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1.
Di Bussolo V Caselli M Romano MR Pineschi M Crotti P 《The Journal of organic chemistry》2004,69(21):7383-7386
The reaction of alpha vinyl oxirane 5, prepared through a new route to the d-gulal system, with O-nucleophiles (alcohols and di-O-isopropylidene-alpha-d-monosaccharides) and C-nucleophiles (lithium alkyls) affords, in a completely stereoselective way, the corresponding 2-unsaturated alpha O- and C-glycosides having the same configuration as the starting epoxide. 相似文献
2.
Madeddu M 《Solid state nuclear magnetic resonance》2002,22(1):83-90
23Na and 31P MAS NMR spectra and spin-lattice relaxation times in a solid sample of Na-DNA were measured under very carefully controlled conditions of relative ambient humidity. The observed substantial changes of the NMR parameters are related to the water-induced transitions between the different molecular configurations of DNA, with the transition between A- and B-DNA occurring in the 30-60% range of relative humidity. Our work demonstrates that the previously measured NMR parameters are in error because the relative humidity of the system had not been controlled, rendering the results irreproducible. 相似文献
3.
Laura Zanetti-Polzi Paolo Marracino Massimiliano Aschi Isabella Daidone Antonella Fontana Francesca Apollonio Micaela Liberti Guglielmo D’Inzeo Andrea Amadei 《Theoretical chemistry accounts》2013,132(11):1-10
A benchmark biochemical reaction is here theoretically investigated by means of a perturbative approach in order to model each reaction step. The reaction is the flavin-indole electron transfer, involving also a spin-state relaxation of the ionic complex. The whole reaction path is modeled and the kinetics of the process is studied. The dipolar interaction between the two radicals is explicitly considered during the dynamic evolution of the system in order to investigate the proper conditions for the triplet-to-singlet transition to occur. 相似文献
4.
Electrodes/Electrolyte Interfaces in the Presence of a Surface‐Modified Photopolymer Electrolyte: Application in Dye‐Sensitized Solar Cells
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Dr. Adriano Sacco Federico Bella Stefano De La Pierre Dr. Micaela Castellino Dr. Stefano Bianco Prof. Roberta Bongiovanni Prof. Candido Fabrizio Pirri 《Chemphyschem》2015,16(5):960-969
Since hundreds of studies on photoanodes and cathodes show that the electrode/electrolyte interfaces represent a key aspect at the base of dye‐sensitized solar cell (DSSC) performances, it is reported here that these interfaces can be managed by a smart design of the spatial composition of quasi‐solid electrolytes. By means of a cheap, rapid, and green process of photoinduced polymerization, composition‐tailored polymer electrolyte membranes (PEMs) with siloxane‐enriched surfaces are prepared, and their properties are thoroughly described. When assembled in DSSCs, the interfacial action promoted by the composition‐tailored PEMs enhances the photocurrent and fill factor values, thus increasing the global photovoltaic conversion efficiency with respect to the non‐modified PEMs. Moreover, the presence of the siloxane‐chain‐enriched surface increases the hydrophobicity and reduces the water vapor permeation into the device, thus enhancing the cell′s durability. 相似文献
5.
María G. Hernández-Cruz Micaela Hernández-Sandoval María J. Rosales-Hoz Verónica Salazar Francisco J. Zuno-Cruz 《Journal of organometallic chemistry》2011,696(10):2177-4078
The reaction between [Ru3(CO)10(NCMe)2] and [AuClPPh3] gave compound [Ru3(CO)10(μ-Cl)(μ-AuPPh3)] (1) in quantitative yield under very mild conditions. The reaction of 1 with 4-mercaptopyridine (4-pyS) using ultrasonic reaction conditions gave the heteronuclear compound [Ru3(CO)10(μ-AuPPh3)(μ-SC5H4N)] (2) in moderate yield. There was no spectroscopic evidence that indicates the formation of the hydride isolobal analog in this reaction. The homonuclear cluster [Ru3(CO)8(μ-H)(μ-SC5H4N)(μ-dppe)] (3) was prepared by a selective reaction employing the ruthenium-diphosphine derivative [Ru3(CO)10(μ-dppe)] (dppe = 1,2-bis(diphenylphosphine)ethane) with 4-pyS in THF solution. The isolobal analog to compound 3, compound [Ru3(CO)8(μ-AuPPh3)(μ-SC5H4N)(μ-dppe)] (4) was synthesized by the reaction between compound 2 and dppe in refluxing dichloromethane. Compounds 1-4 were characterized in solution by spectroscopic methods and the molecular structure of compounds 2 and 3 in the solid state was obtained by single crystal X-ray diffraction studies. 相似文献
6.
Serrano A Sousa MM Hallett J Lopes JA Oliveira MC 《Analytical and bioanalytical chemistry》2011,401(2):735-743
A new analytical approach based on high-performance liquid chromatography with diode array detector (HPLC-DAD) and multivariate
data analysis was applied and assessed for analyzing the red dye extracted from cochineal insects, used in precious historical
textiles. The most widely used method of analysis involves quantification of specific minor compounds (markers), using HPLC-DAD.
However, variation in the cochineal markers concentration, use of aggressive dye extraction methods and poor resolution of
HPLC chromatograms can compromise the identification of the precise insect species used in the textiles. In this study, a
soft extraction method combined with a new dye recovery treatment was developed, capable of yielding HPLC chromatograms with
good resolution, for the first time, for historical cochineal-dyed textiles. After principal components analysis (PCA) and
mass spectrometry (MS), it was possible to identify the cochineal species used in these textiles, in contrast to the accepted
method of analysis. In order to compare both methodologies, 7 cochineal species and 63 historical cochineal insect specimens
were analyzed using the two approaches, and then compared with the results for 15 historical textiles in order to assess their
applicability to real complex samples. The methodology developed here was shown to provide more accurate and consistent information
than the traditional method. Almost all of the historical textiles were dyed with Porphyrophora sp. insects. These results emphasize the importance of adopting the proposed methodology for future research on cochineal
(and related red dyes). Mild extraction methods and HPLC-DAD/MSn analysis yield distinctive profiles, which, in combination with a PCA reference database, are a powerful tool for identifying
red insect dyes. 相似文献
7.
Silva C Aranda FJ Ortiz A Martínez V Carvajal M Teruel JA 《Journal of colloid and interface science》2011,358(1):192-201
The effect of sterols composition in a lipid bilayer was investigated on membranes of 1,2-dipalmitoyl-sn-glycero-3-phosphocholine (DPPC) and mixtures with the plant sterols β-sitosterol and stigmasterol. Differential scanning calorimetry, 1,6-diphenyl-1,3,5-hexatriene (DPH) fluorescence polarization and infrared spectroscopy studies showed that both sterols changed the packing of the membrane and the hydration of the polar headgroup of the phospholipids, disordering the gel phase and, vice versa, ordering the membrane in the liquid crystalline phase. In all cases some differences among β-sitosterol and stigmasterol could be observed, being β-sitosterol slightly more efficient than stigmasterol in ordering a fluid membrane, bringing the membrane to a more packed liquid ordered phase. Molecular dynamic simulations were carried out to better characterize the distinct behavior of both sterols in a DPPC-membrane. The calculated parameters agreed quite well with the experimental results and a molecular model is proposed to explain differences in the sterols molecules and their effect on the DPPC-bilayer. 相似文献
8.
Sousa MM Melo MJ Parola AJ Seixas de Melo JS Catarino F Pina F Cook FE Simmonds MS Lopes JA 《Journal of chromatography. A》2008,1209(1-2):153-161
A simple and rapid liquid chromatographic method with diode-array UV-vis spectrophotometric detection has been developed for the authentication of dragon's blood resins from Dracaena and Daemonorops trees. Using this method it was discovered that the flavylium chromophores, which contribute to the red colour of these resins, differ among the species and could be used as markers to differentiate among species. A study of parameters, such as time of extraction, proportion of MeOH and pH, was undertaken to optimise the extraction of the flavyliums. This method was then used to make extracts from samples of dragon's blood resin obtained from material of known provenance. From the samples analysed 7,6-dihydroxy-5-methoxyflavylium (dracorhodin), 7,4'-dihydroxy-5-methoxyflavylium (dracoflavylium) and 7,4'-dihydroxyflavylium were selected as species markers for Daemonorops spp., Dracaena draco and Dracaena cinnabari, respectively. The chromatograms from these samples were used to build an HPLC-DAD database. The ability to discriminate among species of dragon's blood using the single marker compounds was compared with a principal components analysis of the chromatograms in the HPLC-DAD database. The results from the HPLC-DAD method based on the presence of these flavylium markers was unequivocal. The HPLC-DAD method was subsequently applied to 37 samples of dragon blood resins from the historical samples in the Economic Botany Collection, Royal Botanic Gardens, Kew. The method identified anomalies in how samples in this collection had been labelled. It is clear that the method can be used to evaluate the provenance of samples used in different areas of cultural heritage. It also could be used to monitor the trade of endangered species of dragon's blood and the species being used in complex formulations of traditional Chinese medicine. 相似文献
9.
Mezcua M Ferrer C García-Reyes JF Martínez-Bueno MJ Albarracín M Claret M Fernández-Alba AR 《Rapid communications in mass spectrometry : RCM》2008,22(9):1384-1392
In this work, two analytical methods based on liquid chromatography coupled to electrospray time-of-flight mass spectrometry (LC/ESI-TOFMS) and tandem mass spectrometry (LC/ESI-MS/MS) are described for the identification, confirmation and quantitation of three insecticides non-authorized in the European Union (nitenpyram, isocarbophos and isofenphos-methyl) but detected in recent monitoring programmes in pepper samples. The proposed methodologies involved a sample extraction procedure using liquid-liquid partition with acetonitrile followed by a cleanup step based on dispersive solid-phase extraction. Recovery studies performed on peppers spiked at different fortification levels (10 and 50 microg kg(-1)) yielded average recoveries in the range 76-100% with relative standard deviation (RSD) (%) values below 10%. Identification, confirmation and quantitation were carried out by LC/TOFMS and LC/MS/MS using a hybrid triple quadrupole linear ion trap (QqLIT) instrument in multiple-reaction monitoring (MRM) mode. The obtained limits of quantitation (LOQs) were in the range 0.1-5 microg kg(-1), depending on each individual technique. Finally, the proposed methods were successfully applied to the analysis of suspected pepper samples. 相似文献
10.
Micaela Fedele 《Journal of statistical physics》2014,155(2):223-236
We consider a bipartite generalization of the Curie–Weiss model in a critical regime. In order to study the asymptotic behavior of the random vector of the total magnetization we apply the change of variables that diagonalizes the Hessian matrix of the pressure functional associated to the model. We obtain a new vector that, suitably rescaled, weakly converges to the product of a Gaussian distribution and a distribution proportional to $\exp (-\xi x^{4})$ , where the positive constant $\xi $ can be computed from the pressure functional. 相似文献