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71.
Eker F Griebenow K Schweitzer-Stenner R 《Journal of the American Chemical Society》2003,125(27):8178-8185
Determination of the precise solution structure of peptides is of utmost importance to the understanding of protein folding and peptide drugs. Herein, we have measured the UV circular dichroism (UVCD) spectra of tri-alanine dissolved in D(2)O, H(2)O, and glycerol. The results clearly show the coexistence of a polyproline II or 3(1)-helix and a somewhat disordered flat beta-strand conformation, in complete agreement with recent predictions from spectroscopic data (Eker et al. J. Am. Chem. Soc. 2002, 124, 14 330-14 341). A thermodynamic analysis revealed that enthalpic contributions of about 11 and 17 kJ/mol stabilize polyproline II in D(2)O and H(2)O, respectively, but at room temperature they are counterbalanced by entropic contributions, which clearly favor the more disordered beta-strand conformation. It is hypothesized that this delicate balance is the reason for the variety of structural propensities of amino acid residues in the absence of nonlocal interactions. The isotope effect yielding a higher occupation of polyproline II in H(2)O with respect to D(2)O strongly suggests that a hydrogen-bonding network involving the peptide and water molecules in the hydration shell plays a major role in stabilizing this conformation. The equilibrium between polyproline II and beta-strand is practically maintained in glycerol, which suggests that glycerol can substitute water as stabilizing solvent for the polyproline II conformation. We also measured the UVCD spectra of tri-valine and tri-lysine (both at acidic pD) in D(2)O and found them to adopt a flat beta-strand and left-handed turn structure, respectively, in accordance with recent analyses of vibrational spectroscopy data. Generally, the present study adds substantial evidence to the notion that the so-called random coil state of peptides is much more structured than generally assumed. 相似文献
72.
A pre-column fluorescence derivatization method is described for the high-performance liquid chromatographic determination of tyrosine-containing peptides. A tyrosyl residue in the peptide is first formylated in an alkaline medium in the presence of chloroform, and the resulting aldehyde is then converted into a fluorescent derivative by reaction with 1,2-diamino-4,5-dimethoxybenzene. The derivative is separated on a reversed-phase column (LiChrosorb RP-18) by isocratic elution with an aqueous acetonitrile-containing potassium chloride-hydrochloric acid buffer (pH 2.2) and sodium 1-hexanesulphonate. The method is selective and fairly sensitive; the lower limits of detection for the tyrosine-containing peptides tested are in the range 3.4-26.2 pmol in a 100-microliter injection volume. 相似文献
73.
Duanjun Xu Kunio Miki Yasushi Kai Nobutami Kasai Masanori Wada 《Journal of organometallic chemistry》1985,287(2):265-273
The structure of a nickel(II) complex, trans-[Ni(C6Cl5)(PMe2Ph)2{C(OMe)Me}]BF4, containing the simplest alkyl(alkoxy)carbene ligand has been determined by X-ray crystallography (R = 0.091). The geometry around the nickel atom is square-planar. The comparatively short NiC(1) bond length of 1.843(10) Å showed the presence of π-bonding in the nickel-carbene bond. 相似文献
74.
Huang WL Cui SH Liang KM Gu SR Yuan ZF 《Journal of colloid and interface science》2002,246(1):129-134
Silica xerogels were prepared by thermal drying wet gels in an electric oven (70 degrees C) after certain duration of ambient drying, and the relevant effect is investigated on the mesopore structures and surface fractal dimensions of the resultant xerogels. The silica gels were derived from a hydrochloric acid-catalyzed TEOS (tetraethylorthaosilicate) system, and both magnetic stirring and ultrasonic vibration were adopted during sol preparation. The percentage mesoporosity and surface fractal dimensions are evaluated using image analysis methods, based on FE-SEM (field emission gun-scanning electron microscopy) images. The results show that the mesoporosity of the resultant xerogels decreases with the duration of ambient drying for samples prepared using magnetic stirring and low-intensity ultrasonic vibration, while samples subjected to high-intensity ultrasound show a somewhat reverse trend. Samples prepared with magnetic stirring have almost constant surface fractal dimensions (nearly 3), irrespective of the ambient drying before thermal drying. The surface fractal dimensions of samples prepared using ultrasound increase with the duration of ambient drying. 相似文献
75.
Jian Zhang Zhao‐Ji Li Yi‐Hang Wen Yao Kang Jian‐Kai Cheng Yuan‐Gen Yao 《无机化学与普通化学杂志》2004,630(15):2731-2735
Two new metal succinates modified by rigid bipyridines, Cd(4, 4′‐bpy)(C4H4O4)·1/4H2O ( 1 ) and Cu(2, 2′‐bpy)(C4H4O4)0.5(NO3)(H2O) ( 2 ) (bpy = bipyridine), have been synthesized by hydrothermal reactions and structurally determined. Complex 1 crystallizes in the orthorhombic space group Cmca with the cell parameters a = 11.696(2), b = 15.554(2), c = 15.874(3) Å, α = β = γ = 90.00°, V = 2888(3) Å3, Z = 8. Complex 2 crystallizes in the triclinic space group with a = 7.077(1), b = 9.838(2), c = 10.461(2) Å, α = 71.941(3)°, β = 73.078(3)°, γ = 74.502(3)°, V = 649.8(2) Å3, Z = 2. In complex 1 , a 2‐D network was formed by Cd‐succinato bonding. The 2‐D networks are pillared by 4, 4′‐bpy ligands, forming a 3‐D grid framework. The 2‐fold interpenetration of the resulting 3‐D frameworks completes the molecular structure. In complex 2 , the CuII atom adopts a distorted octahedral in which the CuII atoms are bridged by two H2O molecules into an infinite zigzag chain, [Cu2(H2O)2(C4H4O4)]n. The neighboring chains are further linked by π‐π stacking interactions into a 2‐D network, and the interlayer hydrogen bonds lead to the final 3‐D crystal structure. 相似文献
76.
A new activation method has been developed for electroless copper plating on silicon wafer based on palladium chemisorption on SAMs of APTS without SnCl2 sensitization and roughening condition.A closely packed electroless copper film with strong adhesion is successfully formed by AFM observation.XPS study indicates that palladium chemisorption occurred via palladium chloride bonding to the pendant amino group of the SAMs. 相似文献
77.
78.
能量选择中子成像技术是利用特定范围波长(能量)的中子进行成像。在热/冷中子范围内(<25meV),能量选择中子成像技术主要基于布拉格边效应和衍射机制,相比常规中子成像技术不但可以显著提高图像对比度,而且能分析应变、应力、织构。在超热中子范围内(>1eV),能量选择中子成像技术主要基于中子共振吸收,中子截面随能量变化是同位素特有的,存在明显的共振吸收峰,因此可以进行同位素的“指纹”识别。能量选择中子成像技术在工程、材料、化学、物理、生物、考古等众多科研领域中有着非常广阔的应用前景。 相似文献
79.
Kai Sun Anzai Shi Yan Liu Xiaolan Chen Panjie Xiang Xiaotong Wang Lingbo Qu Bing Yu 《Chemical science》2022,13(19):5659
General photoactivation of electron donor–acceptor (EDA) complexes between arylsulfonium salts and 1,4-diazabicyclo[2.2.2]octane with visible light or natural sunlight was discovered. This practical and efficient mode enables the production of aryl radicals under mild conditions, providing an unrealized opportunity for two-step para-selective C–H functionalization of complex arenes. The novel mode for generating aryl radicals via an EDA complex was well supported by UV-vis absorbance measurements, nuclear magnetic resonance titration experiments, and density functional theory (DFT) calculations. The method was applied to the regio- and stereo-selective arylation of various N-heterocycles under mild conditions, yielding an assembly of challengingly linked heteroaryl–(hetero)aryl products. Remarkably, the meaningful couplings of bioactive molecules with structurally complex drugs or agricultural pharmaceuticals were achieved to display favorable in vitro antitumor activities, which will be of great value in academia or industry.General photoactivation of EDA complexes between arylsulfonium salts and 1,4-diazabicyclo[2.2.2]octane was discovered. This practical mode enables the generation of aryl radicals for C–H functionalization of arenes. 相似文献
80.
原子荧光光谱分析是一种非常实用的痕量分析技术。酸化过的小麦粉溶液中的汞与还原剂硼氢化钾反应,生成氢化物;过量氢气和气态氢化物与载气混合,进入原子化器,汞空心阴极灯激发氩氢焰中的汞原子,跃迁回基态时发出的荧光信号被日盲光电倍增管接收,然后经放大、解调、再由数据处理系统得到结果。在使用AFS2202E型原子荧光光度计检测小麦粉中汞时,应注意以下几个问题。1试样消解以微波消解最为理想,但消解装置价格太高;常压回流消解耗时太长;与单体高压消解罐相比较经济、省时。(1)消解时应注意烘箱温度的控制,以120℃为宜,3 h即可;温度高些,… 相似文献