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111.
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113.
Two-center nuclear attraction integrals over Slater type orbitals with integer and noninteger principal quantum numbers in nonlined up coordinate systems have been calculated by means of formulas in our previous work (T. Özdoan and M. Orbay, Int. J. Quant. Chem. 87 (2002) 15). The computer results for integer case are in best agreement with the prior literature. On the other hand, the results for noninteger case are not compared with the literature due to the scarcity of the literature, but also compared with the limit of integer case and good agreements are obtained. The proposed algorithm for the calculation of two-center nuclear attraction integrals over Slater type orbitals with noninteger principal quantum numbers in nonlined-up coordinate systems permits to avoid the interpolation procedure used to overcome the difficulty introduced by the presence of noninteger principal quantum numbers. Finally, numerical aspects of the presented formulae are analyzed under wide range of quantum numbers, orbital exponents and internuclear distances. 相似文献
114.
Agopcan S Çelebi-Ölçüm N Üçışık MN Sanyal A Aviyente V 《Organic & biomolecular chemistry》2011,9(23):8079-8088
In this study, the origins of diastereoselectivity in the hydrogen bonding assisted Diels-Alder reactions of chiral dienes with achiral dienophiles have been investigated with density functional methods. The distortion/interaction model has been applied to shed light on the origins of selectivity. C9-Substituted chiral anthracene templates (R = (CH(3))(OCH(3))(H), R = (CH(3))(OH)(H), R = (CH(3))(CH(2)CH(3))(H) and R = (-CH(2)-C(CH(3))(OCH(3))(H)) are used to rationalize the role of a stereogenic center and H-bonding on the product distribution ratio. Even though hydrogen bonding increases the reactivity of the diene, the stereoselectivity is reduced because of the hydrogen bonding capacity of both diastereomeric transition states. The interaction energies of the studied anthracene templates with N-methyl maleimide at the transition state correlate linearly with an increase in reactivity. The selectivity is determined by both favorable distortion and interaction energies. The π-facial selectivity induced by the presence of a chiral auxiliary in 1-substituted 1,3-pentadienes (R1 = (CH(3))(OCH(3))(H) and R1 = (CH(3))(OH)(H)) has also been modeled in order to rationalize the role of the stereogenic center and H-bonding on the stereoselectivity of an aliphatic diene. In both parts, the product distribution ratios calculated from Boltzmann distributions based on Gibbs free energies are in reasonable agreement with the experimental results. Finally the role of OH-substituted five-membered pyrrolidine on C9 of anthracene is investigated since the successful usage of the conformationally rigid pyrrolidines in asymmetric synthesis is well known. Overall, both in the acyclic system and in anthracene, the facilitation due to H-bonding is reflected in the interaction energies: the higher the difference in interaction energies in the transition structures of the two diastereomers, the more selective the H-bonding assisted Diels-Alder reaction is. 相似文献
115.
Nihat Özcan Süleyman Akman 《International journal of environmental analytical chemistry》2019,99(4):357-368
Amitraz is a non-systemic acaracide and insecticide. Current maximum residue limits for amitraz are stated as ‘Amitraz including the metabolites containing the 2,4-dimethylaniline moiety’. Therefore, determination of amitraz and its all degradation products are important. In this study, we develop a gas chromatography/mass spectrometry (GC/MS) method for determination of amitraz and its degradation products 2,4 dimethylaniline (DMA), 2,4 dimethylformamidine (DMF) and N-(2,4-dimethyl phenyl)-N’-methylformamidine (DMPF) in cucumber and quince. The mechanism of the degradation process was monitored at different temperatures. Amitraz and its degradation products were extracted using the QuEChERS method. To determine amitraz and its degradation products, we used GC/MS. Quantification was carried out by using selected ion monitoring, and total ion chromatogram was used to monitor additional degradation products. The method was validated by studying linearity, limit of detection (LOD) and limit of quantification (LOQ), recovery and precision. The mechanism of the degradation process was monitored at different temperatures. Degradation of amitraz mainly to three degradation products, namely DMA, DMF and DMPF, increased with temperature. Besides these three main degradation products, two other new degradation products were detected. 相似文献
116.
Hasan Kırmızıbekmez Yiğit İnan Rengin Reis Hande Sipahi Ahmet C. Gören Erdem Yeşilada 《Natural product research》2019,33(17):2541-2544
Phytochemical investigations on the EtOH extract of Clematis viticella led to the isolation of six flavonoid glycosides, isoorientin (1), isoorientin 3′-O-methyl ether (2), quercetin 7-O-α-L-rhamnopyranoside (3), quercetin 3,7-di-O-α-L-rhamnopyranoside (4), manghaslin (5) and chrysoeriol 7-O-β-D-glucopyranoside (6), one phenylethanol derivative, hydroxytyrosol (7), along with three phenolic acids, caffeic acid (8), (E)-p-coumaric acid (9) and p-hydroxybenzoic acid (10). The structures of the isolates were elucidated on the basis of NMR and HR-MS data. All compounds were isolated from C. viticella for the first time. Compounds 7 and 8 showed significant anti-inflammatory activity at 100 μM by reducing the release of NO in LPS-stimulated macrophages comparable to positive control indomethacin. Compounds 3 and 7 exhibited anti-inflammatory activity through lowering the levels of TNF-α while 1, 3 and 5 decreased the levels of neopterin better than the positive controls. 相似文献
117.
Francisco José Aguilar Troyano Frederic Ballaschk Marcel Jaschinski Yasemin Özkaya Dr. Adrián Gómez-Suárez 《Chemistry (Weinheim an der Bergstrasse, Germany)》2019,25(62):14054-14058
The synthesis of tertiary alkyl fluorides through a formal radical deoxyfluorination process is described herein. This light-mediated, catalyst-free methodology is fast and broadly applicable allowing for the preparation of C−F bonds from (hetero)benzylic, propargylic, and non-activated tertiary alcohol derivatives. Preliminary mechanistic studies support that the key step of the reaction is the single-electron oxidation of cesium oxalates—which are readily available from the corresponding tertiary alcohols—with in situ generated TEDA2+. (TEDA: N-(chloromethyl)triethylenediamine), a radical cation derived from Selectfluor®. 相似文献
118.
Ion chromatography–inductively coupled plasma-mass spectrometry (IC–ICP-MS) was used for the identification and quantification of chromium species. Chromium(III) and chromium(VI) were separated and determined by IC–ICP-MS. The separation was achieved using an anion exchange column with 0.55?M HNO3 as mobile phase. It was a particular goal of this work to exclusively use nitric acid for elution in order to reduce interferences in the ICP-MS system. Analytical figures of merit were calculated under the optimum conditions by developing calibration plots in a concentration range of 0.50–250?µg/L for both species. The detection limits for Cr(III) and Cr(VI) were 0.09 and 0.03?µg/L, respectively. Spiked recovery tests were used to evaluate the applicability of the analytical method in environmental samples, and the recoveries ranged between 97 and 103% for both analytes. The accuracy of the method for total chromium content was validated through the analysis of a spring water-certified reference material (UME 1201), and the obtained results were in good agreement with the certified value. Lettuce seedlings were cultivated to evaluate the intake levels of these species. In addition, the bioaccessibility of Cr(III) and Cr(VI) from the lettuce seedlings in simulated gastric and intestinal fluids media was examined. 相似文献
119.
Ahmet Karadağ Ali Aydin Şaban Tekin Hüseyin Akbaş Süreyya Dede 《Journal of Coordination Chemistry》2019,72(5-7):860-878
The synthesis of three bimetallic cyanido complexes with edbea [2,2′-(ethylenedioxy)bis(ethylamine)] ligand is reported. [NiII(μ-edbea)2{Au(μ-CN)2}2]n (1), [{CuII(edbea)}2{Au(μ-CN)2}4]n (2) and [CdII(edbea)2][Au(CN)2]2·H2O (3) were fully characterized by elemental, infrared, XRD (3), ESI-MS and thermal analysis. The DNA/BSA binding properties of these complexes were evaluated by spectrophotometric titration, fluorometric ethidium bromide kinetics, and DNA electrophoresis studies and their partially minor groove binding mode between the base pairs of DNA and electrostatic interaction between the amino acid residues of BSA were explained. The complexes were tested for their pharmacological properties. These molecules had excellent in vitro antiproliferative activity and also exhibited a strong tumor inhibiting effect against HT29, HeLa, C6 and Vero cell lines. These complexes had metastatic features as they are able to reduce cell migration activity and suppress tumor growth in vitro. Analysis of the DNA topoisomerase I relaxing activity indicates that the complexes do not inhibit topoisomerase I which regulates the topological states of the DNA double helix during DNA processing reactions. The TUNEL and DNA laddering assay results indicated that these compounds may destroy cell maintenance by triggering apoptosis. Immunohistochemistry staining analysis demonstrated that these complexes significantly decreased the expression of Bcl-2 in HeLa and HT29 cells while increasing the expression of P53 levels. Overall, the potent antiproliferative activity, low cytotoxic effect, good solubility, and micro molar range dosage observed for these complexes emphasizes their potential as anticancer drug candidates. 相似文献
120.
The protonation constants of two nitro-Schiff bases SB1, SB2 and three asymmetric tetradentate diimines H2L1, H2L2 and H2L3 and the stability constants of their ML type binuclear Ni(II) and Fe(III) complexes have been determined potentiometrically. The asymmetric diimines are (2OH) RCHNC6H4CHNR′ (2OH) type compounds [where R = R′ = phenyl for H2L1; R = naphthyl, R′ = phenyl for H2L2 and R = R′ = naphthyl for H2L3]. The effect of tautomeric forms on the acid-base properties of the diimines has been investigated and discussed. In addition, dimeric and binuclear Ni(II) and Fe(III) complexes of the diimines have been synthesized and characterized by physical and spectroscopic techniques. Also, in vitro antimicrobial activities of the diimines and the complexes have been evaluated against three bacteria: Micrococcus luteus (NRLL B-4375), Bacillus cereus (RSKK 863), Escherichia coli (ATCC 11230) and the fungus: Candida albicans (ATCC 10239). 相似文献