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31.
Low temperature infrared spectra of light induced metastable states MS1 and MS2 of the nitroprusside anion in Na(2)[Fe(CN)(5)NO].2H(2)O, isotopically normal and substituted with (15)NO and N(18)O, are presented and discussed. As a consequence of the relatively high population of the MS2 state achieved by further irradiation with 1064 nm light of samples previously irradiated with 488.0 nm light, new bands were seen for the first time, and others, previously reported, were confirmed. The comparison of the spectral data obtained for the FeNO moiety of the isotopically normal as well as of the (15)NO and N(18)O substituted anion with the results of quantum chemical (DFT) calculations support the assignment of the bands which appear after successive irradiations to MS1, the linear Fe(eta(1)-ON) linkage isomer, and to MS2, the side-bound Fe(eta(2)-NO) isomer. 相似文献
32.
Cristina ZuccaPierfrancesco Bravo Luciana MalpezziAlessandro Volonterio Matteo Zanda 《Journal of fluorine chemistry》2002,114(2):215-223
Aldol reactions of titanium enolates of N-acyl-1,3-oxazolidin-2-ones with ethyl trifluoropyruvate occurred with low to good stereoselectivity depending on the steric properties of the N-acyl group. Attempts to transform the resulting aldols into peptidomimetics incorporating stereo-defined α-trifluoromethyl (Tfm)-malic units are described. 相似文献
33.
Xin-Liang Li Lars G. Ljungdahl Eduardo A. Ximenes Huizhong Chen Carlos R. Felix Michael A. Cotta Bruce S. Dien 《Applied biochemistry and biotechnology》2004,113(1-3):233-250
A β-glucosidase (BglA, EC 3.2.1.21) gene from the polycentric anaerobic fungus Orpinomyces PC-2 was cloned and sequenced. The enzyme containing 657 amino acid residues was homologous to certain animal, plant, and
bacterial β-glucosidases but lacked significant similarity to those from aerobic fungi. Neither cellulose- nor protein-binding
domains were found in BglA. When expressed in Saccharomyces cerevisiae, the enzyme was secreted in two forms with masses of about 110 kDa and also found in two forms associated with the yeast
cells. K
m
and V
max
values of the secreted BglA were 0.762 mM and 8.20 μmol/(min·mg), respectively, with p-nitrophenyl-β-d-glucopyranoside (pNPG) as the substrate and 0.310 mM and 6.45 μmol/(min·mg), respectively, for the hydrolysis of cellobiose. Glucose competitively inhibited the hydrolysis of
pNPG with a K
i
of 3.6 mM. β-Glucosidase significantly enhanced the conversion of cellulosic materials into glucose by Trichoderma reesei cellulase preparations, demonstrating its potential for use in biofuel and feedstock chemical production.
Names are necessary to report factually on available data; however, the USDA neither guarantees nor warrants the standard
of the product, and the use of the name by USDA implies no approval of the product to the exclusion of others that may be
suitable. 相似文献
34.
A stochastic method of optimization, which combines simulated annealing with simplex, is implemented to fit the parameters of a simple model potential. The main characteristic of the method is that it explores the whole space of the parameters of the model potential, and therefore it is very efficient in locating the global minimum of the cost function, in addition to being independent of the initial guess of the parameters. The method is employed to fit the complex intermolecular potential energy surface of the dimer of water, using as a reference the spectroscopic quality anisotropic site-site potential of Feller et al. The simple model potential chosen for its reparameterization is the MCY model potential of Clementi et al. The quality of the fit is assessed by comparing the geometry of the minimum, the harmonic frequencies, and the second virial coefficients of the parameterized potential with the reference one. Finally, to prove more rigorously the robustness of this method, it is compared with standard nonstochastic methods of optimization. 相似文献
35.
From the de Broglie matter wave hypothesis and Planck’s energy quantization law, and assuming conservation of energy in the
absorption of a photon and its consequent conversion to kinetic energy of motion by a material particle initially at rest,
one can deduce a simple mathematical relationship between the wavelength λ (or frequency ν), of the photon absorbed by the
particle at rest, and the resulting de Broglie matter wave length, λD, of the particle with kinetic energy of motion of mv2/2. The relationship so deduced, λD∝√λ, suggests that visible wavelengths of light, from about 4000 ?, in the violet, to beyond about 7000 ?, in the red, on
absorption by an electron at rest, lead to material electron wavelengths, λD, of the order of the size of the electron transfer proteins seen in the photosynthetic reaction centers of photosynthesizing
organisms, at about a size of 50–100 ?. In addition to understanding the mechanism of photosynthesis as a material wave mediated
phenomenon, further areas of importance of the relations pointed out in this paper are in the design of experiments to gain
a deeper understanding of the basic tenets of wave mechanics, and in the use of tunable lasers to probe various properties
of material waves, and to precisely control their properties for applications including lithography. 相似文献
36.
Francisco M. Ferndez Eduardo A. Castro 《International journal of quantum chemistry》1982,21(5):875-884
New formal results regarding the hypervirial analysis of enclosed systems are given. Novel applications are presented and several previous equations are reformulated in a more appropriate form. 相似文献
37.
Alconchel S Sapiña F Martínez E 《Dalton transactions (Cambridge, England : 2003)》2004,(16):2463-2468
The molybdenum bimetallic interstitial carbides Fe(3)Mo(3)C and Co(3)Mo(3)C have been synthesized by temperature-programmed reaction (TPR) between the molybdenum bimetallic interstitial nitrides Fe(3)Mo(3)N and Co(3)Mo(3)N and a flowing mixture of CH(4) and H(2) diluted in Ar. These compounds have been characterized by X-ray diffraction, laser Raman spectroscopy, elemental analysis, energy dispersive analysis of X rays, thermal analysis (in air) and scanning electron microscopy (field emission). Their structures have been refined from X-ray powder diffraction data. These carbides crystallize in the cubic system, space group Fd3m[a= 11.11376(6) and 11.0697(3)[Angstrom] for Fe and Co compounds, respectively]. 相似文献
38.
An easy method for the determination of the enantiomeric excess (ee) of mixtures of alpha-amino acids, and also for the elucidation of the absolute configuration of each component of the mixture, is reported. The method is based on the formation of diastereoisomers by reaction of the enantiomerically pure acetylacetonate derivative [Pd(acac-O,O')(P(2)-dach)]ClO(4) (4) [P(2)-dach = (1R,2R)-C(6)H(10)(NHPPh(2))(2)] with d,l-mixtures of alpha-amino acids AaH (Pd:AaH = 1:1 molar ratio, refluxing MeOH). The reaction occurs with protonation of the acac ligand and N,O-coordination of the amino acidate group, giving the corresponding [Pd(Aa-N,O)(P(2)-dach)]ClO(4) complexes l-5 and d-6. The composition of these mixtures of amino acidate complexes was analyzed by integration of the corresponding peaks (four doublets, two for each diastereomer) in their (31)P((1)H) NMR spectra. A series of 14 alpha-amino acids was studied (a, alanine; b, 2-aminobutyric acid; c, valine; d, phenylalanine; e, proline; f, leucine; g, isoleucine; h, norleucine; i, serine; j, threonine; k, methionine; l, aspartic acid; m, glutamine; n, cysteine), and excellent agreement between the expected values of ee and those obtained from integration of the (31)P((1)H) NMR spectra was obtained. Moreover, the position of the signals of each isomer is diagnostic, in such a way that the outer doublets are always due to the l-derivatives 5a-l, while the inner ones are due to the d-derivatives 6a-l, allowing the assignation of absolute configurations to each isomer in the mixture. 相似文献
39.
Ramiro Pino Olivier Bokanowski Eduardo V. Ludeña Roberto López Boada 《Theoretical chemistry accounts》2007,118(3):557-561
Bearing in mind the insight into the Hohenberg–Kohn theorem for Coulomb systems provided recently by Kryachko (Int J Quantum
Chem 103:818, 2005), we present a re-statement of this theorem through an elaboration on Lieb’s proof as well as an extension
of this theorem to finite subspaces.
Contribution to the Serafin Fraga Memorial Issue. 相似文献
40.
de Namor AF Chahine S Castellano EE Piro OE Jenkins HD 《Chemical communications (Cambridge, England)》2005,(30):3844-3846
An additive thermodynamic contribution of pendant arms to the complexation of calixarene derivatives with mercury(II) in acetonitrile is for the first time demonstrated. 相似文献