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1.
The use of reagent concentration has resulted in increased rates for all stages of the REM resin synthesis of tertiary amines. These increases in rate translate into faster reaction times, higher yields and lower reagent consumption. Of the methods examined, the most successful was the use of perfluorous solvents, either alone or with a small amount of organic co-solvent. 相似文献
2.
Fe2O3--V2O5 catalysts doped with Cs2SO4 (molar ratio: V:Fe:Cs=1:0.74:0.06) were found to be a rather inhomogeneous mixture of various crystalline and amorphous iron
vanadate phases. After calcination in air the catalyst was divided into three different parts which were analyzed separately
revealing the formation of FeVO4 in the top and bottom fraction of the crucible and Fe2V4O13 in the middle fraction. As compared to the well crystallized FeVO4 reference sample, the quadrupole splittings of FeVO4 in the Cs-doped catalysts were larger pointing to more distorted iron sites which were assumed to be responsible for high
catalytic selectivities. In contrast, the quadrupole splittings of FeVO4 in the less selective K- and Rb-doped Fe2O3--V2O5 catalysts were smaller. Additional components in the bottom fraction were also α-Fe2O3 and Fe1-xS. As indicated by the CEMS spectra the latter is located preferentially on the surface of the catalyst particles.
This revised version was published online in August 2006 with corrections to the Cover Date. 相似文献
3.
KL Britton HF Rogers Y Asano T Dairi Y Kato TJ Stillman DW Rice 《Acta crystallographica. Section D, Biological crystallography》1998,53(4):124-126
The novel NAD+-linked opine dehydrogenase from a soil isolate Arthrobacter sp. strain 1C belongs to an enzyme superfamily whose members exhibit quite diverse substrate specificites. Crystals of this opine dehydrogenase, obtained in the presence or absence of co-factor and substrates, have been shown to diffract to beyond 1.8 ? resolution. X-ray precession photographs have established that the crystals belong to space group P21212, with cell parameters a = 104.9, b = 80.0, c = 45.5 ? and a single subunit in the asymmetric unit. The elucidation of the three-dimensional structure of this enzyme will provide a structural framework for this novel class of dehydrogenases to enable a comparison to be made with other enzyme families and also as the basis for mutagenesis experiments directed towards the production of natural and synthetic opine-type compounds containing two chiral centres. 相似文献
4.
5.
Redox-active tyrosine residues play important roles in long-distance electron reactions in enzymes, including prostaglandin H synthase, galactose oxidase, ribonucleotide reductase, and photosystem II. Magnetic resonance and vibrational spectroscopy provide methods with which to study the structures of redox-active amino acids in proteins. In this report, ultraviolet photolysis was used to generate tyrosyl radicals from polycrystalline tyrosinate or dipeptides, and the structure of the radical was investigated with EPR and reaction-induced FT-IR spectroscopy at 77 K. Photolysis at 77 K is expected to generate a neutral tyrosyl radical through oxidation of the aromatic ring. EPR and FT-IR results obtained from (13)C-labeled tyrosine were consistent with that expectation. Surprisingly, labeling of the tyrosyl amino group with (15)N also resulted in isotope-shifted bands in the photolysis spectrum. The force constant of a NH deformation mode increased when the tyrosyl radical was generated. These data suggest an interaction between the pi system of the tyrosyl radical and the amino group. In spectra acquired from the dipeptides, evidence for a sequence-dependent interaction between the tyrosyl radical and the amide bond of the dipeptide was also obtained. We postulate that perturbation of the amino or the amide/imide groups may occur through a spin polarization mechanism, which is indirectly detected as a change in NH force constant. This conclusion is supported by density functional calculations, which suggest a conformationally sensitive delocalization of spin density onto the amino and carboxylate groups of the tyrosyl radical. These experiments provide a step toward a detailed spectral interpretation for protein-based tyrosyl radicals. 相似文献
6.
The conversion of phosphoenolpyruvate (PEP) to phosphonopyruvate (P-pyr) is catalyzed by PEP mutase via a dissociative mechanism. In this work, we investigate the uncatalyzed reaction using ab initio methods, density functional theory, and the semiempirical MNDO/d method. Comparisons of geometries and relative energies of stationary points (minima and transition states) with density functional results indicate that the semiempirical method is reasonably accurate. Solvent effects are examined using implicit solvent models, including the recently extended smooth conductor-like screening model. Due to the large negative charge carried by the system, solvation is found to drastically alter the location and energy of stationary points along the dissociative reaction pathways. The influence of substituting a nonbridging phosphoryl oxygen by sulfur (thio effects) was also investigated. Implications of these results for the enzymatic reaction are discussed. 相似文献
7.
New methods for the calculation of electrostatic interactions between the active dynamical region and surrounding external solvated macromolecular environment in hybrid quantum mechanical/molecular mechanical (QM/MM) simulations are presented. The variational electrostatic projection (VEP) method, and related variational reverse-mapping procedure (VEP-RVM) utilize an expansion in Gaussian surface elements for representation of electrostatic interactions. The use of a discretized surface that surrounds the active dynamical region greatly reduces the number of interactions with the particles of the external environment. The methods are tested on two catalytic RNA systems: the hammerhead and the hairpin ribozymes. It is shown that with surface elements numbering from 302 to 1202 points the direct VEP and VEP-RVM methods are able to obtain relative force errors in the range of 0.5-0.05% and 0.09-0.0001%, respectively, using a 4.0 A projection buffer. These results are encouraging and provide an essential step in the development of new variational macromolecular solvent-boundary methods for QM/MM calculations of enzyme reactions. 相似文献
8.
Sadowsky JD Schmitt MA Lee HS Umezawa N Wang S Tomita Y Gellman SH 《Journal of the American Chemical Society》2005,127(34):11966-11968
Molecules that bind to specific surface sites on proteins are of great interest from both fundamental and practical perspectives. We are exploring a ligand development strategy that is based on oligomers with discrete folding propensities ("foldamers"); we target a specific cleft on the cancer-associated protein Bcl-xL because this system is well characterized structurally. In vivo, this cleft binds to alpha-helical segments (BH3 domains) of other proteins. We evaluated several types of helical foldamer, built entirely from beta-amino acid residues or from mixtures of alpha- and beta-amino acid residues, and ultimately identified foldamers in the latter class that bind very tightly to Bcl-xL. Our results suggest that combining different types of foldamer backbones will be an effective and general strategy for creating high-affinity and specific ligands for protein surface sites. 相似文献
9.
Complete basis set extrapolations of alkali halide (LiF, LiCl, NaF, NaCl) energy, dipole, and polarizability surfaces are performed with and without applied fields along the internuclear axis using state-averaged multireference configuration interaction. Comparison between properties (equilibrium separation, dissociation energy, crossing distance, diabatic coupling constant, dipole, and polarizability) derived from the extrapolated potential energy (or dipole) surfaces are made with those obtained from direct extrapolation from the basis set trends. The two extrapolation procedures are generally found to agree well for these systems. Crossing distances from this work are compared to those of previous work and values obtained from the Rittner potential. Complete basis set extrapolated crossing distances agree well with those derived from the Rittner potential for LiF, but were significantly larger for LiCl, NaF, and NaCl. The results presented here serve as an important set of benchmark data for the development of new-generation many-body force fields that are able to model charge transfer. 相似文献
10.
Residual stresses are found in the majority of multilayer thin film structures used in modem technology. The measurement and modeling of such stress fields and the elucidation of their effects on structural reliability and device operation have been a “growth area” in the literature, with contributions from authors in various scientific and engineering disciplines.
In this article the measurement of the residual stresses in thin film structures with X-ray diffraction techniques is reviewed and the interpretation of such data and their relationship to mechanical reliability concerns are discussed. 相似文献