质子化丙酮分子团簇的结构和振动光谱

用密度泛函B3LYP/ 6 3 1G(d)方法 ,对质子化丙酮分子团簇 (CH3COCH3) nH+ (n =1～ 7)弱相互作用体系进行了全自由度能量梯度优化 ,得到了该系列团簇的稳定结构及其对应的体系能量 .通过对构型的分析得出了质子化丙酮分子团簇 (CH3COCH3) nH+ (n =1～ 7)的生长规律 .计算了中性丙酮分子团簇体系的质子亲合能并总结出其变化趋势 .分析讨论了质子化团簇的红外振动光谱 ,发现质子化团簇的振动光谱普遍较中性环型团簇的振动光谱复杂 ,最强的振动峰来源于质子在溶剂壳中两个氧原子之间的振动 ,而且随着团簇尺寸的增加羰基的伸缩振动峰的数目也随之增多     

New aspects of the protonation of biliverdins

Biliverdins undergo appreciable self association in acidic solutions especially if solvents like benzene or chloroform are employed. The population of aggregates further depends on the concentration of both the acid and the solute. In chloroform and benzene solutions at high acidity a doubly protonated species is formed. This is concluded from a combinatory evaluation of the CD and electronic absorption spectra of chiral optically active biliverdins (1–6) in benzene, chloroform, and ethanol solutions containing trifluoroacetic acid or hydrochloric acid. The aggregates formed at medium acid concentrations exhibit largeCotton effects in the long-wavelength absorption bands and thus dominate the CD spectra. Similarly, agrregates are the main contributors to theCotton effects of achiral, protonated biliverdins in (S)-(–)-ethyl lactate (SICD) at usual concentrations. The consequence and relevance of these findings with regard to the recent literature is briefly discussed.Dedicated to Prof. Dr.Karl Schlögl on occasion of his 60^th birthday.     

Molar heat capacities and volumes of transfer of cytosine,thymine, caffeine and 1,3-diethylthymine to aqueous solutions of glycyl-glycine and L-α-alanyl-L-α-alanine at 25°C

Densities and specific heat capacities of ternary aqueous systems containing dipeptides (glycyl-glycine or L--alanyl-L--alanine) and nucleic acid bases (cytosine or thymine) or their alkyl derivatives (1,3-diethylthymine or caffeine) were determined at 25°C by flow calorimetry and flow densimetry. The partial molar volumes and heat capacities of transfer at infinite dilution of the different nucleic acid bases from water to water+dipeptide solutions were obtained therefrom. Except for the case of the transfer of cytosine to aqueous glycyl-glycine solutions where a small positive dependence of the transfer quantities was observed with the dipeptide concentration, the values of the heat capacities of transfer were in general low, positive or negative, depending on the compensation of hydrophobic-hydrophilic interactions between the dipeptide and the base. The volumes of transfer of most of the bases are very small, within the limit of the experimental error.     

Interaction of adenine and thymine with aqueous sugar solutions

The solubility of the nucleic acid bases, adenine and thymine, in aqueous erythritol, xylose, glucose, and sucrose solutions has been studied. The solubility of adenine increases linearly with glucose and sucrose concentration, whereas with the other reagents a nonlinear increase is observed. Below 1.5M reagent concentration, the solubility of adenine increases in the order erythritol < robose, xylose < glucose < sucrose. The solubility of thymine in these solutions, on the other hand, decreases, increases, or does not change depending upon the reagent. The effect of temperature on the solubility of adenine and thymine in sugar solution indicates that the transfer of these molecules from water to sugar solution is exothermic.Presented in part at the VIIth All-India Symposium in Biophysics held at Visva Bharati University during October 1976.     

Application of pure silica gel as cation-exchange stationary phase in lon chromatography with indirect photometric detection for common mono-and divalent cations using aromatic monoamines as eluents

Summary A pure silica gel (Pia Seed 5S-60-SIL), synthesized by the hydrolysis of pure tetraethoxysilane [Si(OCH₂CH₃)₄], was applied as a cation-exchange stationary phase in ion chromatography with indirect photometric detection for common mono-and divalent cations (Li⁺, Na⁺, NH₄ ⁺, K⁺, Mg²⁺, and Ca²⁺) using various protonated aromatic monoamines (tyramine [4-(2-aminethyl) phenol], benzylamine, phenylethylamine, 2-methylpyridine and 2,6-dimethylpyridine) as eluet ions. When using 0.75 mM tyramine-0.25 mM oxalic acid-1.5 mM 18-crown-6 (1,4,7,10,13,16-hexaoxacyclooctadecane) at pH 5.0 as the eluent, excellent simultaneous separation and highly sensitive detection at 275 nm for these mono-and divalent cations were achieved on the Pia Seed 5S-60-SIL column (150×4.6 mm I.D.) in 20 min.     

On the Effect of Organic Substitution of Silicon Alkoxides in Poly(Vinyl Acetate) Organic-Inorganic Composites

Abstract

Organic-inorganic composites (OICs) were prepared via the in-situ polymerization of an organically (phenyl) substituted trialkoxysilane, phenyltriethoxysilane (PhTEOS), in the presence of poly(vinyl acetate) (PVAc). The mechanical reinforcement above T _g previously observed in OICs of unfunctionalized organic polymers such as PVAc with acid catalyzed in-situ polymerized tetraalkoxysilane was not observed when the tetraalkoxysilane was replaced with PhTEOS. Although both systems are optically transparent and both exhibit a high degree of hydrogen bonding between the carbonyl of PVAc and the residual hydroxyls of the silicate, the polymerization of the alkoxide is different. The tetra-functional alkoxide polymerizes to form a load-supporting silicate network, leading to a high plateau in the tensile modulus above T _g, whereas the trifunctional alkoxide reacts to form primarily low molecular weight oligomers. These increase the T _g of the PVAc but do not provide mechanical reinforcement.     

Prebiotic Route to Thymine from Formamide—A Combined Experimental–Theoretical Study

Synthesis of RNA nucleobases from formamide is one of the recurring topics of prebiotic chemistry research. Earlier reports suggest that thymine, the substitute for uracil in DNA, may also be synthesized from formamide in the presence of catalysts enabling conversion of formamide to formaldehyde. In the current paper, we show that to a lesser extent conversion of uracil to thymine may occur even in the absence of catalysts. This is enabled by the presence of formic acid in the reaction mixture that forms as the hydrolysis product of formamide. Under the reaction conditions of our study, the disproportionation of formic acid may produce formaldehyde that hydroxymethylates uracil in the first step of the conversion process. The experiments are supplemented by quantum chemical modeling of the reaction pathway, supporting the plausibility of the mechanism suggested by Saladino and coworkers.     

多光子电离下醇类团簇中的反应

应用Nd:YAG(Spectra-Physics LAB-170)脉冲激光器输出的355nm紫外激光实现了对甲醇、乙醇及正丙醇的多光子电离,对每一种样品通过质谱技术都观测到了两个质子化团簇离子系列:(R..3OH)nH 和(R1,2,3OH)n(H2O)H (R1,2,3代表CH2、CH2CH2及CH2CH3CH2),结合在HF/STO-3G和B3LYP/6-31G 水平上的从头计算对其反应通道做了分析,发现其产生经过了团簇内部的质子转移反应及离子-分子反应,且质子主要来自于羟基上的氢离子.并结合从头算分析了(R1,2,3OH)nH 的结构,给出了幻数团簇(R1,2,3OH)3H 的构型.同时对(R1,2,3)n(H2O)H 系列只在n值较大时出现做了相应的解释.     

Identification of radiation-induced cross-linking between thymine and tryptophan by electrospray ionization-mass spectrometry

Upon exposure to ionizing radiation, DNA undergoes a variety of modifications including the production of a covalent bond between the nucleobase thymine and aromatic amino acids. In this work, electrospray ionization-mass spectrometry(ESI-MS) was used to identify the gamma radiation-induced covalent cross-linking of model peptides (sequence YPPW and pYPPW) with the nucleobase thymine. Tandem electrospray ionization-mass spectrometry (ESI-MSn) was employed to investigate the cross-linking sites. The results showed that irrespective of whether tyrosine was phosphorylated or not, the nucleobase thymine was cross-linked with the tryptophan residue. Possible cross-linking mechanisms are proposed by investigating the related mass peaks.