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111.
Four new lignans, 3',4'-O,O-demethylenehinokinin (1), chamalignolide (2), 8'beta-hydroxyhinokinin (3) and 7beta,8beta-epoxyzuonin A (4), as well as (-)-hinokinin (5), and (-)-zuonin A (6), were isolated from the heartwood of Chamaecyparis obtusa var. formosana. The structures of these lignans were unambiguously determined by spectroscopic methods. And the absolute configuration of 1 was elucidated with a circular dichroism (CD) spectrum. 相似文献
112.
Chiang LY Padmawar PA Canteenwala T Tan LS He GS Kannan R Vaia R Lin TC Zheng Q Prasad PN 《Chemical communications (Cambridge, England)》2002,(17):1854-1855
The first, highly two-photon active C60 derivative comprised of a A-sp3-D conjugate structure was synthesized showing effective two-photon absorption cross-sections (sigma 2' = 196 x 10(-48) cm4 sec-1 molecule-1) in the nanosecond regime among the best values for diphenylaminofluorene-based AFX chromophores. 相似文献
113.
The charge transport properties of mer-tris(8-hydroxyquinolinato)aluminum(III) (mer-Alq), which is the most widely used electron transport material in OLED, were investigated by quantum chemistry calculations within the framework of the charge hopping model and Marcus electron transfer theory. Internal reorganization energies of 0.276 and 0.242 eV were calculated by the DFT-B3LYP method employing a 6-31 G* basis set for the electrons lambdai(e) and holes lambdai(h), respectively. The relative distances and orientations of Alq molecules in amorphous film were simulated by those in the beta-phase. The intermolecular charge-transfer integrals, Hda(h) and Hda(e), along all 14 hopping pathways were then calculated by the Koopmans Theorem in conjunction with the Hartree-Fock method employing a 6-31 G* basis set as well as by the direct coupling method. The results showed that there were some Hda(e) that were 1 order of magnitude larger than any Hda(h), because hopping pathways with effective overlaps of LUMOs can occur and, thus, large Hda(e). On the other hand, effective overlap of HOMO was absent in all pathways, resulting in a relatively small Hda(h). This difference in the magnitudes of Hda(e) and Hda(h) would predict a 2 orders of magnitude difference in the electron-transfer rate constants and account for the observed 2 orders of magnitude difference in the mobilities of electrons and holes. 相似文献
114.
The use of a low-temperature (0 degrees C) bath-assisted coupled capillary for the separation of naphthalene-2,3-dicarboxaldehyde (NDA)-derivatized dopamine and norepinephrine using the sweeping-micellar electrokinetic capillary chromatography (MEKC) mode is described. In this technique, a capillary consisting of two portions with different inside diameters is used. Therefore, the field strength inside the capillary is different. Hence, the electrophoretic migration velocities of the analytes and the electro-osmotic flow (EOF) also are different. Furthermore, when a portion of the capillary (wide portion, used for sweeping) is immersed in a low-temperature bath, the viscosity of the buffer and the retention factor of the analytes inside are increased. Thus, not only are the interactions between the SDS micelles and the analytes increased, but the SDS-analytes also move more slowly. As a result, a more complete separation can be achieved, even when the sample injection volume is large, up to approximately 2 microL. In general, when the volume of an injected sample is larger, the effects of sweeping and separation would become insufficient, especially when the retention values (k) of the analytes are quite different. However, this limitation can be improved when the low-temperature bath/coupled capillary/sweeping-MEKC mode is used. 相似文献
115.
Experimental analysis of floc size distributions in a 1-L jar under different hydrodynamics and physicochemical conditions 总被引:1,自引:0,他引:1
This study focuses on the relation among hydrodynamics, physicochemical conditions, and floc size. During ortho-kinetic flocculation, the floc size is controlled by a balance between hydrodynamic stress and aggregate strength. Special attention was paid to the influence of a hydrodynamic sequencing on both the aggregate strength and the flocculation processes. Experimental research was conducted in a 1-L jar for two different pH values. The hydrodynamic sequencing was made up of successive slow and rapid mixing periods, and different slow mixing intensities were studied. First, the large floc size was shown to decrease with increasing velocity gradient (G), with an expected trend (d proportional variant epsilon(-1/4)). Then, the aggregate strength was shown to depend on two main factors: the flocculation history and the physicochemical conditions, which control the cohesion forces between primary particles. Finally, flocculation processes are discussed in terms of aggregation and breakup phenomena, with relation to local hydrodynamics and physicochemical conditions. 相似文献
116.
The resolving ability of 2-O-(2-hydroxybutyl)-beta-CD (HB-beta-CD) with different degrees of substitution (DS = 2.9 and 4.0) as a chiral selector in CZE is reported in this work. Fourteen chiral drugs belonging to different classes of compounds of pharmaceutical interest such as beta-agonists, antifungal agents, ageneric agents, etc., were resolved. The effects of the DS of HB-beta-CD on separations were also investigated. The chiral resolution (R(s)) was strongly influenced by the concentrations of the CD derivative, the BGE, and the pH of the BGE. Under the conditions of 50 mmol/L Tris-phosphate buffer at pH 2.5 containing 5 mmol/L HB-beta-CD, all 14 analytes were separated. The very low concentration necessary to obtain separation was particularly impressive. The DS had a significant effect on the resolution of the chiral drugs and the ionic strength of the separation media; hence, the use of a well-characterized CD derivative is crucial. 相似文献
117.
Thermodynamic analysis of the reversed-phase retention behavior of a doxorubicin-peptide conjugate demonstrated that the degree of non-linearity observed in Van't Hoff plots was impacted by mobile phase acetonitrile content over the 25-38% acetonitrile (v/v) range tested. Small decreases in the non-polar surface area of the doxorubicin-peptide conjugate as a function of temperature were estimated from these data using linear solvent strength relationships, suggesting that the retention behavior may be the result of minor analyte conformational changes during the chromatographic experiment. This hypothesis was supported via circular dichroism (CD), Raman and 1H NMR spectroscopic studies of the doxorubicin-peptide conjugate in selected chromatographic mobile phase compositions. The CD and Raman data indicated small changes to the apparent analyte microenvironment as a function of temperature and bulk solvent environment, while 1H NMR studies specifically demonstrated the environmental sensitivity of protons on three non-polar peptide residues and the proximal aromatic region of the analyte. Together, these data suggest that minor changes to the conformational order of the essentially random structure of the doxorubicin-peptide conjugate are sufficient to impact chromatographic performance. 相似文献
118.
A method for the determination of trace Cr(III) in aqueous solution by solid-phase microextraction (SPME) coupled with gas chromatography (GC)-flame photometric detection (FPD) was developed. Aqueous Cr(III) was first converted to the volatile chromium trifluoroacetylacetonate (Cr(tfa)3) by derivatization with 1,1,1-trifluoroacetylacetone (Htfa), followed by SPME extraction using a polyimide-coated silica fiber. The distribution constants (K) of derivatized cis- and trans-Cr(tfa)3 between the polyimide phase and aqueous phase were 2012 and 2214, respectively. The two Cr(tfa)3 isomers extracted can be efficiently separated by a DB-210 GC column within 9 min. Selective detection of Cr was performed by a FPD equipped with a 385-nm long-pass filter. Linearity (r> 0.99) over the concentration range 5-300 ng ml(-1) Cr was obtained and the limit of detection was 2 ng ml(-1) Cr. The relative standard deviation was 7% at 10 ng ml(-1) Cr (n = 5). Applicability of this method to water analysis was tested by analyzing the chromium content in a reference standard water sample and an industrial effluent. 相似文献
119.
A new approach to a CD45 protein tyrosine phosphatase inhibitor, pulchellalactam, is described. The key step of the sequence involves addition and elimination of an enolic lactam in a single step and 70% yield, employing an organocuprate reagent. The resulting alpha,beta-unsaturated lactam could be condensed with isobutyraldehyde to produce Z-pulchellalactam or converted into siloxypyrrole, which was subjected to the BF(3) x Et(2)O-promoted coupling reaction with isobutyraldehyde to afford E-pulchellalactam after E1-cB elimination and TFA deprotection. This first total synthesis afforded Z-pulchellalactam in six steps and 32% overall yield from Boc-glycine. The same sequence of reactions could also be applied to the liquid- or solid-phase synthesis of trifunctionalized pulchellalactam derivatives. 相似文献
120.
This paper presents a system-oriented model for analyzing the dispersion of electrophoretic transport of charged analyte molecules in a general-shaped microchannel, which is represented as a system of serially connected elemental channels of simple geometry. Parameterized analytical models that hold for analyte bands of virtually arbitrary initial shape are derived to describe analyte dispersion, including both the skew and broadening of the band, in elemental channels. These models are then integrated to describe dispersion in the general-shaped channel using appropriate parameters to represent interfaces of adjacent elements. This lumped-parameter system model offers orders-of-magnitude improvement in computational efficiency over full numerical simulations, and is verified by results from experiments and numerical simulations. The model is used to perform a systematic parametric study of serpentine channels consisting of a pair of complementary turn microchannels, and the results indicate that dispersion in a particular turn can contribute to either an increase or decrease of the overall band broadening. The efficiency and accuracy of the system model is further demonstrated by its application to general-shaped channels that occur in practice, including a serpentine channel with multiple complementary turns and a multi-turn spiral-shaped channel. The results indicate that our model is an accurate and efficient simulation tool useful for designing optimal electrophoretic separation microchips. 相似文献