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991.
The quality crystals (Calcitic limestone) were selected using the UV–visible methylene blue adsorption method. The thermostimulated luminescence (TSL) glow curve characteristics of six well crystallized limestone samples were analyzed. The glow curves of unannealed sample show only one peak in the range 320–330 °C. The sample irradiated with a gamma dose of 100 Gy shows two additional peaks in the range of 113–125 °C and 242–260 °C when recorded with linear heating rate of 10 °C/s. The annealed sample also shows the same trend as that of irradiated sample. Annealing treatment above 250 °C increases the sensitivity of all TSL peaks except 320 °C. On the other hand, annealing at 750 °C caused a collapse in the TSL sensitivity. The enhancement in TSL sensitivity was found to depend on the annealing temperature and time. Annealing treatment at 650 °C for 4 h followed by quenching in air is the optimum condition for TSL sensitization. The response to gamma irradiation is linear in the range from 0.5 Gy to 104 Gy. The emission spectra of all the samples show an emission at around 610 nm but with different intensities for each TSL peak. With reference to earlier work, it may be assumed that the recombination site always involves Mn2+ ions. The observation made through infra-red (IR) and X-ray diffraction (XRD) studies with thermal treatment shows the structural changes of calcite from D3h to Cs symmetry at 750 °C. The Thermogravimetric-Differential Thermal Analysis (TG-DTA) analysis shows the calcite gets disordered at 760 °C. Hence, the collapse in the TSL sensitivity at 750 °C is due to structural change or structural disorderedness. 相似文献
992.
Aizpurua JM Sagartzazu-Aizpurua M Monasterio Z Azcune I Mendicute C Miranda JI García-Lecina E Altube A Fratila RM 《Organic letters》2012,14(7):1866-1868
Mesoionic 4,4'-bis(1,2,3-triazole-5,5'-diylidene) Rh(I) complexes having a C2 chiral 4,4'-axis were accessed from 3-alkyltriazolium salts in virtually complete de. Their structure and configurational integrity were assessed by NMR spectroscopy, X-ray crystallography, and chiral HPLC. Computational analysis of the MICs involved in the reaction suggested the formation of a highly stable and unprecedented cation-carbene intermediate species, which could be evidenced experimentally by cyclic voltammetry analysis. 相似文献
993.
Sanchez-Sanchez C Lanzilotto V Gonzalez C Verdini A de Andres PL Floreano L Lopez MF Martin-Gago JA 《Chemistry (Weinheim an der Bergstrasse, Germany)》2012,18(24):7382-7387
The adsorption of C(60), a typical acceptor organic molecule, on a TiO(2) (110) surface has been investigated by a multitechnique combination, including van der Waals density functional calculations. It is shown that the adsorbed molecules form a weakly interacting molecular layer, which sits on the fivefold-coordinated Ti that is confined between the prominent bridging oxygen rows (see figure). 相似文献
994.
Juan Mu?oz-Arnanz Jose Luis Roscales Alba Vicente Jose Ignacio Aguirre Bego?a Jiménez 《Analytical and bioanalytical chemistry》2012,404(9):2765-2773
Dechlorane Plus (DP) and some of its possible degradation products were measured in eggs from the yellow-legged gull (Larus michahellis) and Audouin's gull (Larus audouinii) from a protected area in the southwestern Mediterranean Sea. Statistically significant differences were found between both gull species, with yellow-legged gull eggs showing the highest average total DP concentration (209?pg/g wet weight). According to stable nitrogen and carbon isotope values, variations in DP concentrations in the gull species studied are explained by foraging behavior and diet rather than by the trophic position. Both DP stereoisomers were quantified in all the samples studied, and a slight enrichment of the anti-DP could have occurred in both species. The quantification of anti-[DP-1Cl] only in ~58?% of yellow-legged gulls support the hypothesis of a species-dependent factor influencing the bioaccumulation and/or biotransformation of Dechlorane-related compounds. This study reports on the first measurements of Dechlorane-related compounds in biota from the North African continent, contributing to the knowledge about DP environmental fate and distribution. In the light of our results, more research on differences in species-dependent bioaccumulation and biotransformation capabilities as well as ecological effects is encouraged in future Dechlorane-related compound studies. 相似文献
995.
Cuello S Ramos S Madrid Y Luque-Garcia JL Cámara C 《Analytical and bioanalytical chemistry》2012,404(2):315-324
Understanding the molecular mechanisms underlying MeHg toxicity and the way in which this molecule interacts with living organisms is a critical point since MeHg represents a well-known risk to ecosystems and human health. We used a quantitative proteomic approach based on stable isotopic labeling by amino acids in cell culture in combination with SDS-PAGE and nanoflow LC-ESI-LTQ for analyzing the differential protein expression of hepatic cells associated to MeHg exposure. Seventy-eight proteins were found de-regulated by more than 1.5-fold. We identified a number of proteins involved in different essential biological processes including apoptosis, mitochondrial dysfunction, cellular trafficking and energy production. Among these proteins, we found several molecules whose de-regulation has been already related to MeHg exposure, thus confirming the usefulness of our discovery approach, and new ones that helped to gain a deeper insight into the biomolecular mechanisms related to MeHg-induced toxicity. Overexpression of several HSPs and the proteasome 26S subunit itself showed the proteasome system as a molecular target of toxic MeHg. As for the interaction networks, the top ranked was the nucleic acid metabolism, where many of the identified de-regulated proteins are involved. 相似文献
996.
Chary NS Herrera S Gómez MJ Fernández-Alba AR 《Analytical and bioanalytical chemistry》2012,404(6-7):1993-2006
A new analytical method using stir-bar-sorptive extraction (SBSE) followed by liquid desorption (LD) and gas chromatography with triple-quadrupole mass spectrometric detection (GC-QqQ-MS-MS) has been used for quantitative determination of 25 chlorinated endocrine-disrupting compounds (EDCs) in river water and wastewater. The experimental conditions affecting the SBSE-LD performance were studied and are discussed in detail. Results from systematic assay revealed that a 100-mL water sample, stir bars coated with 47?μL PDMS, an extraction time of 14?h (at 900?rpm), 5?% MeOH as modifier and 10?% NaCl resulted in the best analytical recovery of all the target compounds studied. Use of 1:1 ACN-MeOH as back-extraction solvent and two successive sonication steps, each for 5?min, resulted in the best performance for monitoring EDCs in water matrices. The method detection limits for most of the target compounds were very good- ≤?2?ng?L(-1) and ≤10?ng?L(-1) for river water and wastewater effluents respectively. Experimental recovery for all the compounds was >70?%, with the exception of simazine for which recovery from the matrix was 65?%. Signal enhancement observed for a few of the compounds in wastewater effluents was managed by use of matrix-matched standards and different injection liners. The method was successfully used for analysis of river water samples from Henares River (Spain) and wastewater effluent samples from wastewater-treatment plants (WWTP). Eleven of the 25 compounds studied were detected in both river water and wastewater effluents. Terbutylazine and methoxychlor were detected in almost all the river water and effluent samples; amounts varied between 37-58.5?ng?L(-1) and 15.2-46.8?ng?L(-1), respectively. This method was shown enable reliable, effective, and sensitive monitoring of chlorinated EDCs at nanogram levels in surface water and wastewater effluent. 相似文献
997.
Indirect bandgap semiconductors such as silicon are not efficient light emitters because a phonon with a high momentum is required to transfer an electron from the conduction to the valence band. In a recent study (M.J. Chen et al., 2006) [6] an analytical expression of the optical gain in bulk indirect bandgap semiconductors was obtained. The main conclusion was that the free-carrier absorption was much higher than the optical gain at ambient temperature, which prevents lasing. In this work, we consider the case in which the semiconductor material is engineered to form an optical cavity characterized by a certain Purcell factor. We conclude that although the optical gain is increased, losses due to free carriers increase in the same way so lasing is also prevented even when creating a high-Q optical cavity. 相似文献
998.
Analysis of trans fatty acids production and squalene variation during amaranth oil extraction 总被引:1,自引:0,他引:1
Jose A. Ariza Ortega Arturo Martínez Zavala Maribel Cano Hernández Joel Díaz Reyes 《Central European Journal of Chemistry》2012,10(6):1773-1778
The purpose of this study was to evaluate the decay of squalene and the formation of trans fatty acids (TFAs) in the amaranth oil extracted with hexane with and without heat. Oils were analyzed by determining their chemical values, and the fatty acids were identified and quantified by using Fourier-transform infrared (FTIR) spectroscopy, in the mid-region of 400?C4000 cm?1, and gas chromatography. The FTIR analysis shows that two oil extracts (with and without heat) present a well-defined peak at 968 cm?1, which represents the trans double bonds. The quantified TFAs are <0.5 g per 100 g of oil, which is considered as TFAs-free. The squalene content in the oil extracted without and with heat are 6.98±1.1% and 7.12±1.3%, respectively. Our data suggest that the TFAs formation is directly promoted by thermal processing and that squalene content is not affected by the application of heat during the oil extraction process in amaranth. 相似文献
999.
Efficient simulation and conditional functional limit theorems for ruinous heavy-tailed random walks
The contribution of this paper is to introduce change of measure based techniques for the rare-event analysis of heavy-tailed random walks. Our changes of measures are parameterized by a family of distributions admitting a mixture form. We exploit our methodology to achieve two types of results. First, we construct Monte Carlo estimators that are strongly efficient (i.e. have bounded relative mean squared error as the event of interest becomes rare). These estimators are used to estimate both rare-event probabilities of interest and associated conditional expectations. We emphasize that our techniques allow us to control the expected termination time of the Monte Carlo algorithm even if the conditional expected stopping time (under the original distribution) given the event of interest is infinity–a situation that sometimes occurs in heavy-tailed settings. Second, the mixture family serves as a good Markovian approximation (in total variation) of the conditional distribution of the whole process given the rare event of interest. The convenient form of the mixture family allows us to obtain functional conditional central limit theorems that extend classical results in the literature. 相似文献
1000.
We consider perpetuities of the form where the Yj’s and Bj’s might be i.i.d. or jointly driven by a suitable Markov chain. We assume that the Yj’s satisfy the so-called Cramér condition with associated root θ∗∈(0,∞) and that the tails of the Bj’s are appropriately behaved so that D is regularly varying with index θ∗. We illustrate by means of an example that the natural state-independent importance sampling estimator obtained by exponentially tilting the Yj’s according to θ∗ fails to provide an efficient estimator (in the sense of appropriately controlling the relative mean squared error as the tail probability of interest gets smaller). Then, we construct estimators based on state-dependent importance sampling that are rigorously shown to be efficient. 相似文献
D=B1exp(Y1)+B2exp(Y1+Y2)+?,