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281.
J. Baran A. J. Barnes M. K. Marchewka A. Pietraszko H. Ratajczak 《Journal of Molecular Structure》1997,416(1-3):33-42
The crystal structure of bis(betaine)-selenic acid has been determined by X-ray diffraction as orthorhombic, space group Pbca, with a = 11.591(2), b = 22.930(5), c = 12.045(2) Å and Z = 8. The crystal comprises hydrogen selenate ions, HSeO−4, and two distinct betaine molecules, which are held together into a complex by short hydrogen bonds. One of the betaine molecules is present as the zwitterion form (CH3)3N+---CH2---COO− and the second occurs as the protonated form (CH3)3N+---CH2---COOH. Powder FTIR and Raman spectra were measured. An assignment of the observed bands to vibrations of the hydrogen bonds and internal vibrations of the hydrogen selenate ion and the betaine molecules is proposed. 相似文献
282.
Parameterization of peptide 13C carbonyl chemical shielding anisotropy in molecular dynamics simulations. 总被引:1,自引:0,他引:1
Daniel M Jordan K Maria Mills Ioan Andricioaei Akash Bhattacharya Kim Palmo Erik R P Zuiderweg 《Chemphyschem》2007,8(9):1375-1385
NMR chemical shielding anisotropy (CSA) relaxation is an important tool in the study of dynamical processes in proteins and nucleic acids in solution. Herein, we investigate how dynamical variations in local geometry affect the chemical shielding anisotropy relaxation of the carbonyl carbon nucleus, using the following protocol: 1) Using density functional theory, the carbonyl (13)C' CSA is computed for 103 conformations of the model peptide group N-methylacetamide (NMA). 2) The variations in computed (13)C' CSA parameters are fitted against quadratic hypersurfaces containing cross terms between the variables. 3) The predictive quality of the CSA hypersurfaces is validated by comparing the predicted and de novo calculated (13)C' CSAs for 20 molecular dynamics snapshots. 4) The CSA fluctuations and their autocorrelation and cross correlation functions due to bond-length and bond-angle distortions are predicted for a chemistry Harvard molecular mechanics (CHARMM) molecular dynamics trajectory of Ca(2+)-saturated calmodulin and GB3 from the hypersurfaces, as well as for a molecular dynamics (MD) simulation of an NMA trimer using a quantum mechanically correct forcefield. We find that the fluctuations can be represented by a 0.93 scaling factor of the CSA tensor for both R(1) and R(2) relaxations for residues in helix, coil, and sheet alike. This result is important, as it establishes that (13)C' relaxation is a valid tool for measurement of interesting dynamical events in proteins. 相似文献
283.
Dobrochna Matkowska Maciej Gola Marcin ?nie?ek Piotr Cmoch Krzysztof Staliński 《Journal of organometallic chemistry》2007,692(10):2036-2045
A series of triorganotin hydrides and diorganotin dihydrides containing the optically active 2-(4-isopropyl-2-oxazolinyl)-5-phenyl ligand have been characterized by means of the multinuclear low-temperature NMR investigations, the results of which are discussed. In the corresponding organotin hydrides values of the 1J(1H-117/119Sn) couplings appeared to be temperature dependent, supporting an axial/equatorial position of the hydrogen attached to the tin. 相似文献
284.
Svetlana V. Amosova Vladimir A. Shagun Natalia A. Makhaeva Konstantin A. Lysenko 《Journal of organometallic chemistry》2007,692(16):3307-3315
The structure of 2,4-dibromo-2-dibromomethyl-3,3-dimethyl-1-selena-3-silacyclopentene-4, formed by regioselective electrophilic addition of SeBr4 to dimethyl diethynyl silane, has been determined using X-ray analysis technique. Quantum chemistry methods were used to study elementary stages of the reaction. It was found that the first stage consisted of SeBr4 conversion into bimolecular complex Br2?SeBr2, initiated by dimethyl diethynyl silane. Possible formation of five-membered and six-membered heterocycles involves different cyclization mechanisms. The formation of only five-membered heterocycle is explained by kinetically preferable ring closure through four-center transition state. The conclusions obtained by calculations were confirmed by monitoring of the reaction using 1H NMR method. 相似文献
285.
Fluorometric investigation of the interaction of bovine serum albumin with surfactants and 6-mercaptopurine 总被引:2,自引:0,他引:2
Hu YJ Liu Y Jiang W Zhao RM Qu SS 《Journal of photochemistry and photobiology. B, Biology》2005,80(3):235-242
Fluorescence quenching in solutions of bovine serum albumin has been investigated in the presence of 6-mercaptopurine and ionic surfactants. Spectroscopic analysis of the emission quenching at different temperatures revealed that the quenching mechanism of bovine serum albumin by 6-mercaptopurine was dynamic quenching mechanism. The Stern–Volmer quenching model has been successfully applied, and the activation energy of the interaction between 6-mercaptopurine and bovine serum albumin as much as 4.26 kJ mol−1 was calculated. The distance r between donor (bovine serum albumin) and acceptor (6-mercaptopurine) was obtained according to fluorescence resonance energy transfer (FRET). The result of synchronous fluorescence spectra shows that the conformation of bovine serum albumin has been changed at the present of 6-mercaptopurine. 相似文献
286.
L.A. Isupova I.S. Yakovleva I.I. Gainutdinov Yu.T. Pavlyukhin V.A. Sadykov 《Reaction Kinetics and Catalysis Letters》2004,81(2):373-382
The phase composition and microstructure of samples of the La1-xCaxFeO3-y system prepared via a ceramic route were characterized by M?ssbauer spectroscopy. In all cases, iron was found in the 3+ state. The ordering
of anion vacancies in the samples with the composition in the range of 0.8 > x ≥ 0.4, which corresponds to a microheterogeneous
solid solution, generates new distorted octahedral and fivefold/tetrahedral sites revealed by two typical sextets. The disordering
of this solid solution and small (10-100 ?) sizes of domains with a perovskite, braunmillerite or Grenier phase structure
caused the appearance of a superparamagnetic doublet, which grows with the Ca content up to x = 0.8 but disappears in the
sample of pure braunmillerite. The appearance of Fe cations in a distorted coordination correlates with the increased activity
of the samples with a microheterogeneous structure in the CO catalytic oxidation and with their reducibility by H2.
This revised version was published online in August 2006 with corrections to the Cover Date. 相似文献
287.
K. Dimroth A. Berndt F. Br A. Schweig R. Volland 《Angewandte Chemie (International ed. in English)》1967,6(1):34-40
The distribution of the unpaired electron over the oxygen and the 24 carbon atoms in the free 2,4,6-triphenylphenoxy radical was determined by electron spin resonance spectroscopy and quantum-mechanical approximation methods. The hyperfine splitting was evaluated with the aid of the spectra of triphenylphenoxyls deuterated in some or all of the substituent phenyl groups. The results of the quantum-mechanical approximations were checked by recording the ESR spectra of triphenylphenoxyls labeled with 13C in positions 1,2,3, or 4 of the central ring. The spin density distribution permits a first discussion of the 17O-coupling constants of correspondingly labeled triphenylphenoxyl and other organic free radicals. 相似文献
288.
Recent developments in quantitative surface analysis by Auger (AES) and x-ray photoelectron (XPS) spectroscopies are reviewed and problems relating to a more accurate quantitative interpretation of AES/XPS experimental data are discussed. Special attention is paid to consideration of elementary physical processes involved and influence of multiple scattering effects on signal line intensities. In particular, the major features of core-shell ionization by electron impact, Auger transitions and photoionization are considered qualitatively and rigorous approaches used to calculate the respective transition probabilities are analysed. It is shown that, in amorphous and polycrystalline targets, incoherent scattering of primary and signal Auger and photoelectrons can be described by solving analytically a kinetic equation with appropriate boundary conditions. The analytical results for the angular and energy distribution, the mean escape depth, and the escape probability as a function of depth of origin of signal electrons as well as that for the backscattering factor in AES are in good agreement with the corresponding Mote Carlo simulation data. Methods for inelastic background subtraction, surface composition determination and depth-profile reconstructions by angle-resolved AES/XPS are discussed. Examples of novel techniques based on x-ray induced photoemission are considered. 相似文献
289.
Bonnie R. Hames Steven R. Thomas Amie D. Sluiter Christine J. Roth David W. Templeton 《Applied biochemistry and biotechnology》2003,105(1-3):5-16
New, rapid, and inexpensive methods that monitor the chemical composition of corn stover and corn stover-derived samples are
a key element to enabling the commercialization of processes that convert stover to fuels and chemicals. These new techniques
combine near infrared (NIR) spectroscopy and projection to latent structures (PLS) multivariate analysis to allow the compositional
analysis of hundreds of samples in 1 d at a cost of about $10 each. The new NIR/PLS rapid analysis methods can also be used
to support a variety of research projects that would have been too costly to pursue by traditional methods. 相似文献
290.
Most known perylene diimides are lipophilic, with few exceptions of hydrophilic derivatives. Even in the latter case, the compounds have limited water solubility and show a strong tendency to self-aggregation. In this paper we present the synthesis of four new perylene derivatives with three and four basic side chains, obtained by functionalizing the bay-area of perylene. These molecules show great solubility in aqueous media as hydrochlorides and their tendency to self-aggregate is remarkably reduced with respect to the previously synthesized two-chained perylene diimides. Their different spectroscopic properties in various solvents and conditions are reported and discussed. 相似文献