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101.
Wilson SR Yurchenko ME Schuster DI Khong A Saunders M 《The Journal of organic chemistry》2000,65(9):2619-2623
Fullerene (C60) Diels-Alder adducts with perfluoroalkylated 1,3-cyclopentadiene (1a,b) were synthesized and studied. The perfluoroalkylated cyclopentadiene was found to be less reactive toward C60 than cyclopentadiene itself, possibly because of the electron-withdrawing effect of the side chain. Because of the same effect, the temperature of the retro-Diels-Alder reaction for the fluorinated adducts was lower (70 degrees C) than the reported value (95 degrees C) for the cyclopentadiene adducts of C60. Higher adducts of the fluorous diene and C60 were found to be soluble in perfluorohexane and to show visible partitioning between organic (toluene) and fluorous phases. Also, the Diels-Alder addition of the fluorous diene was accompanied by extensive oxidation of the fullerene core, as revealed by MALDI-TOF data. 相似文献
102.
Mineral and short-chain carboxylic acid vapours and NO(x) gases were reacted with cyclohexene oxide (1,2-epoxycyclohexane) to quantitatively produce specific, thermally stable cyclohexyl derivatives. Subsequent analysis of these derivatives by gas chromatography with mass spectroscopy and flame ionisation detection afforded a multi analyte method for the assay of these gaseous acidic atmospheric species. Derivatisation was found to be quantitative for the derivatives tested and the method highly sensitive (to 0.3 mg/m3 for a 30 l sample), accurate, precise and free from apparent interferences. The technique has been applied to "acid stack gases" and a number of other acid rich atmospheres and the results obtained show good agreement with the single analyte wet chemical determinations indicating that the approach has considerable potential as a routine analytical method for measuring such atmospheric pollutants. The high specificity of the reaction mechanism and its potential for the analysis of analyte mixtures is illustrated in the assay of nitric acid and its acid anhydride, dinitrogen pentoxide. 相似文献
103.
Beltrami I Bylsma BG DeBonte R Gan KK Koltick D Loeffler FJ Low EH McIlwain RL Miller DH Ng CR Ong PP Rangan LK Shibata EI Wilson RJ Derrick M Fernandez E Fries R Hyman L Kooijman P Loos JS Musgrave B Price LE Schlereth J Sugano K Weiss JM Wood DE Baranko G Baringer P Blockus D Brabson B Forden GE Gray SW Jung C Neal H Ogren H Rust DR Valdata-Nappi M Akerlof C Bonvicini G Chapman J Errede D Harnew N Kesten P Kooijman S Meyer DI Nitz D Rubin D Seidl AA Thun R Trinko T Willutzky W Cork B Keller L 《Physical review letters》1985,54(16):1775-1778
104.
High resolution conventional AFP NMR/ON studies provide evidence for very small efg's of predominantly negative sign at the nucleus of the nominal S-state ion54Mn in single crystal nickel when the applied field is paralled to the 111 direction. The form of the mid passage signals for opposing sweep directions indicates a unique efg super-imposed upon a random component of comparable magnitude. The advantages of a second analyzing sweep performed during spin lattice relaxation of a conventional post-passage AFP NMR/ON sweep are demonstrated. 相似文献
105.
Edie M. Rasmussen Peter Willett Terence Wilson Gordon A. Manson George A. Wilson 《Analytica chimica acta》1990
The use of two types of parallel computer hardware for increasing the efficiency of processing in chemical structure data bases is discussed. The distributed array processor can be used for the clustering of 2-D chemical structure data bases by using the Jarvis—Patrick clustering method and for the ranking of output in an experimental system for substructure searching in the 3-D macromolecules in the Protein Data Bank. The Inmos transputer can be used in the construction of PC-based systems for 2-D substructure searching and in the identification of the maximal substructures common to pairs of 3-D molecules. 相似文献
106.
Blake AJ Brett MT Champness NR Khlobystov AN Long DL Wilson C Schröder M 《Chemical communications (Cambridge, England)》2001,(21):2258-2259
4,4'-Bipyridine N,N'-dioxide (L) acts as a hydrogen-bond acceptor in the compounds ([M(NO3)2(H2O)4].L2) (M = Co, Ni) to form doubly-interpenetrated framework materials with sixfold topological connectivity. 相似文献
107.
Multiconfiguration calculations have been performed in order to estimate ab initio energies for the configuration 3p4p in Si I. A preliminary attempt has also been made to calculate E2 transition rates for transitions from levels of 3p 2 to those of 3p4p. However, these rates show a gauge dependence, which indicates that further correlation needs to be included to obtain accurate rates and lifetimes. 相似文献
108.
(3-Mercaptopropyl)trimethoxysilane (MTS) forms a unique film on a platinum substrate by self-assembly and sol-gel cross-linking. The gelating and drying states of the self-assembled MTS sol-gel films were probed by use of electrochemical and spectroscopic methods. The thiol moiety was the only active group within the sol-gel network. Gold nanoparticles were employed to detect the availability of the thiol group and their interaction further indicated the physicochemical states of the sol-gel inner structure. It was found that the thiol groups in the open porous MTS aerogel matrix were accessible to the gold nanoparticles while thiol groups in the compact MTS xerogel network were not accessible to the gold nanoparticles. The characteristics of the sol-gel matrix change with time because of its own irreversible gelating and drying process. The present work provides direct evidence of gold nanoparticle binding with thiol groups within the sol-gel structures and explains the different permeability of "aerogel" and "xerogel" films of MTS on the basis of electrochemical and spectroscopic results. Two endogenous species, hydrogen peroxide and ascorbic acid, were used to test the permeability of the self-assembled sol-gel film in different states. The MTS xerogel film on the platinum electrode was extremely selective against ascorbic acid while maintaining high sensitivity to hydrogen peroxide in contrast to the relatively high permeability of ascorbic acid in the MTS aerogel film. This study showed the potential of the MTS sol-gel film as a nanoporous material in biosensor development. 相似文献
109.
The solid-state structure of 4-iodobenzoic acid has been confirmed by variable temperature X-ray diffraction, variable temperature solid-state NMR and differential scanning calorimetry. 4-iodobenzoic acid crystallizes in the space group P2(1)/n, and dimerizes in the solid state about a center of inversion. Using extensive X-ray crystallographic data collections, the placement of the carboxylate H atoms from the residual electron density in difference Fourier maps was determined. The position of the electron density associated with the proton is found to vary with temperature in that the population of the disordered sites changes with varying temperature. Determination of the crystal structure between the temperatures of 248 and 198 K was not possible due to a phase transition, an endothermic event occurring at 230.77 K. The phase transition is also indicated by a change in the relaxation time of the ring carbon atoms in the solid-state NMR data. Though the dominating force in the dimeric unit in the solid state is the presence of strong hydrogen bonds, there are also van der Waals forces present between the iodine atoms. In the layered structure, the iodine-iodine distance is within the van der Waals contact radii, an interaction which causes a deformation in the electron density of the iodine atoms. 相似文献
110.
The molecular conformations and packing of [(tBuCO2)3M2(mu-X)M2(O2CtBu)3], where M = Mo and W, and X = oxalate and perfluoroterephthalate, determined in the solid-state from powder X-ray diffraction analysis, reveal one-dimensional coordination polymers involving pivalate-oxygen to metal interactions (X = perfluoroterephthalate), and oxalate--as well as pivalate-oxygen to metal bonds (X = oxalate), and allows explanation of the unusual state-dependent chromic properties of these compounds. 相似文献