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961.
Barberá J Gimeno N Monreal L Piñol R Ros MB Serrano JL 《Journal of the American Chemical Society》2004,126(23):7190-7191
The synthesis and characterization of reactive banana-shaped compounds have been carried out, and their ability to be photopolymerized in their SmCP mesophase has been assessed. The presence of a SmCP liquid crystalline phase in these compounds has been confirmed by X-ray studies. The polymerization of these molecules has been demonstrated by calorimetric techniques as well as by the preparation and characterization of SmCP-ordered free films that are mechanically stable at room temperature. Furthermore, polymerized films exhibit second harmonic generation activity at room temperature in the absence of an electric field. 相似文献
962.
Hildebrand M Waggoner LE Liu H Sudek S Allen S Anderson C Sherman DH Haygood M 《Chemistry & biology》2004,11(11):1543-1552
"Candidatus Endobugula sertula," the uncultivated bacterial symbiont of Bugula neritina, is the proposed source of the bryostatin family of anticancer compounds. We cloned a large modular polyketide synthase (PKS) gene complex from "Candidatus Endobugula sertula" and characterized one gene, bryA, which we propose is responsible for the initial steps of bryostatin biosynthesis. Typical PKS domains are present. However, acyltransferase domains are lacking in bryA, and beta-ketoacyl synthase domains of bryA cluster with those of PKSs with discrete, rather than integral, acyltransferases. We propose a model for biosynthesis of the bryostatin D-lactate starter unit by the bryA loading module, utilizing atypical domains homologous to FkbH, KR, and DH. The bryA gene product is proposed to synthesize a portion of the pharmacologically active part of bryostatin and may be useful in semisynthesis of clinically useful bryostatin analogs. 相似文献
963.
The laser flash photolysis in a very low-pressure flow system with mass spectrometry detection technique was developed for the study of oxidation reactions of chlorofluorocarbons. In this work, we have studied the UV photolysis of O3 in the presence of Cl2 at room temperature, which presents two catalytic cycles of O3 depletion with efficiencies dependent on the partial pressures in the photoreactor. The ozone dissociation was initiated with fourth harmonic pulses of a Nd:YAG laser. The detection of the reactants and the final and intermediate reaction products was performed with real-time mass spectrometry. The variations of the O3, Cl2 and ClO concentration were measured. The equations system associated to a proposed kinetic scheme was solved numerically and excellent agreement with the experimental results was obtained. The results from this work allowed the determination of the wall loss rates of the O(1D), Cl and ClO radicals. 相似文献
964.
Zuccaccia D Pirondini L Pinalli R Dalcanale E Macchioni A 《Journal of the American Chemical Society》2005,127(19):7025-7032
The interionic structure, kinetic stability, and degree of anion encapsulation of coordination cages 1 were studied by PGSE, NOE, and EXSY NMR techniques. The rate constants for the formation/dissociation processes at 296 K were obtained independently via (1)H-NOESY and (19)F-NOESY experiments giving, respectively, k(obs) = 0.30 +/- 0.04 s(-1) in CDCl(3) and k(obs) = 5.2 +/- 0.8 s(-1) in CD(3)NO(2)/CDC(13) (7.1) mixture with the proton probe, and k(obs) = 0.33 +/- 0.06 s(-1) in CDCl(3) and k(obs) = 5.0 +/- 0.8 s(-1) in CD(3)NO(2)/CDC(13) (7/1 mixture) with the (19)F probe. PGSE experiments showed that in CDCl(3) not only the encapsuled anion but also the external anions translate with the same rate as the cage. (19)F,(1)H-HOESY experiments indicated that an average of five external triflate anions are located in the equatorial sites close to the palladium moieties, while two of them approach the polar pockets formed by the alkyl chains. In a CD(3)NO(2)/CDCl(3) (7/1) mixture only one or two anions are in close proximity with the cage, while the others are solvated. In all the considered solvents (benzene, chloroform, methylene chloride, and nitromethane) the inclusion of a single unsolvated triflate anion in the cage is quantitative. (19)F,(1)H-HOESY experiments indicated that the charged guest head points toward one metal center. Therefore, while the ionic aggregation level and kinetic stability of coordination cages 1 are solvent dependent, anion encapsulation is not. 相似文献
965.
Spiegel DA Wiberg KB Schacherer LN Medeiros MR Wood JL 《Journal of the American Chemical Society》2005,127(36):12513-12515
Trialkylboranes (BMe3, BEt3, and BBu3) have been shown to mediate reductive deoxygenation reactions of O-alkyl-S-methyl dithiocarbonates (methyl xanthates) in which water or deuterium oxide functions as the source of hydrogen or deuterium. This method has proven versatile with regard to substrate scope and is capable of providing protio- or deuterioalkane products in high yields with excellent levels of D-incorporation. Ab initio calculations suggest that the trialkylborane-water complex possesses an unusually low O-H bond dissociation energy (73 kcal/mol) and support a radical chain mechanism for this process. Taken together, this report provides evidence for fundamentally novel and previously overlooked modes of reactivity for water and trialkylboranes of wide ranging importance in both theoretical and applied investigations. 相似文献
966.
A thin chip microsprayer system coupled to Fourier transform ion cyclotron resonance mass spectrometry for glycopeptide screening 总被引:1,自引:0,他引:1
Bindila L Froesch M Lion N Vukelić Z Rossier JS Girault HH Peter-Katalinić J Zamfir AD 《Rapid communications in mass spectrometry : RCM》2004,18(23):2913-2920
A thin polymer microchip was coupled with a Fourier transform ion cyclotron resonance (FTICR) 9.4 T mass spectrometer and the method was optimized in negative ion mode for glycopeptide screening. The interface between the polymer microchip and FTICR mass spectrometer consists of an in-laboratory conceived and designed mounting system that exhibits robust and controllable alignment of the chip toward the inlet of the mass spectrometer. The particular attribute of the polymer chip coupled to the FTICR mass spectrometer, to achieve an increase in ionization efficiency and sensitivity under the premise of high mass accuracy of detection, is highlighted by the large number of major and minor glycopeptide structures detected and identified in highly heterogeneous mixtures obtained from urine matrices. Glycoforms expressing various saccharide chain lengths ranging from tri- to dodecasaccharide, bearing up to three sialic acid moieties, could be detected and assigned based on the accuracy of the mass measurement (average mass deviation below 6 ppm) of their molecular ions. -Thin chipESI-FTICRMS is a potent novel system for glycomic screening of complex mixtures, as demonstrated for identification of singly sialylated O-glycosylated amino acids and peptides from urine matrices, and could be considered for general applicability in the glycoanalytical field. 相似文献
967.
Laura Ribeiro Francisco Veiga 《Journal of inclusion phenomena and macrocyclic chemistry》2002,44(1-4):251-256
Inclusion complexation between -cyclodextrin (-CD),hydroxypropyl--cyclodextrin (HP--CD), water-solublepolymers (PVP and HPMC) and vinpocetine was studied in aqueous solution and in the solid state.Phase solubility studies were used to evaluate the complexation in aqueous solution at roomtemperature. Stability constants (Kc) of binary and ternary complexes were determined spectrophotometrically. Differential scanning calorimetry (DSC)was used to characterize kneaded, co-evaporated and lyophilised binary and ternary systems.The Kc values obtained were 70.14 M-1 and 35.01 M-1 for vinpocetine--CD and vinpocetine-HP--CD and increased in a range of 17% to 94%by addition of water-soluble polymers. Some preliminary evidences ofinclusion complexation were obtained from DSC suggesting that co-evaporated and lyophilised binary andternary systems were truly inclusion complexes. 相似文献
968.
The U+O chemi-ionization reaction has been investigated by quantum chemical methods. Potential-energy curves have been calculated for several electronic states of UO and UO(+). Comparison with the available spectroscopic and thermodynamic values for these species is reported and a mechanism for the chemi-ionization reaction U+O-->UO(+)+e(-) is proposed. The U+O and Sm+O chemi-ionization reactions are the first two metal-plus-oxidant chemi-ionization reactions to be studied theoretically in this way. 相似文献
969.
Giorgi G Salvini L Attanasi OA Guidi B Santeusanio S 《Journal of mass spectrometry : JMS》2002,37(2):169-178
Electron ionisation mass spectrometry was usefully used to characterize structurally 2-aryl-5-acetylthiazole derivatives in the gas phase. The compounds show characteristic fragmentation pathways depending on the chemical nature of the substituent at position 2, consisting mainly in the cleavage of both the 1,2- and 3,4-bonds of the thiazole ring. Liquid secondary ion mass spectrometry was applied to study the effects of protonation on the gas-phase unimolecular reactions of this class of compound. Tandem mass spectrometric experiments, carried out on molecular and protonated molecular ions, and also on fragment ions produced in the source, allowed the elucidation of gas-phase decompositions of low-internal energy ions. 相似文献
970.
Bordiga S Vitillo JG Ricchiardi G Regli L Cocina D Zecchina A Arstad B Bjørgen M Hafizovic J Lillerud KP 《The journal of physical chemistry. B》2005,109(39):18237-18242
Hydrogen storage is among the most demanding challenges in the hydrogen-based energy cycle. One proposed strategy for hydrogen storage is based on physisorption on high surface area solids such as metal-organic frameworks (MOFs). Within this class of materials, MOF-5 has been the first structure studied for hydrogen storage. The IR spectroscopy of adsorbed H2 performed at 15 K and ab initio calculations show that the adsorptive properties of this material are mainly due to dispersive interactions with the internal wall structure and to weak electrostatic forces associated with O13Zn4 clusters. Calculated and measured binding enthalpies are between 2.26 and 3.5 kJ/mol, in agreement with the H2 rotational barriers reported in the literature. A minority of binding sites with higher adsorption enthalpy (7.4 kJ/mol) is also observed. These species are probably associated with OH groups on the external surfaces present as termini of the microcrystals. 相似文献