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161.
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
162.
[reaction: see text] Regioselective metalation of pyrazines and cross-coupling reactions provides an easy access to botryllazines A and B and to an isomer of botryllazine A with good yields from chloropyrazine. 相似文献
163.
The advantage of high-speed time-of-flight-mass spectrometry (TOF-MS) detection for ultrafast qualitative supercritical fluid chromatography/mass spectrometry (SFC/MS) applications allows the superior resolving power of SFC to be exploited in high-throughput analysis. A chromatographic comparison of quadrupole MS and TOF-MS shows high-speed TOF total ion current data point sampling to be more indicative of fast SFC separations and corresponding short (1-2 s) baseline peak widths. Results shown for analysis of a six-compound mixture with two peaks eluting at 0.86 and 0.89 min exhibit >50% resolution by high-speed TOF data sampling, whereas the same peaks appear to coelute using quadrupole MS data sampling. Additionally, a marked improvement in the peak baseline widths is afforded by fast TOF data acquisition of 0.1 s/spectrum, resulting in a reduction in the baseline width, 1.6 s, of sulfanilamide in a four-compound mixture that is more than 2-fold greater than that achieved at the slower data acquisition of 0.5 s/spectrum. The resulting increase in resolution and improved peak shapes allow automatic integration routines to perform more effectively. For most classes of compounds amenable to high performance liquid chromatography, including druglike species, steroids, and polymers, the union of SFC with TOF-MS provides the maximum density of chemical information per unit time available with any high-speed chromatographic/mass spectrometric method. 相似文献
164.
Ability of porous graphitic carbon to support electroosmotic flow in capillary electrochromatography
The existence of a cathodic EOF (electroosmotic flow) in the case of a porous graphitic carbon (PGC) partially packed column has been demonstrated. Then, the ability of PGC to afford electroosmosis has been brought to the fore with a fully PGC packed column. Experimental data have shown that PGC particles are negatively charged and their electrophoretic mobility has been evaluated. In order to investigate the conditions of existence of EOF different mobile phases have been tested. An EOF occurs when the conductivity of the PGC packed column is larger than the conductivity of an empty fused-silica capillary operating in the same conditions i.e. when the PGC participates in the electric conduction. Since the local electric fields in the two segments of the column are different, an evaluation of the electroosmotic mobility is not possible and the effect of the operational parameters such as the composition of the mobile phase (acetonitrile ratio and total ionic strength) has been studied in term of electroosmotic velocity V(eo). 相似文献
165.
A. Oumghar J. C. Legrand A. M. Diamy N. Turillon R. I. Ben-Aïm 《Plasma Chemistry and Plasma Processing》1994,14(3):229-249
Conversion of CH4 with a N2 microwave plasma (2.45 GHz) is studied. The experiments cover the absorbed microwave power range 300–700 W with 17–62% of methane in the gas mixture, with pressures of 10–40 mbar and flow rates of 140–650 ml· min–1. The yields of C2 hydrocarbons and dihydrogen are analyzed by gas chromatography. The distance of methane addition downstream of the plasma plays an important role on the composition and the concentration of the products obtained. This distance mainly determines the energy concentrated in the active species of the plasma when they react with methane. Different behaviors for acetylene formation, on the one hand, and for ethane and ethene formation, on the other hand, have been observed, and this finding allows us to propose a kinetic mechanism for the decay of methane and for the formation of C2 hydrocarbons. 相似文献
166.
Frank J. Quaeyhaegens Herman O. Desseyn Spiros P. Perlepes John C. Plakatouras Ben Bracke Albert T. H. Lenstra 《Transition Metal Chemistry》1991,16(1):92-101
Summary The synthesis of the NiII, PdII and CuII complexes of N, N-bis(aminoalkyl)oxamides (LH2) is described and structures are proposed on the basis of their physical and spectroscopic properties. With NiII and PdII only one complex is formed with general formula NiL or PdL, characterised by coordination through two deprotonated amide N-atoms and two terminal NH2 groups. With CuII it proved possible to obtain three structurally different compounds, depending on the pH, with general formulae Cu(LH2)X2, Cu2(L)X2 and CuL in which X=Cl, Br or NO3. The structure of [Cu2(C8O2N4H16](NO3)2 was solved by means ofx-ray diffraction; Mr=451.33, monoclinic, space group P21/n, a=9.503(4), b=7.614(1), c=10.407(3) Å, =98.43(3)°, V=744.3(7)Å3, Z=2, Dx=1.202 g cm–3, =1.33 cm–1, (MoK)=0.71073 Å, F(000)=520, room temperature, R=0.043, wR=0.047 for 1080 observed [I>-3(I)] not systematically absent reflections out of 1423 measurements and 137 variables. The compound has a conformational chair/boat disorder with 82% in the more stable chair form. 相似文献
167.
Microwave irradiation effectively accelerates cross-coupling metathesis reactions between deactivated olefins. Reactions have been carried out with the phosphine-free Hoveyda-Grubbs catalyst and the "second generation Grubbs' catalyst." While there have been reports that a "microwave effect" is observed in various transformations, the accelerations we observe are due to the efficient and rapid heating and increased pressure in the microwave apparatus. 相似文献
168.
The open-circuit potential drop of an oxidatively pretreated nickel electrode in 0.1 M NaOH was used to develop a technique for the determination of alcohols, amino acids, carbohydrates, etc., in aqueous solution. The electrode pretreatment consisted of the formation of nickel hydrated oxides on the electrode surface with an oxidation state > 2. Both electrochemical and chemical pre-oxidation of the electrode surface were examined. The analytical signal was the enhancement of the potential drop corresponding to analyte concentration. The analytical signal was linearly related to the logarithm of the analyte concentration. The limits of determination ranged from 1 mM for low-molecular-weight to 0.02 mM for alkyl polyether alcohols. The flow-injection technique allows convenient pretreatment and direct observation of the analytical signal. Interferences from chloride and calcium can be readily eliminated by excluding them during electrode pretreatment. Potentiometric measurements were correlated with amperometric anodic responses at the nickel oxide electrode, allowing an unusual direct comparison of the two methods. 相似文献
169.
Gruy F 《Journal of colloid and interface science》2001,237(1):28-39
Aggregation of silica powder in water has been experimentally studied by turbidimetry. Aggregation was carried out in a stirred tank under physicochemical conditions corresponding to attractive interparticle forces. The effects of different primary particle sizes and stirring rates on aggregation dynamics have been studied. The scattering cross sections of silica aggregates were calculated in the framework of the anomalous diffraction approximation of light scattering theory. Aggregation has been studied by using Kusters's and Brakalov's approaches. By comparison between experimental and theoretical turbidity changes with time it has been shown that aggregates are small and slightly porous. The aggregation process is characterized by a weak fractal dimension D(wf) and an aggregate limit size L.D(wf) is found in the range 2.4-2.5. D(wf) (respectively L) is a weakly increasing (respectively decreasing) function of the stirring rate or of the shear rate. Copyright 2001 Academic Press. 相似文献
170.
The stereochemistry of the cyclodehydration of (±)- and meso-2,5-hexanediol on the action of various dehydrating agents was investigated. The earlier assumed and confirmed intramolecular SN2 mechanism for acid-catalysed ring-closure was found to hold in most cases. Various extents of racemisation can be observed on the action of certain Lewis acids, and the solvents concentrated H2SO4 and HMPT (hexamethyl phosporic acid triamide) under previously unexamined reaction conditions. 相似文献