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31.
Eulogio Jimenez Luis Romani Maria Inmaculada Paz Andrade Geneviève Roux-Desgranges Jean-Pierre E. Grolier 《Journal of solution chemistry》1986,15(11):879-890
Molar excess volumes V
E
at 25°C have been determined by vibrating-tube densimetry, as a function of mole fraction x for different series of an alkanoate (H
2m+1
C
m
COOC
n
H
2n+1
)+cyclohexane. Three types of alkanoates were investigated, i.e., methanoates (m=0, with n=3 and 4), ethanoates (m=1, with n=2, 3, and 4) and propanoates (m=2, with n=1, 2, and 3). In addition, a Picker flow calorimeter was used to obtain molar excess heat capacities C
p
E
at constant pressure at the same temperature. V
E
is positive for all systems and rather symmetric, with V
E
(x=0.5) amounting to almost identical values in a series of mixtures containing an alkanoate isomer of same formula (say C4H8O2, C5H10O2, or C6H12O2). The composition dependence of C
p
E
is rather unusual in that two more or less marked minima are observed for most of the mixtures, especially when the alkanoate is a methanoate or an ethanoate. These results are discussed in terms of possible changes in conformation of both the ester and cyclohexane. 相似文献
32.
Stephen de Mora Jean-Pierre Villeneuve Eric Wyse 《Accreditation and quality assurance》2007,12(11):587-592
Aspects of the International Atomic Energy Agency (IAEA) Analytical Quality Control Services (AQCS) for marine environmental
studies are discussed, focusing on recent laboratory performance studies (LPS) and the production of reference materials for
trace metals and organic compounds in various marine matrices. The IAEA has organized seventeen global interlaboratory studies
for a range of organic contaminants. Of note has been the inclusion of numerous polychlorinated biphenyl congeners (PCBs)
and some sterols of anthropogenic origin. Concurrently, there have been eleven worldwide intercomparison exercises for trace
metals in the marine environment, most of which included methylmercury. Although such interlaboratory studies can help improve
performance in individual laboratories and regional laboratory networks, the results reveal that problems remain in the determination
of some metals and many organic contaminants. 相似文献
33.
Abstract— In order to investigate the intramolecular "quenching" of the photoexcitation of some 5-alkenyloxypsoralen derivatives, we have prepared model compounds in which a psoralen moiety was linked at position 5 to a terminal double bond via a polymethylenic chain of various length (n = 2-9). The isolation and characterization of photocycloadducts obtained for each compound after irradiation at 365 nm in a polar solvent was performed. The results on the photoreactivity of this series of compounds show that the 3,4-pyrone double bond of 5-alkoxypsoralens is the most reactive. Four kinds of intramolecular photocycloadducts between the 3,4-pyrone double bond and the chain unsaturation were obtained according to the length of the linking chain: cis-syn, trans-syn, cis-anti and trans-anti. Their structures were established by a combination of 1 H and 13 C NMR and fully assigned by l H NOE (nuclear Overhauser effect) and 1 H-13 C HMQC (heteronuclear multiquantum correlation) spectroscopies. No traces of 4',5' adducts were detected. 相似文献
34.
The alkylation of 8-lithiopurine trimethylsilyl nucleosides at carbon 8 can be carried out conveniently by reaction with various electrophilic reagents. 相似文献
35.
Christine Bonal Jean-Pierre Morel Nicole Morel-Desrosiers 《Journal of solution chemistry》1998,27(4):361-372
The apparent equilibrium constants and enthalpies of complexation of Nd3+, Sm3+, Eu3+, and Gd3+ by xylitol in aqueous solutions containing NaNO3 at an ionic strength of 2.0 mol-kg–1 have been determined by microcalorimetry at 25°C. Since nitrate anion weakly complexes the lanthanide cations, these values are analyzed in terms of competition between xylitol and NO
3
-
The method leads to the apparent equilibrium constants and enthalpies of complexation of the lanthanide cations by NO
3
-
at this particular ionic strength. Despite the difficulties encountered in characterizing rather weak associations, the results are, whenever comparison is possible, in good agreement with those obtained by direct microcalorimetry. The advantage of this competition method is that it can be used when the enthalpic effects are too weak and insufficiently concentration dependent for direct microcalorimetric determination. In the present case, it allows us to thermodynamically characterize the formation of SmNO
3
2+
and EuNO
3
2+
, processes we have not been able to study directly. 相似文献
36.
Maria A Girault JP Saatov Z Harmatha J Dinan L Lafont R 《Journal of chromatographic science》2005,43(3):149-157
Ecdysteroid glycosides are found in both animals and plants. The chromatographic behavior of these molecules is characteristic, as they appear much more polar than their corresponding free aglycones when analyzed by normal-phase high-performance liquid chromatography (HPLC), whereas the presence of glycosidic moieties has a very limited (if any) impact on polarity when using reversed-phase HPLC. Biological activity is greatly reduced because the presence of this bulky substituent probably impairs the interaction with ecdysteroid receptor(s). 2-Deoxy-20-hydroxyecdysone 22-O-beta-D-glucopyranoside, which has been isolated from the dried aerial parts of Silene nutans (Caryophyllaceae), is used as a model compound to describe the rationale of ecdysteroid glycoside purification and identification. 相似文献
37.
An efficient preparation of N-methyl-O-tert-butylhydroxylamine hydrochloride has been settled, which allowed the synthesis of modified Weinreb amides. Nucleophilic addition of organolithium and Grignard reagents on these N-tert-butoxy-N-methylamides afforded efficiently the corresponding ketones and reduction with DIBAL furnished the corresponding aldehydes in good yields up to 97%. 相似文献
38.
Maria Vittoria SpaneddaVu Dinh Hoang Benoit Crousse Danièle Bonnet-Delpon Jean-Pierre Bégué 《Tetrahedron letters》2003,44(2):217-219
Hexafluoroisopropanol and trifluoroethanol are found to promote imino-Diels-Alder reactions of the N-aryl aldimine 1 with alkyl vinyl ethers to afford the corresponding tetrahydroquinolines in good yields without Lewis acid under mild and neutral conditions. The reaction is also efficient in a three component process from aldehyde, amine and vinyl ethers. 相似文献
39.
Robert Faure Jean-Pierre Galy Emile-Jean Vincent Jos Elguero 《Journal of heterocyclic chemistry》1977,14(8):1299-1304
The substituent effects on azido/tetrazole equilibrium on a series of 2-substituted thiazoles, benzothiazoles, thiadiazoles, benzoxazoles and isoxazoles has been studied by proton magnetic resonance in two solvents (DMSO-d6 and deuteriochloroform). For thiazole an excellent Hammett relationship was found, both for the 4 and 5 positions. 相似文献
40.
Jean-Philippe Demaret † Simone Brunie Jean-Pierre Ballini Paul Vigny 《Photochemistry and photobiology》1989,50(1):7-21
The results of molecular mechanical calculations on intercalation complexes of 3-carbethoxypsoralen, 5-methoxypsoralen, 8-methoxypsoralen, 7-methylpyrido[3,4-c]psoralen (MepyPs) and 7-methylpyrido[4,3-c]psoralen (2N-MePyPs) with the double stranded duodecanucleotide d(CGCGATATCGCG)2 are presented. In the energy-minimized structures, the psoralens are intercalated with their plane orthogonal to the helix axis. Stacking interactions between the furan ring of the psoralen and the adjacent bases are maximized in most derivatives studied, whereas the effect of the various substituents of the psoralen ring is to specifically push part of the molecule towards either the minor or the major groove, preventing a symmetrical intercalation (with respect to the two strands of the DNA). The relative position of the psoralen ring and of the adjacent thymine foreshadows the formation of furan-side monoadducts in 3-CPs, MePyPs and 2N-MePyPs, whereas the formation of a pyrone-side monoadduct appears as geometrically more favourable in 5-MOP and both furan- and pyrone-side monoadducts can be geometrically envisaged in 8-MOP. A good correlation therefore exists between the more or less favourable equilibrium geometries and the experimentally observed photoreactions. The present study is the first attempt to characterize the geometrical parameters as part of a complex set of geometrical, dynamical and excited state parameters governing the overall DNA-psoralen photoreaction. 相似文献