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81.
Sophie Bourcier Clémentine Poisson Yasmine Souissi Said Kinani Stéphane Bouchonnet Michel Sablier 《Rapid communications in mass spectrometry : RCM》2010,24(20):2999-3010
With the future aim of elucidating the unknown structures of estrogen degradation products, we characterized the dissociation pathways of protonated estrone (E1) under collisional activation in liquid chromatography/tandem mass spectrometry (LC/MS/MS) experiments employing a quadrupole time‐of‐flight mass spectrometer. Positive ion and negative ion modes give information on the protonated and deprotonated molecules and their product ions. The mass spectra of estrone methyl ether (CH3‐E1) and estrone‐d4 (E1‐d4) were compared with that of E1 in order (i) to elucidate the dissociation mechanisms of protonated and deprotonated molecules and (ii) to propose likely structures for each product ions. The positive ion acquisition mode yielded more fragmentation. The mass spectra of E1 were compared with those of estradiol (E2), estriol (E3) and 17‐ethynylestradiol (EE2). This comparison allowed the identification of marker ions for each ring of the estrogenic structure. Accurate mass measurements have been carried out for all the identified ions. The resulting ions revealed to be useful for the characterization of structural modifications induced by photolysis on each ring of the estrone molecule. These results are very promising for the determination of new metabolites in the environment. Copyright © 2010 John Wiley & Sons, Ltd. 相似文献
82.
Dr. Abdelkrim El Kadib Prof. Mosto Bousmina 《Chemistry (Weinheim an der Bergstrasse, Germany)》2012,18(27):8264-8277
Recently, organic–inorganic hybrid materials have attracted tremendous attention thanks to their outstanding properties, their efficiency, versatility and their promising applications in a broad range of areas at the interface of chemistry and biology. This article deals with a new family of surface‐reactive organic–inorganic hybrid materials built from chitosan microspheres. The gelation of chitosan (a renewable amino carbohydrate obtained by deacetylation of chitin) by pH inversion affords highly dispersed fibrillar networks shaped as self‐standing microspheres. Nanocasting of sol–gel processable monomeric alkoxides inside these natural hydrocolloids and their subsequent CO2 supercritical drying provide high‐surface‐area organic–inorganic hybrid materials. Examples including chitosan–SiO2, chitosan–TiO2, chitosan–redox‐clusters and chitosan–clay‐aerogel microspheres are described and discussed on the basis of their textural and structural properties, thermal and chemical stability and their performance in catalysis and adsorption. 相似文献
83.
84.
Ranganathan A El-Ghayoury A Mézière C Hartê E Clérac R Batail P 《Chemical communications (Cambridge, England)》2006,(27):2878-2880
The ionic character of a set of two redox linkages and strong, directional halogen bonding at the organic-inorganic interface compromise to produce two materials sharing a common two-dimensional net, eventually extended in a third dimension, although two of the six symmetrical halogen bond acceptors ultimately remain uninvolved as a result of charge densification. 相似文献
85.
Hikov T Schroeter MK Khodeir L Chemseddine A Muhler M Fischer RA 《Physical chemistry chemical physics : PCCP》2006,8(13):1550-1555
A novel, non-aqueous, organometallic route to nanocomposite Cu@TiO2 materials is presented. TiO2 nanorods stabilized with oleic acid (OLA) were used as support for the photo-assisted deposition of Cu using the organometallic Cu(II) precursor [Cu(OCH(CH3)CH2N(CH3)2)2] (1). The copper precursor penetrates through the shell of OLA and is photo reduced to deposit Cu0 directly at the surface of the TiO2 rods. The obtained Cu decorated nanorods were still soluble in nonpolar organic solvents without change of the morphology of nanorods. The Cu@TiO2 colloid was characterized by means of UV-VIS, XRD, AAS, and HRTEM. FTIR CO adsorption studies provide evidence for Cu0 anchored at the titania surface by a characteristic absorption at 2084 cm-1. Comparative studies of Cu-deposition were performed using CuCl2 as simple Cu source which proved that the concept of organometallic disguise of the metal centre results in a higher reaction rate and the circumvention of non-selective reduction, parasitic side reactions and undesired agglomeration of the OLA stabilized titania nanorods. 相似文献
86.
Bouabdallah I M'Barek LA Zyad A Ramdani A Zidane I Melhaoui A 《Natural product research》2006,20(11):1024-1030
The evaluation of the cytotoxic properties in vitro of three synthetic tripods containing pyrazole: N,N-bis[(3,5-dimethylpyrazol-1-yl)methyl]aniline (1); N,N-tetrakis[(3,5-dimethylpyrazol-1-yl)methyl]-para-phenylenediamine (2); and N,N-tetrakis-[(1,5-dimethylpyrazol-3-yl)methyl]-para-phenylenediamine (3), was examined for their cytotoxic activity on two tumor cell lines: P815 (murin mastocytoma) and Hep (human laryngeal carcinome). While the compound 2 shows a small cytotoxic activity, compounds 1 and 3 are more cytotoxic against both cell lines. However, this cytotoxicity is more pronounced against Hep cell line (IC50: 3.25 microg mL(-1) for compound 1 and 6.92 microg mL(-1) for compound 3) than P815 cell line (IC50: 17.82 microg mL(-1) for compound 1 and 37.21 microg mL(-1) for compound 3). Statistical analysis shows that the compound 1 is two- to threefold more cytotoxic than compound 3 (P < 0.05). Interestingly, the cytotoxicity induced by compound 1 against Hep cell line is more important than that induced by adriamycin used as a positive control. 相似文献
87.
Leonhard H. Urner Maiko Schulze Yasmine B. Maier Waldemar Hoffmann Stephan Warnke Idlir Liko Kristin Folmert Christian Manz Carol V. Robinson Rainer Haag Kevin Pagel 《Chemical science》2020,11(13):3538
Mass spectrometry enables the in-depth structural elucidation of membrane protein complexes, which is of great interest in structural biology and drug discovery. Recent breakthroughs in this field revealed the need for design rules that allow fine-tuning the properties of detergents in solution and gas phase. Desirable features include protein charge reduction, because it helps to preserve native features of protein complexes during transfer from solution into the vacuum of a mass spectrometer. Addressing this challenge, we here present the first systematic gas-phase study of azobenzene detergents. The utility of gas-phase techniques for monitoring light-driven changes of isomer ratios and molecular properties are investigated in detail. This leads to the first azobenzene detergent that enables the native mass spectrometry analysis of membrane proteins and whose charge-reducing properties can be tuned by irradiation with light. More broadly, the presented work outlines new avenues for the high-throughput characterization of supramolecular systems and opens a new design strategy for detergents in membrane protein research.Here, L. H. Urner and co-workers identify a new detergent design strategy for the non-denaturing structural analysis of membrane proteins by studying the gas-phase properties of azobenzene-based oligoglycerol detergents. 相似文献
88.
89.
Qi Wang Qile Wang Yuexiang Zhang Yasmine M. Mohamed Carlos Pacheco Nan Zheng Richard N. Zare Hao Chen 《Chemical science》2021,12(3):969
Although synthetic organic electrochemistry (EC) has advanced significantly, net redox neutral electrosynthesis is quite rare. Two approaches have been employed to achieve this type of electrosynthesis. One relies on turnover of the product by the reactant in a chain mechanism. The other involves both oxidation on the anode and reduction on the cathode in which the radical cation or the radical anion of the product has to migrate between two electrodes. Herein, a home-built electrochemistry/mass spectrometry (EC/MS) platform was used to generate an N-cyclopropylaniline radical cation electrochemically and to monitor its reactivity toward alkenes by mass spectrometry (MS), which led to the discovery of a new redox neutral reaction of intermolecular [3 + 2] annulation of N-cyclopropylanilines and alkenes to provide an aniline-substituted 5-membered carbocycle via direct electrolysis (yield up to 81%). A chain mechanism, involving the regeneration of the substrate radical cation and the formation of the neutral product, is shown to be responsible for promoting such a redox neutral annulation reaction, as supported by experimental evidence of EC/MS.We report the use of an online electrochemistry/mass spectrometry platform to develop a redox neutral electrosynthesis of 5-membered rings via [3 + 2] annulation of N-cyclopropylanilines and alkenes, without additional oxidant, reductant or catalyst. 相似文献
90.
The chromatographic and electrophoretic methods developed for the chiral and achiral analyses if antifungal agents are reviewed. The aim of this review is to compare different methodologies of analytical methods and to explore still the existing analytical problems. Last decade is characterized by dynamic development of instrumental methods that results in advance and diversity of applied analytical procedures. The enantiomeric separation of several compounds, including an antifungal drug and several of its precursors, using high-performance liquid chromatography (HPLC) and capillary electrophoresis (CE) is described in this work. The main focus was given to HPLC, the technique of choice in the analysis of most of the pharmaceutical formulations and biological samples. The columns used were based on polysaccharide derivatives. However, the results show that most of the separations obtained by CE are better, in terms of high resolution and short analysis time. The review discusses the chromatographic analysis of the following triazole antifungal drugs: fluconazole, itraconazole, and terconazole from the first generation and posaconazole, voriconazole, ravuconazole, isavuconazole, and albaconazole from the second generation in their pharmaceutical formulations and biological samples. 相似文献