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31.
A simple equation has been derived relating the temperature dependence of activity functions with excess enthalpies and excess heat capacities. Using experimentally determined parameters at 298.15°K, it is possible to predict osmotic coefficients and mean activity coefficients of alkali halides in water up to 1 m from 273°K to about 350°K. In general, the predicted functions agree with the measured values within the uncertainty of the activity data. An equation is also given for the pressure dependence of the excess free energies, but it was not possible to check the limitation of this equation due to lack of activity data at various pressures.To whom correspondence should be addressed. 相似文献
32.
Christophe Thurieau Christel Guyard Serge Simonet Tony J. Verbeuren Jean-Luc Fauchre 《Helvetica chimica acta》1994,77(3):679-684
The synthesis on solid phase of a new derivative of the anticoagulant protein hirudin is described (see Scheme and Fig.1, I ). The henicosapeptide is a bivalent conjugate of the C-terminus of hirudin and of the active-site-binding tetrapeptide D -Phe-Pro-Arg-Pro linked via a tetraglycine spacer. The peptide, for which the name hirufos was coined, incorporates a stable phosphono derivative of L -phenylalanine which, combined with the other structural modifications, leads to a potent anticoagulant agent. Synthesis was readily achieved by the (9H-fluoren-9-yl)-methoxycarbonyl (Fmoc) strategy followed by acidolytic cleavage from the resin and deprotection, including the liberation of the crucial phosphonic group on L -phenylalanine. 相似文献
33.
Jean-Luc Decout Alain Lablache-Combier Claude Loucheux 《Journal of polymer science. Part A, Polymer chemistry》1980,18(7):2371-2390
Vinylpyridine-N-oxide units were introduced in polymeric chains in order to study their photocrosslinking. Copolymers of styrene and 4-vinylpyridine-N-oxide were especially synthesized and studied. The methods used for characterization of photocrosslinked films were a “photoresist test” or the measurement of the insolubility and of the swelling ratio. The Cleavage of the N-oxide bond was responsible for the photocrosslinking. The competitive formation of carbonyl compounds took place and decreased the rate of photocrosslinking. This last reaction is favored by triplet-state quenchers. The photosensitivity of the copolymers was determined as a function of the wavelength of the radiation used. When the photocrosslinking proceeded, a film of the copolymeric material became transparent in the 280–320-nm range. Thick films could therefore be completely photocrosslinked when irradiated in this range of wavelength. 相似文献
34.
Jones SC Coropceanu V Barlow S Kinnibrugh T Timofeeva T Brédas JL Marder SR 《Journal of the American Chemical Society》2004,126(38):11782-11783
A complex featuring two triarylamine redox centers bridged by Pt, trans-bis(triethylphosphine)-bis{4-[bis(4-methoxyphenyl)amino]phenylethynyl} platinum(II), has been synthesized as a model system for pi-conjugated Pt-containing polymers. Analysis of the intervalence charge-transfer band displayed by its mixed-valence monocation affords a quantitative assessment of electronic delocalization through the Pt bridge; this is found to be only slightly smaller than that determined for a benzene-bridged analogue. These results are supported by density functional theory calculations, which show that the active orbitals involved in the electron-transfer process in both cases have similar delocalization through the bridging unit. 相似文献
35.
Reversed phase high performance liquid chromatography (RPLC) is currently the method of choice for the analysis of basic compounds. However, with traditional silica materials, secondary interactions between the analyte and residual silanols produce peak tailing which can negatively affect resolution, sensitivity, and reproducibility. In order to reduce these secondary interactions, which comprise ion exchange, hydrogen bonding, and London forces interactions, chromatographic analyses can be carried out at low or high pH values where silanol groups and basic compounds are mostly uncharged. The chromatographic behaviour of a particular bidentate stationary phase, Zorbax Extend C18, was studied with a set of basic and neutral compounds. Thanks to a higher chemical stability than traditional silica based supports, analyses were carried out with a high pH mobile phase, which represents a good alternative to the acidic mobile phases generally used to reduce ion exchange interactions. The performance of this bidentate stationary phase was also compared with that of other supports and it was proved that it is advantageous to work with high pH mobile phases when analyzing basic compounds. 相似文献
36.
Summary In this paper, we extend recent work of one of us [Br] to investigate an old problem of the other one [B2]. Given a connected semisimple complex Lie-groupG with Lie-algebrag, we study the representation
of the enveloping algebra of
by global differential operators on a complete homogeneous spaceX=G/P. It turns out that the kernelI
x
of
X
is the annihilator of a generalizedVerma-module. On the other hand, we study the associated graded ideal grI
x
, and relate it to the geometry of a generalizedSpringer-resolution, that is a map
of the cotangent-bundle ofX onto a nilpotent variety in
, as studied e.g. in [BM1]. We prove, for instance, that grI
x
is prime if and only if
X
is birational with normal image. In general, we show that
is prime. Equivalently, the associated variety ofI
x
in
is irreducible: In fact, it is the closure of theRichardson-orbit determined byP. For the homogeneous spaceY=G/(P, P), we prove that the analogous idealI
y
has for associated variety the closure of theDixmier-sheet determined byP. From this main result, we derive as a corollary, that for any module induced from a finitedimensional LieP-module the associated variety of the annihilator is irreducible, proving an old conjecture [B2], 2.5. Finally, we give some applications to the study of associated varieties of primitive ideals. 相似文献
37.
(Z)-Ethyl-3-perfluoroalkyl-3-magnesiated crotonates were prepared from (Z)-ethyl-3-perfluoroalkyl-3-iodo enoates by iodine-magnesium exchange reaction with isopropylmagnesium bromide in THF at -78 degrees C. These new reagents reacted with a range of electrophiles, leading to polyfunctional products bearing a perfluoroalkyl group. 相似文献
38.
Bernard Loubinoux Jean-Luc Colin Samir Tabbache 《Journal of heterocyclic chemistry》1984,21(6):1669-1672
The preparation of 1-aryloxymethyl-1,2,3-triazoles, potential biologically active compounds particularly in the pesticide field, is described. The action of sodium azide on aryloxymethyl halides gave aryloxymethyl azides. The cycloaddition reactions of azides with acetylenic compounds provided the expected triazoles in good yields. 相似文献
39.
Hans Fritz Rolf Gleiter Michel Nastasi Jean-Luc Schuppiser Jacques Streith 《Helvetica chimica acta》1978,61(8):2887-2898
3-Substituted 1-iminopyridinium ylides 1 undergo photo-induced ring enlargement to 1H-1,2-diazepines. With strongly electron-withdrawing substituents the ring expansion process is regiospecific and leads exclusively to 4-substituted 1 H-1, 2-diazepines. Weak electron-donating substituents, like a methyl group and halogen atoms, do not have any directing effect since both 4- and 6-substituted 1 H -1,2-diazepines are obtained. With strong electron-donating substituents no diazepines are formed; instead one observes photo-induced isomerization to the 2-aminopyridine derivatives, the process being non-regiospecific. Regiospecific photo-induced ring expansion processes are explained in terms of a simple HMO model. 相似文献
40.
Plasticized protein films were prepared by the casting method from water solution of sodium caseinate and plasticizers with the aim to obtain environmentally friendly materials for packaging applications. Mechanical properties (tensile strength, elongation and Young’s modulus) of caseinate based films were determined versus ratio of protein to plasticizer, plasticizer type and relative humidity conditions. Among the different polyol-type plasticizers tested, glycerol (Gly) and triethanolamine (TEA) were the most efficient for the improvement of mechanical properties (high strains for low stresses). Further, chemical crosslinking between formaldehyde (HCHO) and free amino groups (ε-NH2) of sodium caseinate was performed to increase water resistance of TEA plasticized films. Optimal mechanical properties, i.e. elastic modulus of 105 MPa, tensile strength of 8-9 MPa for elongation at break about 110-125% were obtained for HCHO/ε-NH2 ratios higher than 1.35. Protein specific water solubility was determined from a 280 nm absorbance. For convenient crosslinker (HCHO) content sodium caseinate solubility can be lowered to less than 5 wt% after 24 h immersion in water. 相似文献