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141.
The electronic effects of X substituents in aromatic molecules XC6H5, XC6H4Me and XC6H4OMe are studied by measurements of the bonded OH frequencies of phenol-π-base complexes. A judicious choice of the experimental conditions (solvent, π-base concentration, phenol acidity, temperature) permits the following substituents to be studied: Me, Et, CH(Me)2, OMe, OEt, OC6H5, NHMe, N(Me)2, N(Et)2, NHC6H5, C6H5, CHCH2, CCH, CCMe, SMe, SC6H5, F, Cl, Br and I.Halogenated benzenes, benzotrichloride and benzotrifluoride were found to act solely as π-bases. Electronic effects are accurately measured by means of the linear combination ?1σ1 + ?R?°R. The ratio ?R/?1 shows that inductive and mesomeric effects are of the same importance. This ratio may be considered as an argument in favour of the symmetric configuration of the complex. Electronic effects are found to be additive in disubstituted benzenes. 相似文献
142.
Sebastián Ceria Cécile Cordier Hugues Marchand Laurence A. Wolsey 《Mathematical Programming》1998,81(2):201-214
We investigate the use of cutting planes for integer programs with general integer variables. We show how cutting planes arising from knapsack inequalities can be generated and lifted as in the case of 0–1 variables. We also explore the use of Gomory's mixed-integer cuts. We address both theoretical and computational issues and show how to embed these cutting planes in a branch-and-bound framework. We compare results obtained by using our cut generation routines in two existing systems with a commercially available branch-and-bound code on a range of test problems arising from practical applications. © 1998 The Mathematical Programming Society, Inc. Published by Elsevier Science B.V.Corresponding author.This research was partly performed when the author was affiliated with CORE, Université Catholique de Louvain. 相似文献
143.
144.
Laurence S. Rothman Louise D.G. Young 《Journal of Quantitative Spectroscopy & Radiative Transfer》1981,25(6):505-524
Energy levels and rotational constants are provided for all carbon dioxide infrared absorption transitions of significance for terrestrial atmospheric transmission. Constants have been recalculated using new FTS measurements in the 4.3 μm region at elevated temperature, new FTS measurements in the 15, 5, and 2 μm regions, precise laser measurements around 10 μm, and high resolution grating spectrometer measurements of isotopically enriched samples. Band centers, band strengths, and coriolis coupling constants are given for some 560 bands. 相似文献
145.
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147.
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
148.
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
149.
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
150.
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