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991.
Hennig M Munzarova ML Bermel W Scott LG Sklenar V Williamson JR 《Journal of the American Chemical Society》2006,128(17):5851-5858
Long-range scalar 5J(H1',F) couplings were observed in 5-fluoropyrimidine-substituted RNA. We developed a novel S3E-19F-alpha,beta-edited NOESY experiment for quantitation of these long-range scalar 5J(H1',F) couplings, where the J-couplings can be extracted from inspection of intraresidual (H1',H6) NOE cross-peaks. Quantum chemical calculations were exploited to investigate the relation between scalar couplings and conformations around the glycosidic bond in oligonucleotides. The theoretical dependence of the observed 5J(H1',F) couplings on the torsion angle chi can be described by a generalized Karplus relationship. The corresponding density functional theory (DFT) analysis is outlined. Additional NMR experiments facilitating the resonance assignments of 5-fluoropyrimidine-substituted RNAs are described, and chemical shift changes due to altered shielding in the presence of fluorine-19 (19F) are presented. 相似文献
992.
Braga AL Schneider PH Paixão MW Deobald AM Peppe C Bottega DP 《The Journal of organic chemistry》2006,71(11):4305-4307
A simple and efficient procedure for the synthesis of chiral beta-seleno-amines derivatives from a one-pot indium(I) iodide-mediated aziridine ring opening with diorganoyl diselenides has been developed. As an application, the synthesis of selenocysteine and selenotreonine derivatives has been accomplished. 相似文献
993.
The identification and structure elucidation of drug metabolites is one of the main objectives in in vitro ADME studies. Typical modern methodologies involve incubation of the drug with subcellular fractions to simulate metabolism followed by LC-MS/MS or LC-MS(n) analysis and chemometric approaches for the extraction of the metabolites. The objective of this work was the software-guided identification and structure elucidation of major and minor buspirone metabolites using capillary LC as a separation technique and ion trap MS(n) as well as electrospray ionization orthogonal acceleration time-of-flight (ESI oaTOF) mass spectrometry as detection techniques.Buspirone mainly underwent hydroxylation, dihydroxylation and N-oxidation in S9 fractions in the presence of phase I co-factors and the corresponding glucuronides were detected in the presence of phase II co-factors. The use of automated ion trap MS/MS data-dependent acquisition combined with a chemometric tool allowed the detection of five small chromatographic peaks of unexpected metabolites that co-eluted with the larger chromatographic peaks of expected metabolites. Using automatic assignment of ion trap MS/MS fragments as well as accurate mass measurements from an ESI oaTOF mass spectrometer, possible structures were postulated for these metabolites that were previously not reported in the literature. 相似文献
994.
A J M Barros J C O Santos S Prasad V D Leite A G Souza L E B Soledade M S B Duarte V D dos Santos 《Journal of Thermal Analysis and Calorimetry》2006,83(2):291-295
The conventional treatments
of effluents containing heavy metals produce significant quantities of byproducts
with recalcitrant characteristics, making necessary looking after alternative
techniques in order to avoid the production of new contaminated residues.
Sorption process of chromium and zinc in vertical columns loaded with sewage
sludge and organic solid waste has been studied in this work. The data from
the TG curves of the two sorbents presented significant differences when they
were submitted to the metal uptake, being noticed the displacement of the
thermal events towards lower temperatures for both types of sorbents studied.
As it was expected, for both sorbents, an increase in the mass of samples
has been observed at the completion of the thermal tests upon metal uptake.
Therefore, these facts demonstrate that during the biosorption process a physico-chemical
interaction took place between sorbents and metals, as it was evidenced by
the more than 100 K increase in the decomposition temperatures as well as
the variation of the ΔH values of the
samples. 相似文献
995.
The
reaction of ilmenite titanium raw material with sulphuric acid was investigated
in ‘hazard’ type calorimetric system. The investigations show
the essential influence of initial temperature, particle size distribution
and concentration of sulphuric acid on rate and heat power of reaction and
determine the limits of safety of the process and also its efficiency. 相似文献
996.
Mathieu Allix Philip P.C. Frampton Rocío Ruiz-Bustos 《Journal of solid state chemistry》2006,179(3):775-792
Polycrystalline samples of bilayered brownmillerite-like Ca2.5Sr0.5GaCo0.15Mn1.85O8 and Ca2.5Sr0.5Ga1.2Mn1.8O8 have been prepared and characterised by magnetometry and neutron diffraction over a wide temperature range. The structural chemistry and magnetic properties are compared to those of Ca2.5Sr0.5GaMn2O8. Ga enrichment has a significant effect on the former but not on the latter, whereas changes in both occur when paramagnetic Co3+ cations enter the parent phase on the 4-coordinate sites. The coupling between the environment around the 4-coordinate cations and the transition to an antiferromagnetic ordered state that was observed in Ca2.5Sr0.5GaMn2O8 is not apparent in the cation-substituted compositions, although both show long-range antiferromagnetic order at low temperatures. 相似文献
997.
Clovis Peppe Paola de Azevedo Mello Rafael Pavão das Chagas 《Journal of organometallic chemistry》2006,691(11):2335-2339
The organoindium compound derived from indium monobromide and dibromoacetonitrile reacts with carbonyl compounds to afford the corresponding 2-bromo-2-cyano-indium(III) alkoxide. The action of a second equivalent of indium monobromide onto the alkoxides derived from aldehydes promotes the Boord elimination of the β-related oxygen and bromine atoms leading to 2-alkenenitriles. 相似文献
998.
Several specific synthetic protocols were developed for the preparation from cyanuric chloride of a range of symmetric and non-symmetric di- and tri-substituted 1,3,5-triazines containing alkyl, aromatic, hindered, chiral and achiral hydroxyalkyl, ester and imidazole groups via sequential nucleophilic substitution of the C-Cl bond by C-O, C-N and C-S bonds. 相似文献
999.
Cristiane P. de Macedo Charles A. B. Negrão Luiz G. M. de Macedo José R. Zamian Geraldo N. da Rocha Filho Carlos E. F. da Costa 《Journal of Thermal Analysis and Calorimetry》2014,115(1):31-36
The Al-MCM-41 molecular sieve with Si/Al = 20 molar ratio was synthesized at room temperature and characterized by X-ray diffractometry, surface area, thermogravimetry, and infrared spectroscopy. The kinetic study was conducted by Vyazovkin and Ozawa method, in order to verify the activation energy during the Hofmann degradation between 130 and 370 °C, in which most of surfactant removal occurs. The results suggest that the activation energy for template removal is close to 80 kJ mol?1 lower in Al-MCM-41 synthesized at room temperature, when compared to results obtained for mesopores Al-MCM-41 and MCM-41 synthesized by hydrothermal method. This lower activation energy may be understood as consequence of textural properties, such as higher pore size. 相似文献
1000.
Single Crystal to Single Crystal (SC‐to‐SC) Transformation from a Nonporous to Porous Metal–Organic Framework and Its Application Potential in Gas Adsorption and Suzuki Coupling Reaction through Postmodification 下载免费PDF全文
Dr. Rupam Sen Debraj Saha Dr. Subratanath Koner Dr. Paula Brandão Dr. Zhi Lin 《Chemistry (Weinheim an der Bergstrasse, Germany)》2015,21(15):5962-5971
A new amino‐functionalized strontium–carboxylate‐based metal–organic framework (MOF) has been synthesized that undergoes single crystal to single crystal (SC‐to‐SC) transformation upon desolvation. Both structures have been characterized by single‐crystal X‐ray analysis. The desolvated structure shows an interesting 3D porous structure with pendent ?NH2 groups inside the pore wall, whereas the solvated compound possesses a nonporous structure with DMF molecules on the metal centers. The amino group was postmodified through Schiff base condensation by pyridine‐2‐carboxaldehyde and palladium was anchored on that site. The modified framework has been utilized for the Suzuki cross‐coupling reaction. The compound shows high activity towards the C?C cross‐coupling reaction with good yields and turnover frequencies. Gas adsorption studies showed that the desolvated compound had permanent porosity and was microporous in nature with a BET surface area of 2052 m2 g?1. The material also possesses good CO2 (8 wt %) and H2 (1.87 wt %) adsorption capabilities. 相似文献