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91.
May JP Fournier P Pellicelli J Patrick BO Perrin DM 《The Journal of organic chemistry》2005,70(21):8424-8430
This work describes a rapid and high yielding oxidation of 14 tryptophanylated amino acid methyl esters to the corresponding 3a-hydroxypyrrolo[2,3-b]indoline (Hpi) amino acids with generally facile separation of syn-cis and anti-cis diastereomers. Structural X-ray diffraction data are presented for both diastereomers of Tr-Hpi-Gly-OMe, which allow for a putative assignment of the other 13 pairs of diastereomers reported herein, based on correlations with 1H NMR chemical shifts. Selective and high yielding deprotection at either the N or C terminus is described, allowing the Hpi motif to be introduced efficiently into potential targets with minimal protecting group manipulation. Two tripeptides containing Hpi and cysteine were prepared and treated with acid in the Savige-Fontana reaction to produce a cyclic tryptathionine linkage, characteristic of both amatoxins and phallotoxins. 相似文献
92.
Omid Ranaei Siadat Andrée Lougarre Lucille Lamouroux Caroline Ladurantie Didier Fournier 《BMC biochemistry》2006,7(1):12-7
Background
Acetylcholinesterase is irreversibly inhibited by organophosphate and carbamate insecticides allowing its use in biosensors for detection of these insecticides. Drosophila acetylcholinesterase is the most sensitive enzyme known and has been improved by in vitro mutagenesis. However, its stability has to be improved for extensive utilization. 相似文献93.
The chemoselective and stereoselective synthesis of gem-difluoro-β-aminoesters or gem-difluoro-β-lactams was investigated from ethylbromodifluoroacetate and imines during Reformatsky reaction. Influence of various reaction parameters, such as nature of the amine part, nature of the chiral auxiliary, was evaluated. High levels of stereoselectivity (up to 98%) were obtained for gem-difluoro-β-aminoesters and gem-difluoro-β-lactams using either (R)-phenylglycinol or (R)-methoxyphenylglycinol. 相似文献
94.
A new unnatural macrocyclic trichothecene, an analogue of verrucarine A ( 1 ), which was named 3-Isoverrucarin A ((1″-O)(3→4)abeo-verrucarin A; 3 ) was synthesized starting from anguidine ( 5 ). The two key reactions were the removal of the 4β-acetoxy group of anguidine ( 5 ) by a Barton deoxygenation and the final macrolactonization. During the cyclization procedure, two unexpected new macrocyclic by-products, which were named verrucinol ( 19 ) and verrucene ( 20 ), were formed. They represent novel types of macrocyclic trichothecenes, the macrolidic moiety of verrucene ( 20 ) consisting only of the (Z,E)-muconic-acid residue. The formation of the analogous macrolide 26 of verrucene ( 20 ) was not possible, probably because the ring strain is too strong. 相似文献
95.
96.
Massoud SS Corfù NA Griesser R Sigel H 《Chemistry (Weinheim an der Bergstrasse, Germany)》2004,10(20):5129-5137
The first acidity constant of fully protonated xanthosine 5'-monophosphate, that is, of H3(XMP)+, was estimated by means of a micro acidity constant scheme and the following three deprotonations of the H2(XMP)+/- (pKa=0.97), H(XMP)- (5.30), and XMP2- (6.45) species were determined by potentiometric pH titrations; further deprotonation of (XMP-H)3- is possible only with pKa>12. The most important results are that the xanthine residue is deprotonated before the P(O)2(OH)- group loses its final proton; that is, twofold negatively charged XMP carries one negative charge in the pyrimidine ring and one at the phosphate group. Micro acidity constant evaluations reveal that this latter mentioned species occurs with a formation degree of 88 %, whereas its tautomer with a neutral xanthine moiety and a PO3(2-) group is formed only to 12 %; this distinguishes XMP from its related nucleoside 5'-monophosphates, like guanosine 5'-monophosphate. At the physiological pH of about 7.5 mainly (XMP-H)3- exists. The question, which of the purine sites, (N1)H or (N3)H, is deprotonated in this species cannot be answered unequivocally, though it appears that the (N3)H site is more acidic. By application of several methylated xanthine species intrinsic micro acidity constants are calculated and it is shown that, for example, for 7-methylxanthine the N1-deprotonated tautomer occurs with a formation degree of about 5 %; a small but significant amount that, as is discussed, may possibly be enhanced by metal ion coordination to N7, which is known to occur preferably to this site. 相似文献
97.
Christian Miquel Pierre Pigache Benoit Rigo Nicolas Kolocouris 《Journal of heterocyclic chemistry》1980,17(7):1447-1453
Starting from the readily available 5-oxo-2-carboxypyrrolidine, methylene-bis-(N-5-oxo-2-carboxypyrrolidine) was prepared and transformed into a diamine, then into two isomeric diols, which cyclised into one ether. The meso configuration has been assigned for this ether. The reduction of both diols and ether was complete and gave rise to methylene-bis-N-pyrrolidine. 相似文献
98.
Abohachem Laguecir Serge Ulrich Jérôme Labille Nicolas Fatin-Rouge Serge Stoll Jacques Buffle 《European Polymer Journal》2006,42(5):1135-1144
Monte Carlo simulations, experimental titrations and fluorescence correlation spectroscopy experiments were used to investigate the conformational and electrical properties of polyacrylic acids (PAA). On the one hand, titration curves were calculated to get an insight into the role of pH on the degree of ionization and conformation of PAA chains. On the other hand, experimental potentiometric titrations of PAA were also achieved for different PAA molecular weights and compared to the calculated titration curves obtained by Monte Carlo coarse grained simulations. It was found that for a large range at intermediate PAA ionizations, a good correlation is obtained between experimental and simulations data thanks to the prominence of electrostatic interactions in this domain. The effect of ionic concentration and PAA molecular weight on the titration curves was also investigated. In order to get a better understanding of PAA conformational behavior, we also investigated PAA diffusion properties in aqueous solutions as a function of pH and ionic strength by fluorescence correlation spectroscopy (FCS), thanks to its high sensitivity to measure diffusion coefficients of tracer solutes. Good qualitative agreements were observed between experimental diffusivities and polymer properties calculated from MC simulations. It was shown that the high molecular weight PAA chains display more significant changes in diffusivity in agreement with the ionization degrees and conformational changes observed in the simulations. 相似文献
99.
Bonhommeau S Bréfuel N Pálfi VK Molnár G Zwick A Salmon L Tuchagues JP Sanchez Costa J Létard JF Paulsen H Bousseksou A 《Physical chemistry chemical physics : PCCP》2005,7(15):2909-2914
A quasi-quantitative photo-induced low-spin (LS)-->high-spin (HS) conversion of FeII ions has been observed in the [Fe(TRIM)2]Cl2 complex by irradiating the sample with blue light (488 nm) at 10 K. The time dependence of the HS-->LS relaxation has been studied between 10 K and 44 K by means of magnetic susceptibility measurements. These relaxation curves could be satisfactorily fitted by mono-exponential decays including tunnelling effect except for temperatures below 30 K. The introduction of a distribution of vibrational frequencies into this model improved significantly the fits in the low-temperature range and gave a good agreement with the experimental data in the whole temperature range suggesting a multi-rate relaxation process in this complex. 相似文献