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11.
François Couty François Durrat Gwilherm Evano Damien Prim 《Tetrahedron letters》2004,45(40):7525-7528
A synthesis of stereodefined enantiomerically pure 2-alkenyl azetidines is described using Wittig olefination as key step. The quaternary triflate ammonium salts of these heterocycles were prepared in a stereoselective way and treatment of these azetidinium salts with a base (KHMDS or PhLi) induced a regioselective Stevens rearrangement leading to a 3-alkenyl pyrrolidine. An unprecedented SN2′ reaction involving phenyllithium as nucleophile and an ammonium as leaving group was observed in one case. 相似文献
12.
13.
M. Bazin L. K. Patterson J. C. Ronfard-Haret R. Santus 《Photochemistry and photobiology》1988,48(2):177-180
Abstract— Porphyrin radical-cations have been produced using laser flash photolysis via oxidation of the porphyrin triplets by metronidazole. This radical-cation reacts with OJ as shown by its increased half-life in the presence of native superoxide dismutase. Comparable results are obtained when porphyrin radical-cations are formed by Br2 - O2 - oxidation of porphyrins produced in pulse radiolysis of oxygen-saturated aqueous solutions containing 20 mM Br- O- . These results provide an explanation for the enhancement by superoxide dismutase of the photosensitizing capacity of porphyrins in the presence of electrophilic nitroimidazoles (Bazin and Santus, 1986). They may also apply to porphyrin radical-cations formed by monophotonic or biphotonic photoionization processes. 相似文献
14.
J. M. Gaullier M. Bazin A. Valla M. Giraud R. Santus 《Journal of photochemistry and photobiology. B, Biology》1995,30(2-3)
The pyrrole-amino acid and peptide N-conjugates synthesized from tyrosine, histidine and glutathione very effectively quench the 1270 nm singlet oxygen luminescence, at rates ranging from 108 to 109 M−1 s−1. Nuclear magnetic resonance spectroscopy suggests that the electron-donating properties of the methyl groups after 2,5-dimethyl substitution on the pyrrole ring are probably an important determinant of the reactivity of singlet oxygen with the N-conjugate of glutathione. However, intramolecular interactions between the pyrrole ring and the side chain may also modulate the reactivity of the antioxidant as suggested by absorption and fluorescence spectroscopies carried out on tyrosine derivatives. Efficient fluorescence quenching of the phenol ring by the pyrrole ring occurs in the tyrosine derivatives. The reactivities of these antioxidants with 1O2 are comparable in methanol, ethanol and D2O. 相似文献
15.
R. I. Damper Y. Marchand J.-D. S. Marsters A. I. Bazin 《Journal of Sol-Gel Science and Technology》1997,8(2):147-160
A common requirement in speech technology is to align two different symbolic representations of the same linguistic ‘message’.
For instance, we often need to align letters of words listed in a dictionary with the corresponding phonemes specifying their
pronunciation. As dictionaries become ever bigger, manual alignment becomes less and less tenable yet automatic alignment
is a hard problem for a language like English. In this paper, we describe the use of a form of the expectation-maximization
(EM) algorithm to learn alignments of English text and phonemes, starting from a variety of initializations. We use the British
English Example Pronunciation (BEEP) dictionary of almost 200,000 words in this work. The quality of alignment is difficult
to determine quantitatively since no ‘gold standard’ correct alignment exists. We evaluate the success of our algorithm indirectly
from the performance of a pronunciation by analogy system using the aligned dictionary data as a knowledge base for inferring
pronunciations. We find excellent performance—the best so far reported in the literature. There is very little dependence
on the start point for alignment, indicating that the EM search space is strongly convex. Since the aligned BEEP dictionary
is a potentially valuable resource, it is made freely available for research use. 相似文献
16.
Photoreduction of ketones in the presence of amines led to ketyl radicals through photoinduced electron transfer (PET). Tertiary amines, such as triethylamine (Et3N) have frequently been used in these reactions. Different reactions can occur from ketyl radicals such as photoreduction, coupling reactions, additions on activated double bonds, cyclizations, bond cleavage of strained rings, tandem reactions such as cyclization-ring opening or ring opening-cyclization. 相似文献
17.
Alberola A Farley RD Humphrey SM McManus GD Murphy DM Rawson JM 《Dalton transactions (Cambridge, England : 2003)》2005,(24):3838-3845
Selective chlorination of thiophene-2,3-dithiol with SO(2)Cl(2) generates the corresponding sulfenyl chloride, 2,3-C(4)H(2)S(SCl)(2). Subsequent condensation with Me(3)SiN(3) yields the thiophenodithiazolylium salt [C(4)H(2)S(3)N]Cl, [TDTA]Cl. The structure of the cation, TDTA+, was established by X-ray diffraction as both its AsF(6)(-) and HSO(4)(-) salts. Reduction of [TDTA]Cl with Ag powder yields the radical TDTA* which was characterised by X- and Q-band (9 and 34 GHz) EPR and ENDOR studies. The spin density distributions estimated from the EPR/ENDOR measurements were found to be in very good agreement with those determined by DFT (B3LYP/6-31G*) indicating that ca 10% of the spin density is delocalised onto the thiophene ring. Comparison of the spin density distributions in TDTA* and the isoelectronic trithiatriazapentalenyl radical C(2)S(3)N(3), TTTA*, indicates that replacement of N by C-H leads to a localisation of the spin density on the dithiazolyl ring. 相似文献
18.
[reaction: see text] A synthesis of the glutarimide-derived metabolite of thalidomide, 5'-hydroxythalidomide (2), is described. The synthesis employed the lactone derivative of N-benzyloxycarbonyl (CBZ)-protected 4-hydroxyglutamic acid 12, which is prepared by a de novo route from diethyl acetamidomalonate. The reaction of 12 with 4-methoxybenzylamine gave the corresponding isoglutamine, which then provided the key CBZ-protected N-PMB-glutarimide 14 after dehydration. Deprotection of both the CBZ and PMB groups followed by phthalimidation and deacetylation of the 3-amino-5-acetoxyglutarimide 16 afforded 2. 相似文献
19.
We report on the coupling of a polymer-based microfluidic chip to a MALDI-TOF MS using a rotating ball interface. The microfluidic chips were fabricated by micromilling a mold insert into a brass plate, which was then used for replicating polymer microparts via hot embossing. Assembly of the chip was accomplished by thermally annealing a cover slip to the embossed substrate to enclose the channels. The linear separation channel was 50 microm wide, 100 microm deep, and possessed an 8 cm effective length separation channel with a double-T injector (V(inj) = 10 nL). The exit of the separation channel was machined to allow direct contact deposition of effluent onto a specially constructed rotating ball inlet to the mass spectrometer. Matrix addition was accomplished in-line on the surface of the ball. The coupling utilized the ball as the cathode transfer electrode to transport sample into the vacuum for desorption with a 355 nm Nd:YAG laser and analyzed on a TOF mass spectrometer. The ball was cleaned online after every rotation. The ability to couple poly(methylmethacrylate) microchip electrophoresis devices for the separation of peptides and peptide fragments produced from a protein digest with subsequent online MALDI MS detection was demonstrated. 相似文献
20.
N-Cyanomethyl and N-propargyl β-amino alcohols are chlorinated with SOCl2 and treated with NaN3 in DMSO. A substitution/cycloaddition process affords in good yields, with high diastereoselectivity and a regioselectivity depending on the substitution pattern of the starting amino alcohol, fused tri- and tetrazoles-piperazines. These heterocycles were further lithiated with n-BuLi at the benzylic position and reacted diastereoselectively with a range of electrophiles. 相似文献