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31.
Marcela Dvorakova Marie Pribylova Radek Pohl Marie E. Migaud Tomas Vanek 《Tetrahedron》2012,68(33):6701-6711
A migration of methyloxycarbonyl group from secondary to primary hydroxyl was observed in furanosides (ribosides and xylosides) under usual desilylation conditions using tetrabutylammonium fluoride. The migration was studied further on several alkyloxycarbonyl furanosides under either basic or acidic conditions. As follows from 13C labelling experiments and product distribution, the migration in xylosides, proceeds intramolecularly via six-membered cyclic carbonate, whereas in ribosides, the migration is intermolecular. Acidic conditions prevented the migration in ribosides whereas the migration in xylosides was circumvented under neutral conditions. 相似文献
32.
Dayanne Cristiane Mozaner Bordin Marcela Nogueira Rabelo Alves Eduardo Geraldo de Campos Bruno Spinosa De Martinis 《Journal of separation science》2016,39(6):1168-1172
Disposable pipette tips extraction consists of a solid‐phase extraction in which the sorbent is poorly dispersed in a pipette tip, which allows a quick and dynamic contact between the aspirated analyte from the sample and the solid phase. It is a technique used particularly in food and forensic analysis, since it requires a small amount of sample and solvent. This article highlights the principles, advantages and disadvantages of the disposable pipette tips extraction method and reviews recent applications. 相似文献
33.
An amphiphile (surfactant) spread on water can lead to the formation of different aggregates: vesicles, miscelles, emulsions or microemulsions; depending on its concentration; its molecular structure and/or the experimental conditions. Such aggregates, (a) may concentrate products, reactants or analytes and so improve the analytical sensitivity and (b) may solubilize such substances and so favorably change the analytical selectivity. Bilayer membrane vesicles for instance, apart from their wide applications in cosmetic and pharmaceutical industries, have a great analytical potential due to their ability to (i) reversibly sequester metal ions avoiding matrix interference and (ii) improve cold vapor (Hg and Cd) and hydride (As, Se, Pb) chemical generation. Micellar solutions have also found wide applications in different areas of analytical chemistry, showing their capacity to concentrate and separate a significant variety of analytes. Among the numerous micelle-based separation techniques, cloud point extraction offers an excellent enrichment factor for metal ions, allowing their quantification at microgram/litre levels. Also agitating a mixture of water, oil and one or more surfactants under controlled experimental conditions, a cloudy mixture (emulsion) or a transparent solution (microemulsion) can be formed. Adequate formulation is necessary in order to obtain a stable organized media. To fulfill this requirement, a major effort is necessary in order to shorten the gap between the current knowledge on this topic and the promising field of applications that await development. Recent publications show that self-assembly structures from highly viscous samples can be accomplished on-line with the advantages of drastically reducing the time of analysis and assuring the absolute control over the stability of the aggregate. Flow systems allow effective mixing of samples with added surfactant and provide continuous pumping of the resulting mixture to sensitive detectors for the on-line determination of different analytes in complex samples. 相似文献
34.
Kilo M Taylor MA Argirusis C Borchardt G Weber S Scherrer H Jackson RA 《The Journal of chemical physics》2004,121(11):5482-5487
The diffusion of all stable lanthanides was measured both in calcia stabilized zirconia (CSZ) and in yttria stabilized zirconia (YSZ) in the temperature range between 1,286 and 1,600 degrees C. The lanthanide diffusion coefficients obtained increase with increasing ionic radius. The experimental activation enthalpy of diffusion is near 6 eV for CSZ and between 4 and 5 eV for YSZ and is not strongly affected by the type of lanthanide. The results were correlated with defect energy calculations of the lanthanide diffusion enthalpy using the Mott-Littleton approach. An association enthalpy of cation vacancies with oxygen vacancies of about 1 eV (96 kJ/mol) was deduced in the case of CSZ, while there is no association in the case of YSZ. Furthermore, the change in diffusion coefficients can be correlated to the interaction parameter for the interaction between the lanthanide oxide with zirconia: The higher the interaction parameter, the higher the lanthanide diffusion coefficient. 相似文献
35.
Marcela P. Aliste 《Journal of Molecular Structure》2000,507(1-3):1-10
We present a theoretical conformational study of neutral and N-protonated form of dopamine in which we relate its pharmacological activity to the chemical hardness. We have found that the neutral form presents small fluctuations in the energy and the chemical hardness with the conformational variables, whereas the N-protonated form shows significant changes in both properties. An important result is that the Principle of Maximum Hardness is satisfied. The trans coplanar rotamers are postulated as the pharmacophoric conformation(s) because these rotamers show minimal chemical hardness. In addition, we have calculated the hardness of a model of the anionic binding site of the dopamine receptor, which is formed by a formate ion and two benzenes. We have compared the hardness calculated for this model with the hardness of the isolated formate anion, and found that the hardness of the base in the binding site is lower than that of the isolated formate group. Also, it is found that the hardness of the anionic binding site model is similar to that of both trans coplanar rotamers of protonated dopamine, in agreement with the Hard and Soft Acid and Base Principle. 相似文献
36.
Juraj Černák Juraj Kuchár Monika Stolárová Marcela Kajňaková Martin Vavra Ivan Potočňák Larry R. Falvello Milagros Tomás 《Transition Metal Chemistry》2010,35(6):737-744
From the systems Cu(II)–cyclam–[M(CN)4]2? (cyclam = 1,4,8,11-tetraazacyclotetradecane; M = Ni, Pd, Pt), three cyanidocomplexes Cu(cyclam)M(CN)4 [M = Ni (1), Pd (2), Pt (3)] were isolated and characterized by chemical analysis, IR and UV–VIS spectroscopy. The three compounds are isostructural, and their crystal structures are formed by quasi-linear chains exhibiting [–Cu(cyclam)–μ–NC–M(CN)2–μ–CN–]n composition. The Cu(II) atoms reside on centres of symmetry and are coordinated in the form of an elongated octahedron with mean equatorial Cu–N bonds of 2.015(12), 2.017(13) and 2.011(11) Å in (1), (2) and (3), respectively, and weakly N-bonded bridging cyanido ligands in the axial positions [2.5321(9) Å in (1), 2.518(2) Å in (2) and 2.549(3) Å in (3)]. Hydrogen bonds of the N–H···Ncyanido···H–N type link neighbouring chains, and a topologically square network of paramagnetic Cu(II) atoms is formed. The magnetic susceptibilities of all three complexes follow the Curie-Weiss law with a weak antiferromagnetic exchange coupling below 5 K. 相似文献
37.
Aline Machado de Castro Kelly Cristina Nascimento Rodrigues Pedro Juliana Cunha da Cruz Marcela Costa Ferreira Selma Gomes Ferreira Leite Nei Pereira 《Applied biochemistry and biotechnology》2010,162(7):2111-2122
Sugarcane bagasse is an agroindustrial residue generated in large amounts in Brazil. This biomass can be used for the production
of cellulases, aiming at their use in second-generation processes for bioethanol production. Therefore, this work reports
the ability of a fungal strain, Trichoderma harzianum IOC-4038, to produce cellulases on a novel material, xylan free and cellulose rich, generated from sugarcane bagasse, named
partially delignified cellulignin. The extract produced by T. harzianum under submerged conditions reached 745, 97, and 559 U L−1 of β-glucosidase, FPase, and endoglucanase activities, respectively. The partial characterization of this enzyme complex
indicated, using a dual analysis, that the optimal pH values for the biocatalysis ranged from 4.9 to 5.2 and optimal temperatures
were between 47 and 54 °C, depending on the activity studied. Thermal stability analyses revealed no significant decrease
in activity at 37 °C during 23 h of incubation. When compared to model strains, Aspergillus niger ATCC-16404 and Trichoderma reesei RutC30, T. harzianum fermentation was faster and its extract showed a better balanced enzyme complex, with adequate characteristics for its application
in simultaneous saccharification and fermentation processes. 相似文献
38.
Hugo M. Oliveira Marcela A. Segundo José L.F.C. Lima Manuel Miró Victor Cerdà 《Journal of chromatography. A》2010,1217(22):3575-3582
For the first time, an automatic sample pre-treatment/detection method is proposed for the multiclass determination of UV filters (namely, benzophenone-3, ethylhexylmetoxycinnamate, butylmethoxydibenzoylmethane and homosalate) in environmental samples. The new methodology comprises in-line solid-phase extraction (SPE) of the target analytes by exploiting the bead injection (BI) concept in a mesofluidic lab-on-valve (LOV) format, with subsequent determination by liquid chromatography (LC). The proposed microanalytical system, using a multisyringe burette as propulsion unit, automatically performed the overall SPE steps, including the renewal of the sorbent in each analytical cycle to prevent sample cross-contamination and the post-extraction adjustment of the eluate composition to prevent chromatographic band broadening effects. In order to expedite the LC separation, a C18 monolithic column was applied and an accelerated isocratic elution was carried out by using a cationic surfactant as mobile phase additive. The LOV-BI-LC method was proven reliable for handling and analysis of complex matrices, e.g., spiked swimming pool water and seawater, with limits of detection ranging between 0.45 and 3.2 μg L−1 for 9 mL sample volume. Linear calibration was attained up to 160 μg L−1 for homosalate and up to 35 μg L−1 for the other target analytes, with good reproducibility (RSD < 13%, for 5 different SPE columns). The hyphenated scheme is able to process a given sample simultaneously and within the same time frame than the chromatographic separation/determination of the formerly pre-treated sample, providing concentration values every 9 min. Hence, the sample throughput was enhanced up to 33 times when compared with previously reported off-line SPE methods. A drastic reduction in reagent consumption and effluent production was also attained, contributing to the development of an environment-friendly analyzer. 相似文献
39.
Marcela Sanmartino 《Journal of Fourier Analysis and Applications》2001,7(6):615-631
The Calderón Projector, is one of the most important tools in the study of boundary value problems for elliptic operators.
Its construction is well known for elliptic operators with C∞ coefficients on C∞ domains and even for the Laplacian operator on C1 domains. The aim of this article is to extend the results for the Laplacian case to elliptic operators in divergence form
with Lipschitz coefficients on C1 domains. 相似文献
40.