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431.
Péter Szabó Barnabás Kállai-Szabó Nikolett Kállai-Szabó István Sebe Romána Zelkó 《Cellulose (London, England)》2014,21(6):4419-4427
Water-soluble, nonionic cellulose-based fibers were prepared from aqueous hydroxypropyl cellulose gels of 5–13-μm diameter by using a high-speed rotary spinning technique. A combination of texture analysis and viscosity measurement was applied to determine the optimum concentration of hydroxypropyl cellulose gels for fiber formation. The examined concentration range of hydroxypropyl cellulose gels was 38–52 % w/w. The textural properties including the adhesiveness of gels of different concentrations were determined based on the load-distance and load-time curves, while the obtained fiber formation was visually observed with an optical microscope. The texture analysis method enabled the determination of the optimum gel concentration from the point of fiber formation. An unequivocal correlation was determined between the adhesiveness of gels and their fiber-forming ability. The adhesiveness has a local minimum where the productivity of the fiber formation process and the micromorphology of the emitted fibers are optimal. Statistical analysis of the distribution of fiber diameters confirmed that in case of the optimum concentration, the distribution approaches normality. Mechanical properties of the prepared fibers were also evaluated using texture analysis, which indicated that the fibers made of gels of the suggested optimum concentration had the most desirable elastic behavior. An optimum concentration range of hydroxypropyl cellulose exists that enables fiber formation with the required characteristics from the point of further pharmaceutical formulation processing. 相似文献
432.
Sean T. Hunt Tarit Nimmanwudipong Prof. Yuriy Román‐Leshkov 《Angewandte Chemie (International ed. in English)》2014,53(20):5131-5136
Transition‐metal carbides (TMCs) exhibit catalytic activities similar to platinum group metals (PGMs), yet TMCs are orders of magnitude more abundant and less expensive. However, current TMC synthesis methods lead to sintering, support degradation, and surface impurity deposition, ultimately precluding their wide‐scale use as catalysts. A method is presented for the production of metal‐terminated TMC nanoparticles in the 1–4 nm range with tunable size, composition, and crystal phase. Carbon‐supported tungsten carbide (WC) and molybdenum tungsten carbide (MoxW1?xC) nanoparticles are highly active and stable electrocatalysts. Specifically, activities and capacitances about 100‐fold higher than commercial WC and within an order of magnitude of platinum‐based catalysts are achieved for the hydrogen evolution and methanol electrooxidation reactions. This method opens an attractive avenue to replace PGMs in high energy density applications such as fuel cells and electrolyzers. 相似文献
433.
Beobide G Wang WG Castillo O Luque A Román P Tagliabue G Galli S Navarro JA 《Inorganic chemistry》2008,47(12):5267-5277
A series of manganese(II) coordination polymers containing the bridging ligand pyrimidine-4,6-dicarboxylate (pmdc) have been prepared. The stoichiometries and structural features of these materials, which range from the one-dimensional (1D) chains in ([Mn(mu-pmdc)(H2O)3].2H2O)n (1) and ([Mn2(mu-pmdc)2(H2O)5].2H2O)n (2) to the two-dimensional layers in ([Mn(mu3-pmdc)(H2O)].H2O)n (3) or the three-dimensional porous network in ([Mn(pmdc)].2H2O)n (4), are extremely dependent on the synthetic conditions (i.e., temperature and solvent). In spite of the structural diversity of these systems, crystallographic studies revealed that the pmdc ligand typically displays a tetradentate mu-(kappaO,kappaN:kappaO',kappaN') coordination mode with the carboxylate groups almost coplanar with the pyrimidine ring [as in compounds 1 and 2 and compound 5 described below)]. In compound 3, the pmdc moiety adopts a pentadentate mu3-(kappaO,kappaN:kappaO',kappaN':kappaO) coordination mode. The thermal, magnetic, and adsorption properties of these systems were also studied. The results showed that these compounds behave as antiferromagnets as a consequence of efficient magnetic exchange through the pmdc bridges. Compound 4 possesses permanent porosity, as proved by gas sorption data (N2 at 77 K and CO2 at 293 K). Finally, the heteronuclear iron(II)/manganese(II) compound ([FeMn(mu-pmdc)2(H2O)5].2H2O)n (5), which is isomorphous to 2, was also prepared and fully characterized. 相似文献
434.
Fustero S Román R Sanz-Cervera JF Simón-Fuentes A Cuñat AC Villanova S Murguía M 《The Journal of organic chemistry》2008,73(9):3523-3529
The preparation of N-methylpyrazoles is usually accomplished through reaction of a suitable 1,3-diketone with methylhydrazine in ethanol as the solvent. This strategy, however, leads to the formation of regioisomeric mixtures of N-methylpyrazoles, which sometimes are difficult to separate. We have determined that the use of fluorinated alcohols such as 2,2,2-trifluoroethanol (TFE) and 1,1,1,3,3,3-hexafluoro-2-propanol (HFIP) as solvents dramatically increases the regioselectivity in the pyrazole formation, and we have used this modification in a straightforward synthesis of fluorinated analogs of Tebufenpyrad with acaricide activity. 相似文献
435.
López RH Romá F Gargiulo V Sales JL Zgrablich G 《The journal of physical chemistry. B》2008,112(29):8619-8623
A molecular model is proposed to study the enantioselective adsorption of chiral species on metallic surfaces modified through the preadsorption of another chiral species, known as template surfaces. It is found that anisotropic and exclusive interactions among adsorbed species are essential factors in the enantioselective process. It is shown how the formation of compact structures explains the fact that an enantiomer of species B having the same symmetry as the template species A can be preferentially adsorbed with respect to the other enantiomer of species B, thus producing enantioselectivity. The model predicts enantioselectivity peaks on a limited range of the template coverage, as typically observed experimentally in some systems. 相似文献
436.
Pérez-Yáñez S Beobide G Castillo O Cepeda J Fröba M Hoffmann F Luque A Román P 《Chemical communications (Cambridge, England)》2012,48(6):907-909
The presence of butanoic acid excess in the reaction media employed for the synthesis of a MOF with formula [Cu(2)(μ(3)-ade)(2)(μ(2)-OOC(CH(2))(2)CH(3))(2)](n) (ade: adeninate) leads to the formation of micelles that exert a template effect and provide a pronounced increase of its microporosity, doubling the intrinsic adsorption capacity of the pristine crystal network. 相似文献
437.
M Lanchas D Vallejo-Sánchez G Beobide O Castillo AT Aguayo A Luque P Román 《Chemical communications (Cambridge, England)》2012,48(79):9930-9932
The direct acid-base reaction between ZnO/CoO/Co(OH)(2) and imidazolic ligands under moderate heating (100-160 °C), in a closed vessel, leads to the generation of the corresponding zinc/cobalt-imidazolates in a high yield (87-97%) in which network topology is controlled by the addition of small amounts of structure directing agents. Moreover, the fine tuning of the thermal process at the synthetic stage permits us to increase the crystal size, and even to grow X-ray quality single crystals. 相似文献
438.
439.
Absorption and fluorescence properties of methylene blue (MB), a well-known singlet molecular oxygen photosensitizer, and its mixtures with pheophorbide-a (Pheo) sorbed on microgranular cellulose are studied, with emphasis on radiative and nonradiative energy transfer from Pheo to MB. Although pure MB builds up dimeric species on cellulose even at 2 x 10(-8) mol g(-1), addition of 2.05 x 10(-7) mol g(-1) Pheo largely inhibits aggregation up to nearly 10(-6) mol g(-1) MB. At the same time, the absorption spectrum of monomeric MB in the presence of Pheo differs from the spectrum in pure cellulose. Both effects reveal a strong influence of Pheo on the medium properties. A model relying entirely on experimental data is developed, through which energy transfer efficiencies can be calculated for thin and thick layers of dye-loaded cellulose. At the largest concentration of MB assuring no dye aggregation, nonradiative energy transfer efficiencies reach a maximum value of nearly 40%. This value is quite high, taking into account the low fluorescence quantum yield of Pheo, Phi = 0.21, and results from the existence of high local concentrations of the acceptor within the supporting material. These results show that large energy transfer rates can exist in a system devoid of any special molecular organization. 相似文献
440.
Simó C Pérez P Neusüss C Pelzing M San Román J Gallardo A Cifuentes A 《Electrophoresis》2006,27(11):2250-2258
Analytical characterization of dimethacrylate-tyrosine-lysine-tyrosine (DMTLT, a new biodegradable acrylic cross-linker synthesized at our laboratory) is carried out using CE-MS. DMTLT is a pseudopeptide composed by tyrosine-lysine-tyrosine amino acids linked through urea bonds with two methacrylic groups, one at each end of the molecule, making this compound an excellent cross-linker for polymerization reactions and for obtaining new biodegradable materials. A new CE-MS method is developed for the characterization of DMTLT and its products of degradation after basic hydrolysis. In order to carry out an exhaustive examination of such degradation products methods based on CE coupled to IT and TOF-MS are employed. Based on CE-IT-MS results and the elemental composition of the degradation products obtained by CE-TOF-MS, conclusions on the mechanism and kinetic of hydrolysis of DMTLT are obtained confirming both the usefulness of CE-MS to characterize new biomaterials and the applicability of DMTLT for preparing new biodegradable polymers. These results are corroborated through the CE-MS detection of the identified products of degradation in a dimethyl acrylamide polymer cross-linked with DMTLT. 相似文献