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971.
972.
973.
The choice of appropriate density functional for the calculation of static first hyperpolarizability of azochromophores and stacking dimers 下载免费PDF全文
Olga D. Fominykh Anastasiya V. Sharipova Marina Yu. Balakina 《International journal of quantum chemistry》2016,116(2):103-112
The effect of the stacked azo‐chromophore dimer formation on the values of static first hyperpolarizability is studied in the framework of the DFT‐based approach; calculations were also performed at the MP2 level. A number of dispersion‐corrected density functionals—В97D, ωВ97X‐D, and M06‐2X—is tested to calculate the structure of the dimer, the value of binding energy, and molecular nonlinear optical characteristics. According to the QTAIM analysis, the presence of bond critical points is revealed in the intermolecular region, the signs and values of topological characteristics giving evidence for the noncovalent van der Waals interaction between the chromophores. The formation of stacks results in moderate increase of dimer static first hyperpolarizability as compared to that of a single chromophore, the effect depending on the relative shift of the chromophores in dimer. In a special case of greatly shifted chromophores, this enhancement of the first hyperpolarizability becomes appreciable and achieves 72%. © 2015 Wiley Periodicals, Inc. 相似文献
974.
Design,Synthesis, and Application of an Optimized Monofluorinated Aliphatic Label for Peptide Studies by Solid‐State 19F NMR Spectroscopy 下载免费PDF全文
Serhii O. Kokhan Andriy V. Tymtsunik Dr. Stephan L. Grage Dr. Sergii Afonin Dr. Oleg Babii Dr. Marina Berditsch Alexander V. Strizhak Dmytro Bandak Dr. Maxim O. Platonov Prof. Igor V. Komarov Prof. Anne S. Ulrich Dr. Pavel K. Mykhailiuk 《Angewandte Chemie (International ed. in English)》2016,55(47):14788-14792
A conformationally restricted monofluorinated α‐amino acid, (3‐fluorobicyclo[1.1.1]pentyl)glycine (F‐Bpg), was designed as a label for the structural analysis of membrane‐bound peptides by solid‐state 19F NMR spectroscopy. The compound was synthesized and validated as a 19F label for replacing natural aliphatic α‐amino acids. Calculations suggested that F‐Bpg is similar to Leu/Ile in terms of size and lipophilicity. The 19F NMR label was incorporated into the membrane‐active antimicrobial peptide PGLa and provided information on the structure of the peptide in a lipid bilayer. 相似文献
975.
Mohammad Tajul Islam Alessio Montarsolo Marina Zoccola Maurizio Canetti Adriana Cacciamani 《Journal of Macromolecular Science: Physics》2016,55(9):867-883
Cellulose fibrils were manufactured from flax fibers using chemical treatments followed by cryo-crushing and ultrasonication techniques. The fibrils, consisting mainly of cellulose free from lignin, pectin and hemicellulose, were exploited as a biofiller in preparing poly(methyl methacrylate) (PMMA) matrix composites. The effects of incorporating cellulose fibrils on the physical and mechanical properties of the polymer matrix were investigated. In particular, the influence of the fibrils on the thermal stability and degradation of the composites was studied by means of thermogravimetric analysis carried out in both inert and oxidative atmospheres. The runs performed under air flow revealed the efficiency of the cellulose fibrils in delaying the polymer decomposition during thermal oxidation. The weight loss was slowed down in the composites of all compositions and the temperature of degradation increased with increasing the amount of the fibrils. The combustion properties of the fibril-based composites were evaluated by means of pyrolysis combustion flow calorimetry. The addition of cellulose fibrils into the PMMA matrix resulted in a noticeable decrease of the primary combustion parameters. 相似文献
976.
Marina V. Bukhtiyarova Aleksandra S. Ivanova Lyudmila M. Plyasova Galina S. Litvak Anna A. Budneva Evgenii A. Paukshtis 《Reaction Kinetics and Catalysis Letters》2008,93(2):375-387
Hexaaluminates SrAl12O19, BaAl12O19 and LaAl11O18 were prepared by co-precipitation of soluble nitrates of Sr, Ba, or La and Al using NH4HCO3 as a precipitating agent with subsequent calcination at 700–1400°C. The samples were characterized by adsorption methods,
thermal analysis (TA and DTG), X-ray diffraction (XRD), and Fourier transform infrared (FTIR) spectroscopy of adsorbed probe
molecules (CO and CDCl3). It was shown that calcination at 1200°C resulted in the formation of single-phase hexaaluminates in all the samples except
for LaAl11O18, where an additional phase was found. The specific surface area of the samples was obtained in the range 16–22 m2/g. After the treatment at comparable conditions, the total concentrations of both surface Lewis acid sites and basic sites
were found to increase in the series: BaAl12O19 < SrAl12O19 < LaAl11O18. However, the strongest basic sites were detected on the surface of BaAl12O19. 相似文献
977.
Sonia Morante‐Zarcero Antonio L. Crego Isabel del Hierro Isabel Sierra Maria Luisa Marina 《Electrophoresis》2008,29(22):4575-4582
A CE method using CDs as chiral selectors was developed and validated to achieve the separation of glycidyl tosylate enantiomers originated by in situ derivatization of glycidol enantiomers obtained in asymmetric epoxidation of allyl alcohol with chiral titanium‐tartrate complexes as catalysts. The effects of the nature, pH and concentration of the buffer, the nature and concentration of chiral selector, the addition of SDS, methanol, ethanol or 2‐propanol, the capillary temperature, the effective capillary length and the applied voltage on the chiral resolution of glycidyl tosylate enantiomers were investigated. The best separation conditions were achieved using a Tris‐borate buffer mixture (50 and 25 mM, respectively) at pH=9.3 with a dual CD system consisting of 2.5% succinyl‐β‐CD and 1.0% β‐CD w/v at 15°C. A baseline separation (resolution~2.0) of the glycidyl tosylate enantiomers was obtained in a relatively short time (less than 12 min). Satisfactory results were obtained in terms of linearity (r>0.99) and intermediate precision (RSD below 8.5%). The LOD and LOQ were 3.0 and 10.0 mg/L, respectively, and the recoveries ranged from 99.8 to 108.8%. Finally, the method was applied to the determination of the enantiomeric excess and the yield obtained in the asymmetric epoxidation of allyl alcohol employing chiral titanium‐tartrate complexes as catalysts after an in situ derivatization of glycidol enantiomers to glycidyl tosylate. 相似文献
978.
CE with UV detection was used for the first time to determine the enantioselective adsorption of the short-chain tricarboxylic acid, 3-carboxy adipic acid, on minerals as a mean of investigating plausible mechanisms for the origin of biochemical homochirality on Earth. The use of vancomycine as chiral selector in the separation buffer using the partial filling technique enabled the separation of the two enantiomers of this organic acid in about 12 min. Taking into account that this compound has a low absorption of the UV light, and in order to achieve the sensitivity needed to determine the enantiomeric excess of samples of 3-carboxy adipic acid adsorbed on minerals, we applied a strategy consisting of a field-amplified sample stacking together with the use of a bubble capillary and detection at low wavelength (192 nm). This combination enabled an LOD of about 10(-7) M and the determination of the enantiomeric excess of 3-carboxy adipic acid adsorbed on calcite and feldspar mineral samples at subnanomol levels of this acid. Results showed that an enantioselective adsorption of the enantiomers of 3-carboxy adipic acid on minerals took place. 相似文献
979.
Monoglycerides and Diglycerides Synthesis in a Solvent-Free System by Lipase-Catalyzed Glycerolysis 总被引:1,自引:0,他引:1
Fregolente PB Fregolente LV Pinto GM Batistella BC Wolf-Maciel MR Filho RM 《Applied biochemistry and biotechnology》2008,146(1-3):165-172
Five lipases were screened (Thermomyces lanuginosus free and immobilized forms, Candida antarctica B, Candida rugosa, Aspergillus niger, and Rhizomucor miehei) to study their ability to produce monoglycerides (MG) and diglycerides (DG) through enzymatic glycerolysis of soybean oil.
Lipase from C. antarctica was further studied to verify the enzyme load (wt% of oil mass), the molar ratio glycerol/oil, and the water content (wt%
of glycerol) on the glycerolysis reaction. The best DG and MG productions were in the range 45–48% and 28–30% (w/w, based on the total oil), respectively. Using immobilized lipases, the amount of free fatty acids (FFA) produced was about
5%. However, the amount of FFA produced when using free lipases, with 3.5% extra water in the system, is equivalent to the
MG yield, about 23%. The extra water content provides a competition between hydrolysis and glycerolysis reactions, increasing
the FFA production. 相似文献
980.
The present research is aimed at monitoring the evolution of the volatile organic compounds of different samples of aceto balsamico tradizionale of modena (ABTM) during ageing. The flavouring compounds, headspace fraction, of the vinegars of four batterie were sampled by solid phase microextraction technique (SPME), and successively analysed by gas chromatography. Obtaining a data set characterized by different sources of variability such as, different producers, samples of different age and chromatographic profile. The gas chromatographic signals were processed by a three-way data analysis method (Tucker3), which allows an easy visualisation of the data by furnishing a distinct set of graphs for each source of variability. The obtained results indicate that the samples can be separated according to their age highlighting the chemical constituents, which play a major role for their differentiation. The present study represents an example of how the application of Tucker3 models, on gas chromatographic signals may help to follow the transformation processes of food products. 相似文献