1,3-Disubstituted pyrroles were prepared by a microwave-assisted reaction of pyrrolidine and aldehydes in toluene as well as in solvent-free conditions. Reactions were completed in a few minutes in the solvent-free condition but a long time (up to 30 min) was necessary to complete reactions in toluene. Yields of products depended considerably on the aldehyde used. 相似文献
A series of new tetrakis(dialkoxyphenyl) dicyanotetraoxapentacene derivatives ( 1 a – c ) were prepared by reaction of the appropriate terphenyl diols with tetrafluoroterephthalonitrile in good yields. Compounds 1 b and 1 c , which bear hexyloxy and decyloxy side chains, exhibited columnar hexagonal mesophases, as shown by polarized optical microscopy, variable-temperature powder X-ray diffraction, and differential scanning calorimetry. Single-crystal X-ray diffraction of methoxy-substituted 1 a revealed that the dicyanotetraoxapentacene core is highly planar, consistent with the notion that these molecules are able to stack in columnar mesophases. A detailed photophysical characterization showed that these compounds exhibit aggregation-induced emission in solution, emission in nonpolar solvents, weak emission in polar solvents, and strong emission in the solid state both as powder and in thin films. These observations are consistent with a weakly emissive charge-transfer state in polar solvents and a more highly emissive locally excited state in nonpolar solvents. 相似文献
The distribution coefficients and enantioseparation of cyclopentolate were studied in an extraction system containing d-tartaric acid ditertbutyl ester in organic phase and 2-hydroxypropyl-β-cyclodextrin (HP-β-CD) in aqueous phase. Various parameters involved in the enantioseparation such as the type and the concentration of chiral selectors, pH value and a wide range of organic solvents were investigated. The maximum enantioselectivity (α = 2.13) and optimum distribution coefficients (KR = 0.85, KS = 0.40) were obtained under the following conditions: 0.10 mol/L HP-β-CD in aqueous phase and 0.20 mol/L d-tartaric acid ditertbutyl ester in decanol as organic phase. Cyclopentolate is present as a racemic mixture to the aqueous phase. The potentially different biological activities of cyclopentolate enantiomers have not been examined yet. Two chiral liquid chromatography methods have been developed for the direct separation of the enantiomers of cyclopentolate. First method was used for the quantification analysis of cyclopentolate enantiomers in aqueous phase. Second method used two chiroptical detectors: electronic circular dichroism (ECD) and optical rotation (OR) for the identification of individual cyclopentolate enantiomers from the organic phase enriched with (R)-enantiomer. The absolute stereochemistry was determined by means of the comparison of the experimental and computed ECD spectra and signs of OR. The ECD spectra of chiral analytes were measured on-line using HPLC-ECD technique.
The Pd-catalysed conjugate addition of arylboronic acids to α,β-unsaturated cyclic ketones was studied under controlled microwave irradiation conditions. A variety of catalysts, bases and
solvents was explored in order to achieve optimum yields in the shortest possible reaction time. Under optimised conditions
(Pd(OAc)2/2,2′-bipyridine and KF in a mixture of toluene, water, and acetic acid and 10 min microwave irradiation), a range of arylboronic
acids was successfully added to several cyclic enones. With chiral phosphane ligands, a promising enantioselectivity was obtained
(85 % ee). 相似文献
Rhodium(II) complexes with dioximes [Rh(Hdmg)2(PPh3)]2 [I] (Hdmg=monoanion of dimethylglyoxime) and [Rh(Hdmg)(ClZndmg)(PPh3)]2 [II] catalyse hydroformylation and hydrogenation reactions of 1-hexene at 1 MPa CO/H2 and 0.5 MPa H2 at 353 K, respectively. Hydroformylation with complex [I] produces 94% of aldehydes (n/iso=2.2) and 6% 2-hexene whereas the second catalyst [II] gives ca. 40% of aldehydes (n/iso=2.1) and 60% of 2-hexene. Corresponding Rh(III) complexes are inactive in hydroformylation except of RhH(Hdmg)2(PPh3) [III], which shows activity similar to [I]. Complexes [Rh(Hdmg)2(PPh3)]2 [I], [Rh(Hdmg)(ClZndmg)(PPh3)]2 [II], RhH(Hdmg)2(PPh3) [III] and [Rh(Hdmg)2(PPh3)2]ClO4 [V] catalyse 1-hexene hydrogenation with an average TON ca. 18 cycles/mol [Rh]×min. Complex [II] has also been found to catalyse hydrogenation of cyclohexene, 1,3-cyclohexadiene and styrene. 相似文献
In this work, the potential of inductively coupled plasma-mass spectrometry (ICP-MS) coupled to capillary electrophoresis (CE) to determine organophosphorus pesticides (OPPs) is demonstrated. Element specific detection of (31)P with ICP-MS is performed for the detection of OPPs. Three common OPPs, including glyphosate, glufosinate, and aminomethylphosphonic acid (AMPA), were analyzed by CE-ICP-MS to demonstrate its applicability for the analysis of OPPs. The advantages of using ICP-MS with respect to other common detectors, such as flame photometric detection (FPD), for CE analysis of OPPs are shown. Additionally, different CE separation conditions were studied to achieve complete baseline separation of the pesticide compounds in short migration times. Two CE buffer systems were evaluated for the separation of OPPs using ICP-MS detection. A buffer solution containing 40 mmol.L(-1) ammonium acetate at pH 9.0 and an applied voltage of +20 kV were finally selected leading to a separation time of 10.0 min. Both migration time and area relative standard deviations (%RSD) were evaluated and their respective values were in the intervals of 1.1-3.3% and 2.7-5.3%. Detection limits obtained with the CE-ICP-MS system were in the range of 0.11-0.19 mg.L(-1) (as compound) yielding an enhancement of 130- to 230-fold with respect to FPD. The proposed methodology was finally applied for the determination of the OPPs mentioned above in natural river water samples. 相似文献
Twenty-four polymorphic compounds which show between two and four modifications are cited. The compounds described in detail are tetrabutylammonium iodide, tetraheptylammonium bromide, tetraoctylammonium bromide, 3-(3,4,5-trimethoxyphenyl)-2-propenoic acid andl-tyrosine ethyl ester hydrochloride. For the remaining nineteen compounds, only the number of modifications found, and their melting points where possible, are given. 相似文献
Based on pronounced enhancing effects in combination with other DNA-damaging agents the potentials of Ni(II), Cd(II) and
As(III) to interfere with DNA repair processes in HeLa cells was investigated. With respect to oxidative DNA damage, Ni(II)
and Cd(II) induced DNA strand breaks starting at concentrations of 250 μM and 5 μM, respectively. The induction of oxidative
DNA base modifications like 8-hydroxyguanine was restricted to the cytotoxic concentration of 750 μM Ni(II) and not observed
after treatment with Cd(II). In contrast, the removal of oxidative DNA base modifications was inhibited at concentrations
as low as 50 μM Ni(II) and 0.5 μM Cd(II). Regarding nucleotide excision repair, Ni(II) and Cd(II) disturbed the DNA-protein
interactions involved in the damage recognition step when applying HeLa nuclear protein extracts and a UV-damaged oligonucleotide,
while As(III) inhibited the actual incision event. In the case of Ni(II) and Cd(II), this effect was reversible by the addition
of Mg(II) and Zn(II), respectively. Furthermore, Cd(II) inactivated the isolated bacterial Fpg protein, most likely by the
displacement of Zn(II) from its zinc finger structure. Since DNA is continuously damaged by exogenous and endogenous sources,
an impaired repair capacity might well account for the carcinogenic action of the metal compounds.
Received: 30 July 1997 / Revised: 6 October 1997 / Accepted: 10 October 1997 相似文献
Semiconductor alpha-MoTe2 nanorods have been synthesized by annealing Te-seeded particles of an amorphous MoTe2 intermediate. This intermediate is prepared by a solution reaction between Mo(CO)6 and elemental Te in diphenylmethane. The as-synthesized products were characterized by structural, compositional, and morphological techniques of X-ray diffraction, selected area electron diffraction, selected area energy dispersive spectroscopy, energy dispersive X-ray analysis, X-ray photoelectron spectroscopy, transmission electron microscopy, and high-resolution transmission electron microscopy. The results of the annealing process are MoTe2 nanorods with diameters of 50-200 nm and lengths ranging from 0.1 to 3.0 microm. Here, the rodlike structure of MoTe2 is reported for the first time, and added to the list as one kind of new morphology of MoTe2 nanomaterials. A mechanism for the formation of the nanorods is proposed. The sandwich-layered structure of Te-Mo-Te and the similarity in the structure between hexagonal alpha-MoTe2 and hexagonal Te are responsible for the formation of nanorods of MoTe2. 相似文献