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141.
van Beek JD Carravetta M Antonioli GC Levitt MH 《The Journal of chemical physics》2005,122(24):244510
In a nuclear magnetic-resonance (NMR) experiment, the spin density operator may be regarded as a superposition of irreducible spherical tensor operators. Each of these spin operators evolves during the NMR experiment and may give rise to an NMR signal at a later time. The NMR signal at the end of a pulse sequence may, therefore, be regarded as a superposition of spherical components, each derived from a different spherical tensor operator. We describe an experimental method, called spherical tensor analysis (STA), which allows the complete resolution of the NMR signal into its individual spherical components. The method is demonstrated on a powder of a (13)C-labeled amino acid, exposed to a pulse sequence generating a double-quantum effective Hamiltonian. The propagation of spin order through the space of spherical tensor operators is revealed by the STA procedure, both in static and rotating solids. Possible applications of STA to the NMR of liquids, liquid crystals, and solids are discussed. 相似文献
142.
Carlo Gioeli Neil Balgobin Staffan Josephson Jyoti B. Chattopadhyaya 《Tetrahedron letters》1981,22(10):969-972
2-(Trimethylsilyl)ethyl chloroformate reacts with alcohols to give carbonates in high yield. n-Bu4NF in THF(0.2M) solution for 10 min or ZnBr2 or ZnCl2 in CH3NO2 for 10 min regenerate the alcohol at 20°C. 相似文献
143.
Francesco M. Veronese Roberta Largajolli Carlo Visco Paolo Ferruti Adelaide Miucci 《Applied biochemistry and biotechnology》1985,11(4):269-277
Surface modification of enzymes for a potential use in therapy was obtained with a new type of tailor-made copolymers ofNacryloylmorpholine andN-acryloxysuccinimide. The first monomer was designed to confer solubility on the polymer, whereas the second was used to give
it reactivity toward protein amino groups. The reactivity of polymers of different composition towards amino acid derivatives
and model proteins, such as catalase and ribonuclease-A, is described. Water soluble and catalytically active enzyme derivatives
were obained using copolymers prepared with a mixture of N-acryloxysuccinimide andn-acryloylmorpholine in a 1:99 molar ratio. At increasing molar ratio (3:97, 10:90) extensive crosslinking between polymer
and enzymes takes place, yielding insoluble adducts. 相似文献
144.
Martínez-Junza V Rizzi A Jolliffe KA Head NJ Paddon-Row MN Braslavsky SE 《Physical chemistry chemical physics : PCCP》2005,7(24):4114-4125
Photophysical studies with semi-rigid, 1, and flexible, 2, donor-bridge-acceptor (D-b-A2+) molecules with D a porphyrin and A2+ a methyl viologen moiety, were performed in neat polar solvents as well as included in surfactant (DTAB) aqueous and in reverse AOT/n-alkane micelles. The micelles acted as nanoreactors for the photoinduced electron transfer reaction upon laser excitation. In spite of the longer lifetime of the charge separated (CS) state in the semi-rigid tetrad 1(ca. 200 ns vs. ca. 100 ns for the flexible dyad 2), the CS formation quantum yield, for example in acetonitrile, was lower for the former (phi(CS) = 0.13) than for the latter (0.58). Comparison of the time-resolved fluorescence data in neat solvent and in the micelles yielded the phi(CS) values in the dilute micellar solutions. Application of laser-induced optoacoustic spectroscopy at various temperatures to 1 dissolved in a polar organic solvent (benzonitrile, BZN) included in aqueous DTAB nanoreactors afforded structural volume changes for the production in hundreds of ps of the CS state upon excitation of a polar molecule. The contraction during CS formation upon excitation of the collapsed conformer in BZN is attributed to the entering of solvent into the open molecular cavity. The opening upon formation of the CS state due to photoinduced electron transfer in the 1 collapsed conformation arises from the repulsion of the two positively charged ends in this state, as previously calculated. Inclusion of 1 in reverse AOT micelles in various n-alkanes also led to a contraction upon excitation, but the data had much more error due to the limited range of variability of the ratio of thermoelastic parameters. The data obtained with the more flexible "supermolecule" 2 showed the predicted large conformation flexibility of these molecules. 相似文献
145.
Anna Bernardi Silvia Cardani Cesare Gennari Giovanni Poli Carlo Scolastico 《Tetrahedron letters》1985,26(52):6509-6512
MgBr2 mediated addition of Methyl α-methylthio propionate silylketene acetal to α and α,β-alkoxy aldehydes is highly 3,4 -selective (18:1). -α- methylene-β- hydroxy-?-alkoxy esters (6) and (8) are synthesized. 相似文献
146.
The formation and composition of highly fluorescent zinc phosphates in the presence of traces of uranium were investigated and a direct fluorimetric determination of uranium in aqueous media was developed, based on the formation of finely dispersed and stabilized fluorescent precipitates. The standard deviation for 20 μg of uranium, in 25 ml is 5% ; with the fluorimeter described, 10-2 μg of uranium per ml can be determined with an error of 50%. The method is very selective and can be employed for analysis of uranium in ores; it is less sensitive than conventional fluorimetry of fused alkali fluorides but is much simpler and faster. Interferences can often be eliminated by suitable masking reactions. 相似文献
147.
Carlo Carlini Marco Di Girolamo Alessandro Macinai Mario Marchionna Marilena Noviello Anna Maria Raspolli Galletti Glauco Sbrana 《Journal of molecular catalysis. A, Chemical》2003,200(1-2):137-146
The synthesis of isobutanol via the Guerbet condensation between methanol and ethanol was studied by using sodium methoxide (MeONa) as soluble basic component and copper-based catalysts as heterogeneous dehydrogenating/hydrogenating metal species. The effect of the nature of the catalyst and the relative amount of its individual components with respect to the reacting alcohols as well as of temperature on productivity and selectivity of the process was investigated. The collected data indicated that the copper chromite/MeONa was more active than Cu-Raney/MeONa system. The reaction was shown to proceed with the formation only of n-propanol and isobutanol. Ethanol conversion up to 61% with selectivity to isobutanol up to 98.4% was obtained. The same catalytic systems were also employed in the reaction of the methanol/ethanol/n-propanol ternary mixture. Again copper chromite/MeONa resulted more active than the Cu-Raney/MeONa system. Finally, experiments were carried out on methanol/n-propanol mixtures in the presence of the copper chromite/MeONa catalytic system by recycling both the recovered solid copper component and the liquid reaction mixture for evidencing eventual copper leaching by MeONa. On the basis of the obtained results it was concluded that in the Guerbet reaction copper chromite works as heterogeneous catalyst. 相似文献
148.
van Delden RA Mecca T Rosini C Feringa BL 《Chemistry (Weinheim an der Bergstrasse, Germany)》2004,10(1):61-70
Two new structurally related photoswitches are described, in which azobenzene photochromism is combined with the chirality of a 2,2'-dihydroxy-1,1'-binaphthyl unit. In system 1 the chiral binaphthyl moiety is bridged by a methylene tether, locking the biaryl chirality while in system 2 the biaryl core is unbridged and has considerable conformational flexibility. Both compound are capable of inducing cholesteric liquid crystalline phases and proved to be good photoswitches both in solution and in a liquid crystalline matrix. Compound 2 is capable of completely reversing the liquid crystalline chirality which is unique for a chiroptical molecular switch where the switching unit and the chiral moiety are separate entities. 相似文献
149.
Reductive alkylatin of methylvinylketone has been accomplished by hydrogen abstraction from cyclic ethers with the redox couple: t-butyl hydroperoxide-titanous chloride. A redox radical mechanism is proposed and the selectivity of the hydrogen abstraction by t-butoxy radicals and reduction of α-ketoalkyl radical by titanous ions is discussed. 相似文献
150.
Comparison between adsorption isotherm determination techniques and overloaded band profiles on four batches of monolithic columns 总被引:1,自引:0,他引:1
The adsorption isotherms of 4-tert.-butyl phenol were measured on four different monolithic columns, using three different techniques, classical frontal analysis (FA), the perturbation on a plateau method (PP) and the recently introduced numerical procedure known as the inverse numerical method (IN). This last approach requires only the recording of a few overloaded profiles and has the potential advantage of affording a dramatic decrease of the amounts of compounds, solvent, and time needed to determine accurate estimates of the coefficients of the isotherm. The reproducibility of the adsorption data measured on the four columns is discussed with reference to the specific techniques used for obtaining these data and to the most suitable equation used for modeling them. The data obtained for the different columns were highly consistent. The inverse numerical approach was confirmed to provide a powerful, accurate, and economic method for measuring single component adsorption data. 相似文献