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61.
An M Maitra U Neidlein U Bartlett PA 《Journal of the American Chemical Society》2003,125(42):12759-12767
A chemical synthesis of both diastereomers of the tetrahedral intermediate involved in 5-enolpyruvylshikimate 3-phosphate synthase (EPSPS) catalysis has been accomplished. Combination of methyl dibromopyruvate with a protected shikimic acid derivative, phosphorylation, and lactonization afforded the intermediates (S)-15 and (R)-15, whose configurations were assigned by NMR. After introduction of the 3-phosphate group and deprotection, photoinitiated radical debromination of the dibromo analogues (S)-5 and (R)-5 was accomplished with tributyltin hydride in mixed aqueous solvents in the presence of surfactant to give the pyruvate ketal phosphates (R)-TI and (S)-TI, respectively. These compounds are stable at high pH, but decompose at pH 7 with a half-life of ca. 10 min. (R)-TI proved to be inert to EPSPS, while (S)-TI was converted by the enzyme to a mixture of 5-enolpyruvylshikimate 3-phosphate, shikimate 3-phosphate, and phosphoenolpyruvate. The demonstration that the enzymatic intermediate possesses the S-configuration at the ketal center confirms the mechanism as an anti addition followed by a syn elimination. Furthermore, it appears that the syn stereochemistry of the second step requires the phosphate leaving group to serve as the base in catalyzing its own elimination. 相似文献
62.
Manindranath Bera Prasant Kumar Nanda Uday Mukhopadhyay Debashis Ray 《Journal of Chemical Sciences》2004,116(3):151-158
Low-temperature stoichiometric Schiff base reaction in air in 3:1 mole ratio between benzaldehyde and triethylenetetramine
(trien) in methanol yields a novel tetraaza μ-bis (bidentate) acyclic ligand L. It was characterized by elemental analysis, IR, EI mass and NMR (1H and13C) spectra. The formation of a five-membered imidazolidine ring from the ethylenediamine backbone as a spacer-cumbridging
unit gives rise to a new type of imidazolidine-bridged ligand. A geometric optimisation was made of the synthesized ligand
and its complexes by the method of molecular mechanics (MM2) method in order to establish the stable conformations. This hitherto
unknown tetraaza acyclic ligand affords new cationic dicopper(I/I) and dicopper(II/II) complexes in good yield. Dicopper(II/II)
complex displays weakd-d transition bands in the visible region, while dicopper(I/I) complex displays strong MLCT band in the same region. Both the
dinuclear complexes are of non-intimate nature and show interesting solution electrochemical behaviour. EPR spectral study
of μ-bis (imidazolidino) bridged dicopper(II/II) complex also supports the non-communicative nature of the two copper centres within
the same molecule 相似文献
63.
[structure: see text] A novel cholaphane has been synthesized from a naturally occurring bile acid in just two steps. It has an ability to bind two fluoride ions selectively utilizing the glycolate motif in chloroform. This "inside-out" cyclodextrin analogue encapsulates fluoride through O-H...F(-) and C-H...F(-) interaction. 相似文献
64.
Synthesis of nanostructure hydrous iron–titanium binary mixed oxide (NHITBMO) had been reported by a simple method, and characterized by the X-ray diffraction (XRD), thermal analysis, transmission electron microscope (TEM), Föurier Transform Infrared (FTIR), surface area, and zero surface charge pH (pHzpc). The synthetic oxide was hydrated and microcrystalline with 77.8 m2 g?1 BET surface area. The particle size (nm) calculated using XRD peak table and TEM image was ~10–13 and 6–8, respectively. The pHzpc value was 6.0 (±0.05) for the oxide. The NHITBMO showed pH dependent good sorption affinity for arsenic from the aqueous solution and, the Langmuir monolayer capacity (mg g?1) was 80.0 and 14.6, respectively, for the As(III) and As(V). The pseudo-second order equation described the room temperature arsenic sorption kinetic data well. The minimum dose required was 1.6 g NHITBMO per L of water (Astotal = 0.24 mg L?1) to reduce the arsenic level below 0.01 mg L?1 in batch treatment process. 相似文献
65.
Several nonlinear systems such as the Korteweg-de Vries (KdV) and modified KdV equations and lambda phi(4) theory possess periodic traveling wave solutions involving Jacobi elliptic functions. We show that suitable linear combinations of these known periodic solutions yield many additional solutions with different periods and velocities. This linear superposition procedure works by virtue of some remarkable new identities involving elliptic functions. 相似文献
66.
67.
A series of deoxycholic and cholic acid‐derived oligomers were synthesized and their ability to extract hydrophilic dye molecules of different structure, size, and functional groups into nonpolar media was studied. The structure of the dye and “dendritic effect” in the extraction process was examined using absorption spectroscopy and dynamic light scattering (DLS). The efficiency of structurally preorganized oligomers in the aggregation process was evaluated by 1‐anilinonaphthalene‐8‐sulfonic acid (ANS) fluorescence studies. The possible formation of globular structures for higher‐generation molecules was investigated by molecular modeling studies and the results were correlated with the anomaly observed in the extraction process with this molecule. The ability of these molecules for selective extraction of specific dyes from blended colors is also reported. 相似文献
68.
The generalized finite element method (GFEM) is a Galerkin method, where the trial space is obtained by augmenting the trial space of the standard finite element method (FEM) by non-polynomial functions, called enrichments, that mimic the local behavior of the unknown solution of the underlying variational problem. The GFEM has excellent approximation properties, but its conditioning could be much worse than that of the FEM. However, if the enrichments satisfy certain properties, then the conditioning of the GFEM is not worse than that of the standard FEM, and the GFEM is referred to as the stable GFEM (SGFEM). In this paper, we address the higher order SGFEM that yields higher order convergence and suggest a specific modification of the enrichment function that guarantees the required conditioning, yielding a robust implementation of the higher order SGFEM. 相似文献
69.
Makarand A. Kulkarni Uday P. Lad Uday V. Desai Satish D. Mitragotri Prakash P. Wadgaonkar 《Comptes Rendus Chimie》2013,16(2):148-152
An extremely simple, high yielding, highly rapid and solvent-free protocol has been described for hydrophosphylation of aldehydes using potassium phosphate as catalyst. Easy commercial availability of the reusable catalyst, operational simplicity at ambient temperature and avoidance of conventional work-up as well as purification procedure makes this solvent-free protocol a near-ideal synthesis. 相似文献
70.
G. Satish K. Harsha Vardhan ReddyB.S.P. Anil J. ShankarR. Uday Kumar Y.V.D. Nageswar 《Tetrahedron letters》2014
A simple and highly practical method for the synthesis of 2-N-substituted benzothiazoles has been developed by using nano copper ferrite as a magnetically separable, recyclable catalyst. The present tandem process allows to get access to a wide range of 2-N-substituted benzothiazoles in good to excellent yields by the reaction of benzothiazole with nitrogen nucleophiles in the presence of Cs2CO3 as a base. The nano CuFe2O4 could be recovered and reused with no significant loss of catalytic activity. 相似文献