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131.
2,7-Diformyl-3-methyl-4,6-dimethoxyindole (6) has been synthesized and converted by metal template reactions into the macrocyclic complexes (10–12). 相似文献
132.
Guinot C Malvy DJ Latreille J Ezzedine K Galan P Tenenhaus M Ambroisine L Hercberg S Tschachler E 《Photochemistry and photobiology》2005,81(4):934-940
Phototype classifications were initially developed in an attempt to predict the skin reactions of patients to phototherapy and are now widely used to advise individuals with regard to sun protection. A transversal study was conducted on the SU.VI.MAX cohort to estimate the frequency of sun-reactive skin features in a large, general adult population-based sample, and to describe the associations between these features. The data were collected 3 years after the beginning of the SU.VI.MAX nutritional intervention study on 4912 volunteers (2868 women aged 35-60 years and 2044 men aged 45-60 years). A multiple correspondence analysis was performed to study the associations between the features. The results showed that these features correspond to a one-dimensional phenomenon, which allowed us to establish a score to summarize skin sensitivity to sun exposure. Furthermore, we found a link between gender and phototype using the Césarini classification (phototype > or = IV: 37% of women, 47% of men). The analysis of the relationship with sun-reactive skin features and the score revealed the same trend. Phenotypic evaluation appears to be a good estimator of skin sensitivity to sun exposure for clinical screening or for use in research, and is easy to collect at a lower cost. Moreover, the sun sensitivity difference between gender should be considered in education about photoprotection. 相似文献
133.
Chakroune N Viau G Ammar S Poul L Veautier D Chehimi MM Mangeney C Villain F Fiévet F 《Langmuir : the ACS journal of surfaces and colloids》2005,21(15):6788-6796
Monodisperse ruthenium nanoparticles were prepared by reduction of RuCl3 in 1,2-propanediol. The mean particle size was controlled by appropriate choice of the reduction temperature and the acetate ion concentration. Colloidal solutions in toluene were obtained by coating the metal particles with dodecanethiol. High-resolution transmission electron microscopy (HRTEM), X-ray photoelectron spectroscopy (XPS), and X-ray absorption spectroscopy (XANES and EXAFS for the Ru K-absorption edge) were performed on particles of two different diameters, 2 and 4 nm, and in different environments, polyol/acetate or thiol. For particles stored in polyol/acetate XPS studies revealed superficial oxidation limited to one monolayer and a surface coating containing mostly acetate ions. Analysis of the EXAFS spectra showed both oxygen and ruthenium atoms around the ruthenium atoms with a Ru-Ru coordination number N smaller than the bulk value, as expected for fine particles. In the case of 2 nm acetate-capped particles N is consistent with particles made up of a metallic core and an oxidized monolayer. For 2 nm thiol-coated particles, a Ru-S bond was evidenced by XPS and XAS. For the 4 nm particles XANES and XPS studies showed that most of the ruthenium atoms are in the zerovalent state. Nevertheless, in both cases, when capped with thiol, the Ru-Ru coordination number inferred from EXAFS is much smaller than for particles of the same size stored in polyol. This is attributed to a structural disorganization of the particles by thiol chemisorption. HRTEM studies confirm the marked dependence of the structural properties of the ruthenium particles on their chemical environment; they show the acetate-coated particles to be single crystals, whereas the thiol-coated particles appear to be polycrystalline. 相似文献
134.
Geng Y Romsted LS Froehner S Zanette D Magid LJ Cuccovia IM Chaimovich H 《Langmuir : the ACS journal of surfaces and colloids》2005,21(2):562-568
Sphere-to-rod transitions of cetyltrimethylammonium (CTA+) micelles with dichlorobenzoate counterions are remarkably substituent dependent. Simultaneous estimates of the interfacial molarities of H2O, MeOH, and Cl- and 2,6- and 3,5-dichlorobenzoate (2,6OBz and 3,5OBz) counterions were obtained by the chemical trapping method in mixed micelles of CTACl/CTA3,5OBz and CTACl/CTA2,6OBz without added salt. Increasing the CTA3,5OBz mole fraction produces a marked concurrent increase in interfacial 3,5OBz- and a decrease in interfacial H2O concentrations through the sphere-to-rod transition. No abrupt concentration changes are observed with increasing CTA2,6OBz mole fraction. Counterion-specific changes in the interfacial water concentration may be a major contributor to the delicate balance of forces governing micellar morphology. 相似文献
135.
Kinetics studies of the OH-initiated oxidation of 2-butyne, propyne, and acetylene were conducted at 100 Torr and 298 K using turbulent flow chemical ionization mass spectrometry. The major oxidation products were identified, and with the aid of supporting electronic structure thermodynamics calculations, a general OH-initiated oxidation mechanism for the alkynes is proposed. The major product branching ratio and the product-forming rate constants for the 2-butyne-OH adduct + O(2) reaction were experimentally determined as well. The atmospheric implications of the chemical oxidation mechanism and kinetics results are discussed. 相似文献
136.
Charles L Caloprisco S Mohamed S Sergent M 《European journal of mass spectrometry (Chichester, England)》2005,11(4):361-370
The effects of different experimental parameters on arginine electrospray ionization have been investigated with response surface modelling design. This chemometric technique allows a study of the effects of selected experimental variables and their interactions on the response of an experiment by performing a limited number of analyses. Six variables were studied: methanol content in the liquid phase, formic acid concentration, electrospray voltage, orifice voltage, mobile phase flow rate, and sheath gas flow rate. Signal abundance and signal-to-noise ratio of the protonated molecule and the protonated dimer were measured from the electrospray mass spectra and these four responses were tested by the design. The factor that exhibits the greatest influence on MH+ abundance is shown to be the liquid flow rate whereas the formation of protonated dimer is mainly controlled by the percentage of methanol in the mobile phase. A strong synergic effect of methanol content and formic acid concentration in the liquid has also been demonstrated in the study of noise level. Moreover, the capabilities of the multicriteria optimization method have been demonstrated through a successful prediction of a set of optimal experimental conditions. 相似文献
137.
Absorbing boundary conditions have been developed for various types of problems to truncate infinite domains in order to perform computations. But absorbing boundary conditions have a second, recent and important application: parallel computing. We show that absorbing boundary conditions are essential for a good performance of the Schwarz waveform relaxation algorithm applied to the wave equation. In turn this application gives the idea of introducing a layer close to the truncation boundary which leads to a new way of optimizing absorbing boundary conditions for truncating domains. We optimize the conditions in the case of straight boundaries and illustrate our analysis with numerical experiments both for truncating domains and the Schwarz waveform relaxation algorithm.
138.
The rate enhancements of dephosphorylation of p-nitrophenyldiphenyl phosphate by comicelles of cetyltrimethylammonium bromide with a functional cosurfactant are due wholly to increased concentration of the nucleophile in the micelle. 相似文献
139.
The scope of the Ugi reaction has been extended by the use of phenols as carboxylic acid surrogates to afford N-aryl carboxamides. A Smiles rearrangement occurs as the last step of the mechanism instead of the classical final Mumm process.
Various parameters concerning the nature of these inputs have been studied: the use of heteroaromatic derivatives, the substitution
of the hydroxyl moiety by a thio entity (to afford functionalized thioamides), as well as the influence of the nature and
position of substituents on the phenol. A three-component version (Passerini–Smiles) of this coupling has been developed as
well. Following these couplings, various post-condensation transformations have been performed to reach more complex heteroaromatic
fused systems. The easy functionalizations of phenols offer many opportunities for cyclization strategies: the reduction of
the nitro group allows the formation of o-phenylenediamine derivatives, which, in turn, can be transformed into quinoxalines, benzotriazoles, and benzimidazoles. Various
organometallic reactions of the Ugi–Smiles adducts have been successfully carried out, either from iodophenols (Heck couplings
to give indoles, Ullmann reaction to form quinoxalines), or from allyl pyrimidines (azepine formation by RCM strategy) as
starting phenol inputs. Finally, a new palladium-mediated oxidative cyclization led to the formation of tricyclic systems. 相似文献
140.
Soulard P Asselin P Cuisset A Aviles Moreno JR Huet TR Petitprez D Demaison J Freedman TB Cao X Nafie LA Crassous J 《Physical chemistry chemical physics : PCCP》2006,8(1):79-92
CHFClI is among the more favorable molecules for parity violation (PV) measurements in molecules. Despite the fact that calculated PV effects are two orders of magnitude smaller than in some organometallic compounds, CHFClI displays interesting features which could make possible a new experimental PV test on this molecule. Indeed, ultrahigh resolution spectroscopy using an ultrastable CO(2) laser is favored by several intrinsic properties of this molecule. For example, the high vapor pressure of CHFClI allows investigation by supersonic beam spectroscopy. Indeed, the spectroscopic constants have been accurately determined by microwave and millimetre wave spectroscopy. This is important for the subsequent selection of an appropriate absorption band of CHFClI that could be brought to co?ncide with the absorption of CO(2). Partially resolved (+)- and (-)-CHFClI enantiomers with respectively 63.3 and 20.5% ee's have been recently prepared and analyzed by molecular recognition using chiral hosts called cryptophanes. Finally, the S-(+)/R-(-) absolute configuration was ascertained by vibrational circular dichro?sm (VCD) in the gas phase. 相似文献