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31.
Einar Uggerud 《Theoretical chemistry accounts》1997,97(1-4):313-316
The potential energy hypersurface of protonated glycine, GH+, has been investigated. The calculated G2(MP2) value for the proton affinity (PA) of glycine, PA
calc=895kJ mol−1, is in good agreement with the experimental value which has been estimated to lie in the range 864kJ mol−1 < PA
exp
<891kJ mol−1. Ab initio quantum chemical calculations of relevant parts of the potential energy surface of GH+ give a reaction model which is consistent with the observed mass spectrometric fragmentation pattern. The lowest energy unimolecular
reactions of GH+ are two distinct processes: (1) loss of CO, which has a substantial barrier for the reverse reaction, and (2) loss of CO
plus H2O, which has no barrier for the reverse reaction.
Received: 15 November 1996 / Accepted: 6 May 1997 相似文献
32.
文章对5种碳五位(C5)的不同取代基海因的质子北合能(PA),在亚稳状态下采用“动能法”进行了研究。以5,5-甲基海因作为参照,确定了5种样品亲质子能的顺序。 相似文献
33.
P. A. Stuzhin E. A. Pozdysheva O. V. Mal’chugina I. A. Popkova C. Ercolani 《Chemistry of Heterocyclic Compounds》2005,41(2):246-254
AM1 calculations gave the proton affinities of different types of donor sites in tetrakis-3,4-(1,2,5-thiadiazolo)porphyrazine, H2{[SN2)4PA}, and protonation of the meso-nitrogen atoms was found to be favored. A spectrometric study showed that the basicity of the meso-nitrogen atoms of the porphyrazine macrocycle is strongly diminished and these atoms in CF3CO2H are involved in an incomplete acid-base interaction (ABI) to give acid solvates, while a complete ABI (protonation) is found only in the presence of sulfuric acid. The basicity constants of the meso-nitrogen atoms were determined spectrophotometrically in CF3CO2H-H2SO4. The kinetics of decomposition of the macrocyclic chromophore in concentrated sulfuric acid was studied and a possible mechanism for this process was proposed.__________Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 2, pp. 278–287, February, 2005. 相似文献
34.
在苄叉丙二腈衍生物系列中,N,N-二烷基氨基苄叉丙二腈及其类似化合物是研究和应用较多的一类。它们曾作为分子探针应用于高分子微环境特性和高分子聚合过程的研究。作为一种分子内的电荷转移络合物,它们在不同溶剂中的光谱行为也进行过研究,从而为进一步的开拓应用提供了重要依据。和前者相比,对-羟基苄叉丙二腈无论在基础研究或实际应用上都显得比较薄弱。正因如此,本工作合成了该化合物并对它进行了初步研 相似文献
35.
Using a multireferent MBPT method (CIPSI) the electronic affinity (EA) of F, CN and HCC is computed. Results show how UMP2 gives unbalanced truncation of the MP series, while ROMP2 has the correct (balanced) behaviour. The good agreement with the experimental EA found for some compounds is accidental and associated to an error compensation. The good agreement with the experimental data found for the ROMP2 and CIPSI EAs is analysed.This paper was presented at the International Conference on The Impact of Supercomputers on Chemistry, held at the University of London, London, UK, 13–16 April 1987 相似文献
36.
Detlef Schrder Jessica Loos Helmut Schwarz Roland Thissen Jana Roithova Zdenek Herman 《International journal of mass spectrometry》2003,230(2-3):113
Singly and doubly charged C4H3+/2+ ions generated upon electron ionization (EI) of the neutral precursors 1,3-butadiene, benzene, and exo-methylene cyclopropane, respectively, are examined by sector-field mass-spectrometry. Charge stripping of the mass-selected monocations affords the corresponding dications and charge exchange of the C4H32+ dications allows for the reverse redox process. Refined analysis and additional MS/MS studies suggest that the monocations are mixtures of isomeric ions formed upon ionization, whereas only a single type of dication seems to be formed. As an average of energy-resolved measurements, a vertical ionization energy of IEv(C4H3+)=16.5±0.4 eV is derived. In addition to the experimental work, density functional theory is used for a computational exploration of the mono- and dicationic species. The best theoretical estimates are IEa(C4H3+)=16.33 eV and IEv(C4H3+)=16.49 eV for the most stable isomer H2C=C---CCH+. Combination of the experimental and theoretical findings leads to the conclusion that the diacetylene cation C4H2+ has indeed a positive proton affinity of PA(C4H2+)=1.50±0.42 eV. 相似文献
37.
Hiratake J 《Chemical record (New York, N.Y.)》2005,5(4):209-228
Carefully designed molecules that are intimately related to the reaction mechanism of enzymes are often highly selective and potent inhibitors that serve as extremely useful chemical probes for understanding the reaction mechanism and structure of enzymes. This article describes the design, synthesis, and applications of specific inhibitors of two mechanistically distinct groups of enzymes, ATP-dependent amide ligases and Ser- and Thr-hydrolases. Our strategy is based on the premise that stable analogues of the transition state (transition-state analogues) are highly potent inhibitors that serve as good mechanistic probes, and that a key structure of a good inhibitor of one enzyme is also utilized for the inhibitors of other enzymes that share the same chemistry in their catalyzed reactions, irrespective of the degree of structural similarity and evolutionary link between the enzymes. According to these principles, we designed and synthesized a series of phosphinate- and sulfoximine-based transition-state analogue inhibitors of glutathione synthetase, gamma-glutamylcysteine synthetase and asparagine synthetase. For the second group of enzymes, we synthesized a gamma-monofluorophosphono glutamate analogue for mechanism-based affinity labeling of gamma-glutamyltranspeptidase and fluorescent phosphonic acid esters for the active-site titration of lipase. These inhibitors were used successfully as ligands for detailed kinetic analyses, X-ray crystallography, and mass analysis of the enzymes to identify the key amino acid residues responsible for catalysis and substrate recognition in the transition state. 相似文献
38.
The concerted mechanism of phosphate-catalyzed proton exchange in N,N'-dimethylurea has been studied. Kinetic data were measured using the technigue of NMR line-shape analysis. A significant kinetic isotope effect was observed for the concerted proton transfer in N,N'-dimethylurea and is attributed to the tunnelling effect. 相似文献
39.
A Triton X-100-4.0G-D (4.0G-D refers to a 4.0-generation dendrimer) was brought forward as a new phosphorescence labeling reagent. Two types of specific affinity adsorption (AA) reactions (direct method and sandwich method) were carried out between the labeling product of Triton X-100-4:0G-D-Wheat germ agglutinin (WGA) and alkaline phosphatase (ALP), the product of AA reaction preserved the good characteristics of room temperature phosphorescence (RTP) of 4.0G-D and △Ip of the product was proportional to the content of ALP. According to the fact stated above, a new method for the determination of trace ALP by affinity adsorption solid substrate-room temperature phosphorimetry (AA-SS-RTP) was established on the basis of WGA labeled with the Triton X-100-4.0G-D. The detection limits were 0.20 ag·spot^-1 (corresponding concentration: 5.0×10^-16 g·mL^-1, namely 5.0×10^-18 mol·L^-1) for a direct method and 0.14 ag·spot^-1 (corresponding concentration: 3.5×10^-16 g·mL^-1, namely 3.5×10^-18 mol·L^-1) for a sandwich method, respectively. For their high sensitivity, good repeatability and high accuracy, the direct method and sandwich method have been successfully appfied to determine the content of ALP in human serum, and the results were coincided with the clinical detection results of the enzyme-linked immunosorbent assay method by the Zhangzhou Hospital of Traditional Chinese Medicine. Meanwhile, the mechanism for the determination of trace ALP by AA-SS-RTP was discussed. 相似文献
40.
Geometries and electronic structures of W4 and W clusters were studied by use of density functional methods B3LYP, B3P86, B3PW91, BHLYP, BLYP, and MPW1PW91. The calculated results indicate that the three‐dimensional structure of singlet state with either D2d symmetry (B3LYP, B3P86, B3PW91, BLYP, and MPW1PW91) or C2v symmetry (BHLYP) is the ground state for the W4 cluster. For the W cluster, the doublet state is preferred, and the most stable structure is also 3D with either D2d symmetry (B3LYP, B3PW91, BHLYP, BLYP) or C2v symmetry (B3P86 and MPW1PW91). The calculated electron affinity at B3P86 gives the best performance compared with experiment. For the dissociation channel, W + W3 is suggested to be the possible route for the W4 cluster. For the W cluster, W + W is the most likely route for dissociation, in agreement with experiment. © 2004 Wiley Periodicals, Inc. Int J Quantum Chem, 2005 相似文献