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排序方式: 共有244条查询结果,搜索用时 140 毫秒
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2.
Dariush Habibollahzadeh Jane S. Murray Michael Grodzicki Jorge M. Seminario Peter Politzer 《International journal of quantum chemistry》1992,42(2):267-272
The C? H bond dissociation energy of acetylene was computed by both ab initio approaches and density functional theory in a local density approximation (DFT–LDA ). Structures and energies for acetylene and its dissociation products (the ethynyl and hydrogen radicals) are presented and compared. Using directly computed HCCH and HCC· energies and the exact H· value, the DFT–LDA calculations are found to yield C? H dissociation energies ranging from 129 to 131 kcal/mol, in good agreement with recent experimental and the highest level theoretical results. The DFT–LDA results show little dependence upon the computational procedure used to obtain geometries. 相似文献
3.
Guido W Vandermeulen Dariush Hinderberger Hui Xu Sergei S Sheiko Gunnar Jeschke Harm-Anton Klok 《Chemphyschem》2004,5(4):488-494
Herein we describe the structure and dynamics of self-assembled nano-objects generated from poly(ethylene glycol) based (PEG-ylated) coiled-coil hybrid block copolymers. Electron paramagnetic resonance (EPR) experiments on spin-labeled samples provided a strong indication for a parallel alignment of the peptide helices in at least the dimeric coiled-coil nano-object and indicated that the PEG chains are folded rather closely around the peptide core of the nano-objects. The EPR results were supported by AFM studies, which revealed the presence of discrete nanosized objects in thin, spin cast films of the block copolymers on mica substrates. Since their size and structure may be engineered via directed mutations in the amino acid sequence, these nano-objects may be interesting building blocks for the development of supramolecular materials with various potential applications. 相似文献
4.
Khodabakhsh Niknam Dariush Saberi Mojtaba Baghernejad 《Phosphorus, sulfur, and silicon and the related elements》2013,188(4):875-882
Silica bonded S-sulfonic acid (SBSSA) was prepared by the reaction of 3-mercaptopropylsilica (MPS) and chlorosulfonic acid in chloroform. Silica-bonded S-sulfonic acid, as a reusable solid acid catalyst, was used for the condensation reactions of indole with carbonyl compounds at ambient temperature. Tetra-(indolyl)methanes were also obtained by the condensation reaction of indole with dialdehyde compounds. Silica bonded S-sulfonic acid was recovered and reused. Supplemental materials are available for this article. Go to the publisher's online edition of Phosphorus, Sulfur, and Silicon and the Related Elements to view the free supplemental file. 相似文献
5.
Magnetic CuFe2O4/g‐C3N4 hybrids were synthesized through a facile method and their catalytic performances were evaluated in click chemistry for the first time. The structural and morphological characterization of prepared materials was carried out by different techniques such as X‐ray diffraction, high‐resolution transmission electron microscopy, field emission scanning electron microscopy, Fourier infrared spectroscopy, vibrating sample magnetometry, thermogravimetric analysis, and N2 adsorption–desorption analysis (Brunauer–Emmett–Teller surface area). The utilization of magnetic CuFe2O4/g‐C3N4 enabled superior performance in the one‐pot azide–alkyne cycloaddition reaction in water using alkyl halides and epoxides as azide precursors without the need of any additional agents. The present system is broad in scope and especially practical for the synthesis of macrocyclic triazoles and also tetrazoles. In addition, the catalytic system highly fulfills the demands of “green click chemistry” with its convenient conditions, especially easy access to a variety of significant products in low catalyst loading and simple work‐up and isolation procedure. 相似文献
6.
Reducing gas contaminants by affordable and effective adsorbents is a major challenge in the 21st century. In the present study, thorium metal organic framework (Th‐MOF) nanostructures are introduced as highly efficient adsorbents. These compounds were manufactured via a novel route resulting from the development of microwave assisted reverse micelle (MARM) and ultrasound assisted reverse micelle (UARM) methods. The products were characterized utilizing XRD, SEM, TGA/DSC, BET, and FT‐IR analyses. Based on the results, the samples synthesized by MARM had uniform size distribution, high thermal stability, and significant surface area. Calculations using DFT/B3LYP indicated that the compounds have a tendency to the polymeric form, which could theoretically confirm the formation of Th‐MOF. Results of analysis of variance (ANOVA) showed that synthesis parameters played a critical role in the manufacturing of products with distinctive properties. Response surface methodology (RSM) predicted the possibility of creating Th‐MOF adsorbents with the surface area of 2579 m2/g, which was a considerable value in comparison with the properties of other adsorbents. Adsorption studies showed that, in the optimum conditions, the Th‐MOF products had high adsorption capacity for CO and CH4. It is believed that the synthesis protocol developed in the present study and the systematic studies conducted on the samples which lead to products with ideal adsorption properties. 相似文献
7.
Niloufar Afzali Reihaneh Kardanpour Farnaz Zadehahmadi Shahram Tangestaninejad Majid Moghadam Valiollah Mirkhani Adam Mechler Iraj Mohammadpoor‐Baltork Mehrnaz Bahadori 《应用有机金属化学》2019,33(11)
A novel heterogeneous nanocatalyst was established by supporting molybdenum (VI) on Zr6 nodes in the structure of the well‐known UiO‐66 metal–organic framework (MOF). The structure of the UiO‐66 before and after Mo (VI) immobilization was confirmed with XRD, DR‐FTIR and UV–vis spectroscopy, and the presence and amount of Mo (VI) was identified by X‐ray photoelectron spectroscopy and inductively coupled plasma atomic emission spectroscopy. TEM imaging confirmed the absence of Mo clusters on the MOF surface, while SEM confirmed that the appearance of the MOF has not changed upon immobilizing the Mo (VI) catalyst. BET adsorption measurements were used to confirm the porosity of the catalyst. The catalytic activity of this heterogeneous catalyst was investigated in oxidation of sulfides with H2O2 in acetonitrile and oxidative desulfurization of dibenzothiophene. Easy work up, convenient and steady reuse and high activity and selectivity are prominent properties of this new hybrid material. 相似文献
8.
The First Mitsunobu Protocol for Efficient Synthesis of α-Acyloxyphosphonates Using 4,4′-Azopyridine
Nasser Iranpoor Habib Firouzabadi Dariush Khalili 《Phosphorus, sulfur, and silicon and the related elements》2013,188(11):2166-2171
Abstract This is the first report on applying the Mitsunobu protocol for the synthesis of various α-acyloxyphosphonates using 4,4′-azopyridine and PPh3 with diverse aromatic and aliphatic carboxylic acids. Under these conditions, diethyl azodicarboxylate (DEAD) as the traditional reagent for Mitsunobu reaction is not efficient. The insoluble pyridine hydrazine byproduct can be simply isolated and recycled to its azopyridine by an oxidation reaction and reused again. [Supplemental materials are available for this article. Go to the publisher's online edition of Phosphorus, Sulfur, and Silicon and the Related Elements for the following free supplemental resource: Characterization data of compounds 3a–3z2 and NMR spectra.] GRAPHICAL ABSTRACT 相似文献
9.
Rasool Jamshidi Zahra Afzali 《International journal of environmental analytical chemistry》2013,93(9):821-827
A procedure has been proposed for the separation and preconcentration of trace amounts of thallium. It is based on the adsorption of thallium ions onto organo nanoclay loaded with 1-(2-pyridylazo)-2-naphthol (PAN). Thallium ions were quantitatively retained on the column in the pH range of 3.5–6.0, whereas quantitative desorption occurs with 5.0?mL of 5% ascorbic acid and thallium was determined by flame atomic absorption spectrometry. Linearity was maintained between 0.66?ng?mL?1–15.0?µg?mL?1?in initial solution. Detection limit was 0.2?ng?mL?1?in initial solution and preconcentration factor was 150. Eight replicate determinations of 2.0?µg?mL?1 of thallium in final solution gave a relative standard deviation of ±1.48%. Various parameters have been studied, such as the effect of pH, breakthrough volume and interference of a large number of anions and cations and the proposed method was used to determine thallium ions in water and standard samples. Determination of thallium ions in standard sample showed that the proposed method has good accuracy. 相似文献
10.
Dr. Julian Heinrich Dr. Karolina Bossak-Ahmad Mie Riisom Dr. Haleh H. Haeri Tasha R. Steel Vinja Hergl Alexander Langhans Corinna Schattschneider Jannis Barrera Dr. Stephen M. F. Jamieson Prof. Matthias Stein Prof. Dariush Hinderberger Prof. Christian G. Hartinger Prof. Wojciech Bal Prof. Nora Kulak 《Chemistry (Weinheim an der Bergstrasse, Germany)》2021,27(72):18093-18102
Redox-active Cu(II) complexes are able to form reactive oxygen species (ROS) in the presence of oxygen and reducing agents. Recently, Faller et al. reported that ROS generation by Cu(II) ATCUN complexes is not as high as assumed for decades. High complex stability results in silencing of the Cu(II)/Cu(I) redox cycle and therefore leads to low ROS generation. In this work, we demonstrate that an exchange of the α-amino acid Gly with the β-amino acid β-Ala at position 2 (Gly2→β-Ala2) of the ATCUN motif reinstates ROS production (•OH and H2O2). Potentiometry, cyclic voltammetry, EPR spectroscopy and DFT simulations were utilized to explain the increased ROS generation of these β-Ala2-containing ATCUN complexes. We also observed enhanced oxidative cleavage activity towards plasmid DNA for β-Ala2 compared to the Gly2 complexes. Modifications with positively charged Lys residues increased the DNA affinity through electrostatic interactions as determined by UV/VIS, fluorescence, and CD spectroscopy, and consequently led to a further increase in nuclease activity. A similar trend was observed regarding the cytotoxic activity of the complexes against several human cancer cell lines where β-Ala2 peptide complexes had lower IC50 values compared to Gly2. The higher cytotoxicity could be attributed to an increased cellular uptake as determined by ICP-MS measurements. 相似文献