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排序方式: 共有365条查询结果,搜索用时 15 毫秒
1.
Lionel Thibault Nadia Zlateva 《Proceedings of the American Mathematical Society》2005,133(10):2939-2948
Using a quantitative version of the subdifferential characterization of directionally Lipschitz functions, we study the integrability of subdifferentials of such functions over arbitrary Banach space.
2.
Using a high resolution Raman spectrometer, we have measured Ar-broadening coefficients in the ν2Q branch of C2H2 for 22 lines at 295 K, 20 lines at 174 K, and 16 lines at 134 K. These lines with J values ranging from 1 to 23 are located in the spectral range 1970.9-1974.3 cm−1. The collisional widths are obtained by fitting each spectral line with a Rautian profile. The resulting broadening coefficients are compared with theoretical values arising from close coupling and coupled states calculations. A satisfactory agreement is obtained at room as well as at low temperatures, especially for odd J lines. By comparing broadening coefficients at 295, 174, and 134 K from a simple power law, the temperature dependence of these broadenings has been determined both experimentally, and theoretically. 相似文献
3.
A capillary electrophoresis (CE) method using acidic buffers and capillaries coated with Polybrene, a cationic polymer has been developed for the separation of glycoproteins and glycopeptides. Electrophoretic conditions have been optimized to provide resolution of individual glycoforms observed for different glycoprotein preparations. These conditions were found to be entirely compatible with the operation of electrospray mass spectrometry (ESMS), which facilitated the assignments of possible carbohydrate compositions of glycopeptides arising from digests of glycoproteins. By using operating conditions enhancing the formation of oxonium fragment ions prior to mass spectral analysis, selective identification of glycopeptides was achieved for complex samples such as those from proteolytic digests or chemical cleavages. Examples of applications are presented for ribonuclease B, ovalbumin, horseradish peroxidase, and a lectin from Erithrina corallodendron using both CE-ESMS and CE with ultraviolet detection (CE-UV). 相似文献
4.
Cantat T Jaroschik F Nief F Ricard L Mézailles N Le Floch P 《Chemical communications (Cambridge, England)》2005,(41):5178-5180
New samarium carbene complexes have been synthesized and characterized by X-ray diffraction analysis; the carbenic nature was assessed by reactivity studies. 相似文献
5.
Lionel Thibault 《Annali di Matematica Pura ed Applicata》1980,125(1):157-192
Summary We introduce the concept of compactly lipschitzian functions taking values in a topological vector space F. We show that if F is finite dimensional the Lipschitz functions are compactly lipschitizian. We define the notions of generalized directional derivatives and subdifferentials for such functionsf taking values in an ordered topological vector space. It is shown that this notion of subdifferential coincides with the one of F. H. Clarke whenf is Lispchits and F=. Some formulas for this subdifferential concerning the cases of finite sum, composition, pointwise supremum and continuous sum are studied. 相似文献
6.
Quéméner B Cabrera Pino JC Ralet MC Bonnin E Thibault JF 《Journal of mass spectrometry : JMS》2003,38(6):641-648
Partially acetylated and methylated oligogalacturonides produced by enzymatic hydrolysis of sugar beet pectin were analysed by negative electrospray ionization ion trap mass spectrometry (ESI-ITMS). The (18)O labelling of the oligomer reducing end allowed the precise assignment of the fragments resulting from glycosidic bond and cross-ring cleavages. The collisional-induced dissociation of the C(i) and Z(j) fragment ions through sequential MS(n) experiments always displayed (0, 2)A-type cross-ring cleavage ions which were related to C(2)H(4)O(2) losses. These (0, 2)A ions appeared to be highly diagnostic ions allowing the precise location of the acetyl groups to the O-2 and/or O-3 of the acetylated galacturonic acid residues. 相似文献
7.
Banoub J Cohen A Mansour A Thibault P 《European journal of mass spectrometry (Chichester, England)》2004,10(1):121-134
Vitellogenin (VTG) is a protein produced by the liver of oviparous animals in response to circulating estrogens. In the plasma of males and immature females, VTG is undetectable. VTG has been used as a biomarker for exposure to endocrine disruptors in many species. In the present study, characterization of intact Atlantic salmon VTG was effected using matrix-assisted laser desorption/ionization time-of-flight mass spectrometry (MALDI ToF MS). Tryptic digest peptides were analyzed by MALDI ToF MS to obtain a peptide mass fingerprint. De novo sequencing of the tryptic peptides used low-energy collisionally-induced dissociation (CID) in an electrospray ionization quadrupole-ToF orthogonal hybrid mass spectrometer (ESI Q-ToF MS/MS). The interpretation of the product-ion spectra obtained from the ESI Q-ToF MS/MS was done by Lutefisk, a computer-based software algorithm. The molecular mass of the intact protein was found to be 187335 Da. A total of 14 tryptic peptides were sequenced and compared with the complete rainbow trout VTG and the partial Atlantic salmon VTG sequences found in the Swiss-Prot database. De novo sequencing by CID MS/MS of 11 Atlantic salmon tryptic digest peptides with selected precursor ions at m/z 788.24, 700.20, 794.75, 834.31, 889.28, 819.79, 865.27, 843.81, 572.20, 573.66 and 561.68 showed high homology with the known sequence of rainbow trout VTG. The last two precursor peptide ions, found at m/z 573.66 and m/z 561.68, also specifically matched the known portion of the Atlantic salmon VTG sequence. Finally, three tryptic precursor peptide ions found at m/z 795.18, 893.28 and 791.05, provided product-ion spectra, which were exclusive to the unsequenced portion of the Atlantic salmon VTG. 相似文献
8.
Uzun O Sanyal A Nakade H Thibault RJ Rotello VM 《Journal of the American Chemical Society》2004,126(45):14773-14777
Polystyrene functionalized with diamidopyridine (DAP) recognition units self-assembles in nonpolar media to form thermally reversible micrometer-scale spherical aggregates. The size and the thermal stability of these microspheres can be controlled by the molecular weight of the polymer. The addition of thymine-functionalized polymer to these self-assembled microspheres converted them into vesicular aggregates with a controlled size. The morphology change was reversible: the addition of DAP-functionalized polymer converted the vesicles back to microspheres. 相似文献
9.
Alexander B. Weberg Subhajyoti Chaudhuri Thibault Cheisson Christian Uruburo Ekaterina Lapsheva Pragati Pandey Michael R. Gau Patrick J. Carroll George C. Schatz Eric J. Schelter 《Chemical science》2022,13(23):6796
The separation and purification of niobium and tantalum, which co-occur in natural sources, is difficult due to their similar physical and chemical properties. The current industrial method for separating Ta/Nb mixtures uses an energy-intensive process with caustic and toxic conditions. It is of interest to develop alternative, fundamental methodologies for the purification of these technologically important metals that improve upon their environmental impact. Herein, we introduce new Ta/Nb imido compounds: M(tBuN)(TriNOx) (1-M) bound by the TriNOx3− ligand and demonstrate a fundamental, proof-of-concept Ta/Nb separation based on differences in the imido reactivities. Despite the nearly identical structures of 1-M, density functional theory (DFT)-computed electronic structures of 1-M indicate enhanced basic character of the imido group in 1-Ta as compared to 1-Nb. Accordingly, the rate of CO2 insertion into the M Nimido bond of 1-Ta to form a carbamate complex (2-Ta) was selective compared to the analogous, unobserved reaction with 1-Nb. Differences in solubility between the imido and carbamate complexes allowed for separation of the carbamate complex, and led to an efficient Ta/Nb separation (STa/Nb = 404 ± 150) dependent on the kinetic differences in nucleophilicities between the imido moieties in 1-Ta and 1-Nb.A selective separation of the critical metals tantalum and niobium was accomplished from π-bonding-based reactivity differences of imido complexes. New insights into Ta/Nb separations were gained through detailed kinetic and computational studies. 相似文献
10.
Dr. Aurélien Adenot Dr. Lucile Anthore-Dalion Dr. Emmanuel Nicolas Jean-Claude Berthet Dr. Pierre Thuéry Dr. Thibault Cantat 《Chemistry (Weinheim an der Bergstrasse, Germany)》2021,27(72):18047-18053
An air-tolerant Cu-catalyzed sulfonylative Hiyama cross-coupling reaction enabling the formation of diaryl sulfones is described. Starting from aryl silanes, DABSO and aryliodides, the reaction tolerates a large variety of polar functional groups (amines, ketones, esters, aldehydes). Control experiments coupled with DFT calculations shed light on the mechanism, characterized by the formation of a Cu(I)-sulfinate intermediate via fast insertion of a SO2 molecule. 相似文献