesised the model dipeptides t-BuCO-l-Pro-(1S,2R)-c₆Phe-NHMe and t-BuCO-l-Pro-(1R,2S)-c₆Phe-NHMe, incorporating each enantiomer of the trans cyclohexane analogue of phenylalanine (trans-1-amino-2-phenylcyclohexanecarboxylic acid). The orientation of the aromatic side-chain determines the β-turn type accommodated by these peptides to the point that the (1S,2R)-c₆Phe derivative retains the type I β-turn in the crystalline state, in contrast to the behaviour exhibited by the natural counterpart t-BuCO-l-Pro-l-Phe-NHMe.     

Three-dimensional hydrogen-bond geometry and probability information from a crystal survey

Summary An extensive crystal survey of the Cambridge Structural Database has been carried out to provide hydrogen-bond data for use in drug-design strategies. Previous crystal surveys have generated 1D frequency distributions of hydrogen-bond distances and angles, which are not sufficient to model the hydrogen bond as a ligand-receptor interaction. For each hydrogen-bonding group of interest to the drug designer, geometric hydrogen-bond criteria have been derived. The 3D distribution of complementary atoms about each hydrogen-bonding group has been ascertained by dividing the space about each group into bins of equal volume and counting the number of observed hydrogen-bonding contacts in each bin. Finally, the propensity of each group to form a hydrogen bond has been calculated. Together, these data can be used to predict the potential site points with which a ligand could interact and there-fore could be used in molecular-similarity studies, pharmacophore query searching of databases, or de novo design algorithms.     

Syntheses, crystal structures and magnetic properties of a new nitronyl nitroxide NIT2-bithph and its manganese(II) compound [Mn(hfac)2(IMHBithph)]2·(NIT2-bithph)(C6H14)

A new nitronyl nitroxide NIT2-bithph (1) and its manganese(II) compound [Mn(hfac)₂(IMHBithph)]₂·(NIT2-bithph)(C₆H₁₄) (2) (hfac = hexafluoroacetylacetonate; NIT2-bithph = 4,4,5,5-tetramethyl-2-(bithiophenal-2-yl)imidazoline-1-oxyl-3-oxide; IMHBithph = 1-hydroxy-2-bithiophenal-4,4,5,5-tetramethyl-4,5-dihydro- 1H-imidazole) have been synthesized and structurally characterized by X-ray diffraction methods. The units of compound 1 were connected as one-dimensional chain by the intermolecular hydrogen bonds which afford an intermolecular antiferromagnetic interaction between nitronyl nitroxide radicals within the chain (J = −1.89 cm⁻¹). Compound 2 resulting from the reaction of Mn(hfac)₂·2H₂O and NIT2-bithph is dinuclear and includes the reduced amidino-oxide form of NIT2-bithph, it is made up of three parts: a [Mn(hfac)₂(IMHBithph)]₂ dimer unit, an uncoordinated NIT2-bithph radical and a noncoordinated solvent molecule of hexane, the molecule of radical is hydrogen bonded to its reduced form. Two reduced IMHBithph ligands bridge the two manganese(II) ions through their amidino-oxide oxygen atoms resulting in a small intramolecular antiferromagnetic interaction between the manganese ions (J = −1.55 cm⁻¹).     

The predictive accuracy for estimating infinite dilution activity coefficients by γ∞-based UNIFAC

The predictive accuracy for estimating infinite dilution activity coefficients by a modification of the UNIFAC method wherein the group interaction parameters were based on only data (referred to as -based UNIFAC) has been studied. Estimates and measured values were compared for six prototypical solutes in a series of homologous n-alkanes, l-alcohols and alkanenitrile solvents. Despite the fact that the interaction parameters were derived using only data, this approach still gave serious errors due to several inherent problems in the original UNIFAC model. Its performance is sometimes even poorer than that of the original UNIFAC method. For example for nitromethane in alcohols and p-dioxane in nitriles values predicted by the -based UNIFAC are essentially zero. The large errors for these systems are most likely due to inaccurate interaction parameters in the -based UNIFAC method.