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61.
Annie Grouiller Valérie Uteza Istvan Komaromi Jean M. J. Tronchet 《Journal of carbohydrate chemistry》2013,32(9):1387-1391
Abstract Analogues of nucleosides in which the nucleobase is fixed onto the C-4 of the sugar moiety are generally prepared either from 4,5-unsaturated sugar derivatives or via a formaldehyde condensation.1 We tested the furanosyl bromide reactivity of 1 2 towards a series of nucleophiles, mostly azides or cyanides, without success. Conversely, the nucleosidation of 1 using 5-methyl-2,4-bis(trimethyl-silyloxy)pyrimidine in the presence of stannic chloride took place at the second anomeric position (C-4) and led to the isolation in acceptable yield (47%) of a unique anomer 2 (Scheme 1). 相似文献
62.
Karel Lacina Martin Konhefr Jan Novotný David Potěšil Zbyněk Zdráhal Petr Skládal 《Tetrahedron letters》2014
A redox-active affinity ligand suitable for reagentless sensing of cis-diols was synthesised and characterised. 4-[(Ferrocenylamino)methyl]thiophene-3-boronic acid (FcTBA) was allowed to interact with the model cis-diol, sorbitol. A discrete, cathodic shift of the redox potential was observed upon interaction of FcTBA with sorbitol thus providing simultaneous differentiation between the free and bound forms of this sensor molecule. Similar behaviour was observed also for FcTBA co-immobilised with thiophene in a mixed self-assembled monolayer on a gold electrode. 相似文献
63.
A series of 9-(hetero)arylpurine derivatives has been prepared through N-arylation of 6-chloropurine with boronic acids in the presence of copper(II) acetate. Screening reaction conditions in terms of bases and solvents led to the successful coupling of a series of sterically demanding (hetero)arylboronic acids, never described so far. The coupling products were next readily converted into the target adenine derivatives. The described procedure provides easy access to original fragments for screening applications. Moreover these 9-aryl-6-chloropurine derivatives might be useful as intermediates for the preparation of purine derivatives with potential biological properties. 相似文献
64.
Emmanuelle Dubost Silvia Stiebing Thibault Ferrary Thomas Cailly Frédéric Fabis Valérie Collot 《Tetrahedron》2014
A set of variously substituted indazoles and hetero-aromatic derivatives were synthesized from o-halo-(het)arylaldehydes using a palladium catalyzed amination followed by cyclization. Starting from phenones, this process was extended to give 3-substituted indazoles. Moreover, N-1-substituted-indazoles can be reached by this strategy using an optional selective N-1-alkylation step during the process. This methodology offers a general and easy route for the synthesis of regioselectively substituted indazoles. 相似文献
65.
Solid-phase microextraction on-fiber derivatization applied to carbonyl compounds is known, but application to indoor air is poorly developed and the methods deserve to be complemented and optimized. In this work, two derivatization reagents, pentafluorophenylhydrazine and o-2,3,4,5,6-(pentaflurobenzyl)hydroxylamine (PFBHA), and three fiber coatings were tested in order to select the best combination. As Carboxen-based coatings were proven to induce the formation of by-products during the thermal desorption step, a polydimethylsiloxane–divinylbenzene fiber in association with PFBHA was finally chosen. The study of the derivatization kinetics showed that the reaction of PFBHA with carbonyl compounds was instantaneous, except for acetone. Analyses were performed by gas chromatography coupled with flame ionization detection and mass spectrometry. For 5 min fiber exposure, the limits of detection are below 0.5 μg m-3 in selected ion monitoring mode, the reproducibility was 15 % on average, and the linearity of the calibration curves was satisfactory. For on-site application, the influence of air humidity and the conditions in which the impregnated fibers were stored were studied. It is possible to store the fibers for 3 days before and for at least 2 days after sampling. The relative humidity of air was shown to have no influence on solid-phase microextraction sampling in the range from 0 to 70 %. For formaldehyde, the method was compared with sampling on 2,4-dinitrophenylhydrazine cartridges, and the first results showed good agreement. Finally, the method was applied to three different indoor environments to check its feasibility. 相似文献
66.
The aim of this work was to optimize the preparation of an anti-ochratoxin A (OTA) oligosorbent (OS), a solid-phase extraction sorbent based on OTA aptamers covalently immobilized on sepharose. Different syntheses were carried out by modifying the side of the oligonucleotide chain bound to the sepharose, the length of the spacer arm between the aptamer and the sepharose and the amount of the aptamers introduced during the covalent grafting. Indeed, the capacity of OSs prepared using 3′- or 5′-amino-modified sequences with a C6 or a C12 was studied. In the best conditions, the concentration of aptamers sequence used during their grafting was increased and a capacity close to 40 nmol g?1 of OS was reached. The potential of the resulting OSs was also studied in pure media. For this, their selectivity was checked by comparing them to a control sorbent prepared without immobilizing aptamers. Extraction recoveries close to 100 % were obtained on all OSs, while no retention was observed on the control sorbent. OS does not demonstrate any cross-reactivity towards OTA metabolites, i.e., ochratoxin B and ochratoxin hydroquinone. The oligosorbent was finally applied to the clean-up of OTA from wheat sample extracts. Extraction recoveries were not affected by matrix interferences and the resulting chromatogram clearly highlights the selectivity of the sorbent that allows the removal of matrix components thus improving the reliability of the quantitation of OTA in real samples. 相似文献
67.
V.?V.?Val’kovEmail author A.?O.?Zlotnikov T.?A.?Val’kova 《Bulletin of the Russian Academy of Sciences: Physics》2015,79(6):746-748
An effective temperature-dependent scattering matrix for a localized subsystem is obtained in the periodic Anderson model by summing itinerant variables in the diagrammatic series of perturbation theory. The effective interaction that occurs in this case can lead to an antiferromagnetic phase, a superconducting phase, and the phase of coexisting superconductivity and antiferromagnetism observed in heavy-fermion intermetallic compounds. 相似文献
68.
69.
Denis Morsa Valérie Gabelica Edwin De Pauw 《Journal of the American Society for Mass Spectrometry》2014,25(8):1384-1393
During their travel inside a traveling wave ion mobility cell (TW IMS), ions are susceptible to heating because of the presence of high intensity electric fields. Here, we report effective temperatures T eff,vib obtained at the injection and inside the mobility cell of a SYNAPT G2 HDMS spectrometer for different probe ions: benzylpyridinium ions and leucine enkephalin. Using standard parameter sets, we obtained a temperature of ~800 K at injection and 728?±?2 K into the IMS cell for p-methoxybenzylpyridinium. We found that T eff,vib inside the cell was dependent on the separation parameters and on the nature of the analyte. While the mean energy of the Boltzmann distributions increases with ion size, the corresponding temperature decreases because of increasing numbers of vibrational normal modes. We also investigated conformational rearrangements of 7+ ions of cytochrome c and reveal isomerization of the most compact structure, therefore highlighting the effects of weak heating on the gas-phase structure of biologically relevant ions. Figure
? 相似文献
70.
Mariana R. Lopes Carlos J. A. de Souza Marina Q. R. B. Rodrigues Daniela A. Costa Ancély F. dos Santos Leandro L. de Oliveira Humberto J. O. Ramos Valéria M. Guimarães Wendel B. Silveira Flávia M. L. Passos Luciano G. Fietto 《Applied biochemistry and biotechnology》2014,172(5):2412-2424
An extracellular β-glucanase secreted by Kluyveromyces marxianus was identified for the first time. The optimal conditions for the production of this enzyme were evaluated by response surface methodology. The optimal conditions to produce β-glucanase were a glucose concentration of 4 % (w/v), a pH of 5.5, and an incubation temperature of 35 °C. Response surface methodology was also used to determine the pH and temperature required for the optimal enzymatic activity. The highest enzyme activity was obtained at a pH of 5.5 and a temperature of 55 °C. Furthermore, the enzyme was partially purified and sequenced, and its specificity for different substrates was evaluated. The results suggest that the enzyme is an endo-β-1,3(4)-glucanase. After optimizing the conditions for β-glucanase production, the culture supernatant was found to be effective in digesting the cell wall of the yeast Saccharomyces cerevisiae, showing the great potential of β-glucanase in the biotechnological production of soluble β-glucan. 相似文献