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61.
Bassan A Blomberg MR Siegbahn PE Que L 《Chemistry (Weinheim an der Bergstrasse, Germany)》2005,11(2):692-705
The reactivity of [HO-(tpa)Fe(V)=O] (TPA=tris(2-pyridylmethyl)amine), derived from O-O bond heterolysis of its [H(2)O-(tpa)Fe(III)-OOH] precursor, was explored by means of hybrid density functional theory. The mechanism for alkane hydroxylation by the high-valent iron-oxo species invoked as an intermediate in Fe(tpa)/H(2)O(2) catalysis was investigated. Hydroxylation of methane and propane by HO-Fe(V)=O was studied by following the rebound mechanism associated with the heme center of cytochrome P450, and it is demonstrated that this species is capable of stereospecific alkane hydroxylation. The mechanism proposed for alkane hydroxylation by HO-Fe(V)=O accounts for the experimentally observed incorporation of solvent water into the products. An investigation of the possible hydroxylation of acetonitrile (i.e., the solvent used in the experiments) shows that the activation energy for hydrogen-atom abstraction by HO-Fe(V)=O is rather high and, in fact, rather similar to that of methane, despite the similarity of the H-CH(2)CN bond strength to that of the secondary C-H bond in propane. This result indicates that the kinetics of hydrogen-atom abstraction are strongly affected by the cyano group and rationalizes the lack of experimental evidence for solvent hydroxylation in competition with that of substrates such as cyclohexane. 相似文献
62.
The preparative synthesis of a 3-acetamido-3,6-dideoxy-d-galactopyranose N-phenyl-trifluoroacetimidate donor has been accomplished using as key step a silica gel mediated cyclization of an epoxytrichloroacetimidate, while other more conventional routes to aminosugars failed. Test glycosylations with the N-phenyl-trifluoroacetimidate donor are also reported. 相似文献
63.
R. -H. Rinkleff C. Ruhe F. Thorn 《Zeitschrift für Physik D Atoms, Molecules and Clusters》1993,27(1):39-43
The optical pumping method with rf detection and the nonlinear level crossing technique were used in parallel electric and magnetic fields to investigate the Stark splitting of all the fine structure levels of the ground multiplet 4f
7 (8
S) 5d6s
2
9
D in Gd I. The tensor polarizabilities were deduced from the level crossing and the rf signals. The variation of the tensor polarizabilities is well reproduced by the LS coupling approximation, except for the small value of the9
D
5 level. A value of the tensor polarizability of the 5d electron is evaluated from the experimental results, 2(5d)=2.00(6) kHz(kV/cm)2. It is shown that the ratio between the electric quadrupole constant and the tensor polarizability is constant, except for the9
D
5 ratio, which is caused by a breakdown of the central field model. 相似文献
64.
C-peptide radioimmunoassay (C-peptide RIA) is widely used in determination of pancreatic B-cell secretion activity.125I labeled TyrC-peptide is indispensable in C-peptide RIA kit. Herein we discuss a way of obtaining recombinant Tyr-C-peptide.
Arg32Tyr human proinsulin mutant (R32Y-proinsulin) gene was constructed by site-directed mutagenesis and overexpressed inEscherichia coli. Purified R32Y-proinsulin was converted to insulin and Tyr-C-peptide by trypsin and carboxypeptidase B codigestion. Tyr-C-peptide
was isolated through reverse-phase HPLC (RP-HPLC) and identified by C-peptide RIA and amino acid analysis. 相似文献
65.
Conversion of adsorption properties of activated charcoal (C∗) by metal modification towards selenite, selenate and seleno-dl-methionine (Se-Met) was studied. Several metals were included in modification studies and also a procedure was developed for the separation and independent determination of microgram quantities of these selenium species in aqueous solution. Selenium species were collected one by one from the same sample solution onto collector material by adsorbing them directly or after complex formation onto different metal-loaded activated charcoals (MgC∗ and FeC∗). The mass of selenium in these collectors was measured directly by energy dispersive X-ray fluorescence spectrometry (EDXRF). Detection limits for all three selenium species were better than 6 μg corresponding to concentration of 60 μg/l with 0.100 l of initial sample volume. 相似文献
66.
Uwe EilitzChristoph Böttcher Lothar HennigAlois Haas Cecile BoyerKlaus Burger 《Journal of fluorine chemistry》2002,115(2):149-154
Homochiral 2-C-perfluoroalkyl substituted d- and l-riboses were synthesized via Barbier, Grignard and Ruppert type reactions. The influence of the size of the perfluoroalkyl groups, attached to C-2, on the furanose/pyranose as well as on the α-furanose/β-furanose and α-pyranose/β-pyranose ratio in solution was studied. 相似文献
67.
Eckhard Herrmann Moein Nouaman Zdirad
k Gisbert Großmann Gisela Ohms 《无机化学与普通化学杂志》1994,620(11):1879-1888
Tetraarylesters of μ-Imido-Diphosphoric Acid and its Thio Derivatives — Structure Investigations New O,O′,O″,O?-tetratolyl- and ditolyl-diphenylesters of the μ-imido-diphosphoric acid and its mono and dithio derivatives were synthesized, compared with the corresponding tetraphenylesters and investigated by 1H, 13C, and 31P NMR spectroscopy and X-ray crystal structure analysis. Structures of the O,O′,O″,O?-tetrakis-(2-methyl-phenyl)-μ-imidodiphosphate, 1b , as well as of the corresponding ortho-, meta- and para-tolylesters of the μ-imido-monothiodiphosphoric acid ( 2a , 2b , 2c ) were determined. All the compounds form dimers via N? H…?O hydrogen bonds in the crystal as well as in nonpolar solvents. The distances around the phosphorus atoms rise with decreasing electronegativity of the phosphorus substituents. Signs of the 2JP? N? P coupling constants were determined by 13C{1H, 31P} triple resonance experiments for some compounds. These constants become more negative owing to substitution of a phosphoryl by a thiophosphoryl group. 相似文献
68.
69.
Adsorption of proteins and the effect of the chemical nature of membrane surfaces on protein adsorption were investigated
using14C-tagged albumin and several microporous membranes (polyvinilydene fluoride, PVDF; nylon; polypropylene, PP; and polycarbonate,
PC). The membrane surfaces were modified by exposing them to low-temperature plasma of several different monomers (n-butane, oxygen, nitrogen alone or as mixtures) in a radiofrequency plasma reactor. Transients in the permeability of albumin
solutions through the membranes and changes in flux of distilled water through the membranes before and after adsorption of
albumin were used to investigate the role of protein adsorption on membrane fouling. The results show that the extent of adsorption
of albumin on hydrophobic membranes was considerably more than that on hydrophilic membranes. The hydrophilic membranes were
susceptible to electrostatic interactions and less prone to fouling. A pore-blocking model was successfully used to correlate
the loss of water flux through pores of defined geometry 相似文献
70.
E. M. Azaroual P. Luc R. Vetter 《Zeitschrift für Physik D Atoms, Molecules and Clusters》1992,24(2):161-164
The use of an effusive beam of titanium atoms crossed with a CW single-mode tunable dye laser has allowed the high-resolution, Doppler-free study of the isotope shifts between50Ti,48Ti and46Ti, for seven 3d
2 4s
2 a3
F
J
3d
2 4s 4p z
5
D
J
, visible transitions of Ti I. The measurements show without ambiguity the existence of a non-negligible field shift. Using the values of the nuclear radii of titanium (coming from muonic X-ray measurements), it is possible to determine the respective values of the field and mass shifts. 相似文献