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21.
Cyclic and acyclic beta-ketoesters were efficiently trifluoromethylated with 5-trifluoromethyldibenzothiophenium tetrafluoroborate in the presence of a phase-transfer catalyst to afford the corresponding alpha-substituted alpha-trifluoromethyl beta-ketoesters in good to excellent yields. In a second approach, 5-trifluoromethyldibenzothiophenium tetrafluoroborate and tetrabutylammonium difluorotriphenylstannate were used for efficient electrophilic trifluoromethylation of various silyl enol ethers leading to the corresponding alpha-trifluoromethyl ketones in good to high yields. 相似文献
22.
Polypeptides containing a basic amino acid close to their single tryptophan residue were irradiated with monochromatic 302 nm radiation. Tryptophan photolysis was monitored by absorption and fluorescence spectroscopy. Amino acid loss was evaluated by amino acid analysis. Only the protonated residues adjacent to tryptophan in the sequence were destroyed upon tryptophan excitation. This reaction is probably due essentially to direct interaction between the excited tryptophan and the neighbouring residue without electron solvation. 相似文献
23.
Tessore F Roberto D Ugo R Pizzotti M Quici S Cavazzini M Bruni S De Angelis F 《Inorganic chemistry》2005,44(24):8967-8978
Coordination of 4'-(C6H4-p-X)-2,2':6',2'-terpyridines [X = NO2, NBu2, (E)-CH=CH-C6H4-p-NBu2, (E,E)-(CH=CH)2-C6H4-p-NMe2] to Zn(II), Ru(III), and Ir(III) metal centers induces a significant enhancement of the absolute value of the second-order nonlinear optical (NLO) response of the terpyridine, measured by means of both electric field induced second harmonic generation and solvatochromic methods. By varying the nature of the metal center, the enhanced second-order NLO response shifts from positive to negative. Such a shift is controlled by electronic charge-transfer transitions, such as metal-to-ligand or ligand-to-metal transitions, in addition to the intraligand charge transfer. The enhancement generated by coordination is also controlled by the chelation effect and by fine-tuning of the ancillary ligands. 相似文献
24.
J. Yves Laronze Rachida El Boukili Dominique Patigny Seloua Dridi Dominique Cartier Lean L vy 《Tetrahedron》1991,47(48):10003-10014
Upon acid catalyzed rearrangement after Sheradsky, the aryloximes A gave the tricyclic aminals C, which suffered hydrolysis to lactols E. The unique alcohol 29 was then prepared through a highly stereoselective equilibration-reductive alkylation of the epimeric mixture of lactols 22a,b. Two routes, one of which was stereospecific, allowed cyclization of 29 to (±)-aplysin 34. The yield was 2.5 % from oximes 2a,b. The isomeric epi-aplysin 35 and filiformin 36 were also obtained from 29. The debromo analogues 37,38 and 39 and their trideutero derivatives 41,42 and 43 were synthesized along similar line and allowed unequivocal structure elucidation by NMR spectroscopy. 相似文献
25.
The 2-(diphenylphosphino) ethyl group (DPPE) as a new carboxyl-protecting group in peptide chemistry
Dominique Chantreux Jean-Paul Gamet Robert Jacquier Jean Verducci 《Tetrahedron》1984,40(16):3087-3094
The use of the 2-(diphenylphosphino)ethyl group for carboxyl-protection of amino acids or peptides is described. This group is easily introduced by esterification using 2-(diphenylphosphino) ethanol in the presence of dicyclohexylcarbodiimide and 4-(dimethylamino)pyridine. These Dppe esters are stable under the standard conditions for peptide synthesis. Deprotection is carried out under mild conditions by quaternisation using methyl iodide followed by a β-elimination induced by fluoride ion or potassium carbonate. 相似文献
26.
Fruh D Chiarparin E Pelupessy P Bodenhausen G 《Journal of the American Chemical Society》2002,124(15):4050-4057
A method is described to determine long-range cross-correlations between the modulations of an anisotropic chemical shift (e.g., of a C' carbonyl carbon in a protein) and the fluctuations of a weak long-range dipolar interaction (e.g., in cross-correlation between the same C' carbonyl and the H(N) proton of the neighboring amide group). Such long-range correlations are difficult to measure because the corresponding long-range scalar couplings are so small that Redfield's secular approximation is often violated. The method, which combines features of single- and double-quantum NMR spectroscopy, allows one to cancel the effects of dominant short-range dipolar interactions (e.g., between the CSA of the amide nitrogen N and the dipolar coupling to its attached proton H(N)) and is designed so that the secular approximation is rescued even if the scalar coupling between the long-range dipolar coupling partners is very small. The cross-correlation rates thus determined in ubiquitin cover a wide range because of local motions and variations of the CSA tensors. 相似文献
27.
Hirel C Luneau D Pécaut J Ohrström L Bussière G Reber C 《Chemistry (Weinheim an der Bergstrasse, Germany)》2002,8(14):3157-3161
The nitronyl nitroxide 2-cyano-4,4,5,5-tetramethylimidazoline-1-oxyl-3-oxide (1) crystallises in the tetragonal P42(1)m space group with a=7.4050(7), c=8.649(1) A. In the crystal the molecules form layers parallel to the ab plane in which they are orthogonal to each other. In the layers there are close contacts, 2.953(2) A, between the NO groups and the bridging carbon atoms of the O-N-C-N-O fragment of neighbouring radicals. The calculated spin density shows a positive population mainly and equally localised on the NO groups and small but significant negative spin densities on the bridging carbon atom and the cyano nitrogen. Absorption spectra show temperature-dependent transitions related to the magnetic behaviour. The temperature dependence of the magnetic susceptibility in the range 2-300 K reveals that couplings between the radicals are antiferromagnetic, and is interpreted by considering a two-dimensional square array of spin S=1/2 antiferromagnetically coupled (J=-10 cm(-1) and g=2.01). This is interpreted as an exchange coupling through close contact between positive and negative spin densities in orthogonal orbitals on oxygen and carbon atoms, respectively. 相似文献
28.
E. Peter Kündig Chantal Dupr Bernadette Bourdin Allan Cunningham Dominique Pons 《Helvetica chimica acta》1994,77(2):421-428
Two new C2 chiral bidentate phosphorous ligands have been prepared in enantiomerically pure form. The two phosphorous centers bear electron-withdrawing groups ((CF3)2CH? O, C6F5) and are linked by a trans-cyclopentane-1,2-diol-derived bridge. Photolysis of [Cr(η6-C6H6)(CO)3] in the presence of these two new ligands and of two previously reported bidentate phosphites, and fluorophosphinites (L) afforded [Cr(η6-C6H6)(CO)L] complexes. IR Spectral comparison of the complexes shows the new ligands to be intermediate in their bonding properties between alkyl phosphites and CO. 相似文献
29.
Atomic force microscopy imaging of hair: correlations between surface potential and wetting at the nanometer scale 总被引:2,自引:0,他引:2
Dupres V Camesano T Langevin D Checco A Guenoun P 《Journal of colloid and interface science》2004,269(2):329-335
We report investigations of hair surface potential under wetting at the nanometric scale by atomic force microscopy (AFM). Surface potential imaging was used to characterize the electrostatic properties of the hair samples. We found that the surface potential noticeably increases along the edges of the cuticles. These results are correlated with wetting behavior of different liquids performed using AFM in noncontact mode. 相似文献
30.
Smaali M. Issam Gargouri Mohamed Legoy Marie Dominique Maugard Thierry Limam Farid Marzouki Nejib 《Applied biochemistry and biotechnology》2004,112(2):63-77
The filamentous fungus Sclerotinia sclerotiorum, grown on a xylose medium, was found to excrete one β-glucosidase (β-glu x). The enzyme was purified to apparent homogeneity
by ammonium sulfate precipitation, gel filtration, anion-exchange chromatography, and high-performance liquid chromatography
(HPLC) gel filtration chromatography. Its molecular mass was estimated to be 130 kDa by HPLC gel filtration and 60 kDa by
sodium dodecyl sulfate polyacrylamide gel electrophoresis, suggesting that β-glu x may be a homodimer. For p-nitrophenyl β-d-glucopyranoside hydrolysis, apparent K
m and V
max values were found to be 0.09 mM and 193 U/mg, respectively, while optimum temperature and pH were 55–60°C and pH 5.0, respectively. β-Glu x was strongly
inhibited by Fe2+ and activated about 35% by Ca2+. β-Glu x possesses strong transglucosylation activity in comparison with commercially available β-glucosidases. The production
rate of total glucooligosaccharides (GOSs) from 30% cellobiose at 50°C and pH 5.0 for 6 h with 0.6 U/mL of enzyme preparation
was 80 g/L. It reached 105 g/L under the same conditions when using cellobiose at 350 g/L (1.023 M). Finally, GOS structure was determined by mass spectrometry and 13C nuclear magnetic resonance spectroscopy. 相似文献