共查询到20条相似文献,搜索用时 15 毫秒
1.
Andrieu J. Belkova N. V. Besora M. Collange E. Epstein L. M. Lledós A. Poli R. Revin P. O. Shubina E. S. Vorontsov E. V. 《Russian Chemical Bulletin》2003,52(12):2679-2682
The protonation of complexes Cp*M(dppe)H3 (dppe is ethylenebis(diphenylphosphine), M = Mo (1), W (2)) by a variety of fluorinated alcohols of different acid strength (FCH2CH2OH, CF3CH2OH, (CF3)2CHOH, and (CF3)3COH) was investigated experimentally by the variable temperature spectroscopic methods (IR, NMR) and stopped-flow technique (UV-Vis). The structures of the hydrogen-bonded and proton transfer products were studied by DFT calculations. In agreement with the calculation results, the IR data suggest that the initial hydrogen bond is established with a hydride site for complex 1 and with the metal site for complex 2. However, no intermediate dihydrogen complex found theoretically was detected experimentally on the way to the final classical tetrahydride product. 相似文献
2.
《液相色谱法及相关技术杂志》2012,35(6):1245-1264
Abstract The molecular weight distribution and its first moments of selected polymers were experimentally determined through GPC-investigations with additional molecular weight detection. In on-line operation discontinuously functioning Ubbelohde-viscometer was used for the determination of degree of polymerization in dependence on elution volume. The relation between the experimentally determined values and relative kinetic parameters were derived for some polymers prepared by radical mechanism. The relative constants which determines the branching structure in polymer can be now calculated. From the investigated polymers the effect of chemical nature of monomer units for the branching formation was determined. 相似文献
3.
Malik Zaheer Ahmed 《Journal of Coordination Chemistry》2018,71(8):1102-1113
The computational analysis of geometrically different copper-trimethoprim complexes, experimentally formed at two different temperatures, was performed using Density Functional Theory (DFT) method. Initial geometries of copper-trimethoprim complexes 1, 2, and 3 were obtained from crystallographic data. These three geometries of complexes 1, 2, and 3 were fully optimized using B3LYP/BLYP hybrid density functional methods along with 6-31G and LANL2DZ basis sets at two temperatures, 298 and 352 K. The results obtained were compared with the experimental data and show that complex 1 is the most stable geometry while complex 3 is unstable/intermediate geometry and can be converted to stable form after the recrystallization process. Moreover, LANL2DZ basis set gives more accurate (with respect to experimental) results as compared to 6-31G. 相似文献
4.
Ricardo O. Silva Ricardo A. W. Neves Filho Rodrigo Azevedo Rajendra M. Srivastava Hugo Gallardo 《Structural chemistry》2010,21(3):485-494
In this article, we describe the complete 1H and 13C NMR signal assignments of four 1,2,4-oxadiazoles possessing light-emitting liquid crystal properties. These results were
obtained by using one- and two-dimensional NMR techniques as well as GIAO (PCM) calculations at B3LYP/6-311++G(d,p) level
for compounds 1 and 2a–d. The computed values are in good agreement with the ones obtained experimentally. In addition, some previously unexplained
thermotropic features of compounds 2a–d could be clarified with the help of the geometry optimization calculations carried out by us. 相似文献
5.
《Analytical letters》2012,45(12):1097-1107
Abstract The pressure pulse effect, which exhibits itself by a step conductance rise on the response curves of thermistors in the stopped-flow microcalorimeter, is shown theoretically and experimentally to be due to the temperature rise of the solution caused by its adiabatic compression. Thermocouples respond similarly to thermistors in the range of 1 to 400 bars. 相似文献
6.
Santarupa Thakurta Ray J. Butcher Antonio Frontera 《Journal of Coordination Chemistry》2017,70(22):3715-3726
An asymmetrical Schiff base ligand, 4-bromo-2-(2-pyridylmethyliminomethyl)phenol (HL), and its copper(II) complex, [Cu(L)SCN] (1), have been synthesized. Complex 1 is experimentally characterized by elemental analysis, FT-IR and UV–vis spectroscopic techniques, and cyclic voltammetry. The structure of the complex has been established by single-crystal X-ray diffraction studies, which reveal a square planar geometry of the central copper(II) ion in 1. The neighboring molecules of the complex connect each other by π–π stacking interactions with centroid-to-centroid ring distance 3.653 Å. The ligand can display two possible tautomeric forms; therefore, 1 can have an alternate molecular structure. DFT calculations have been employed to investigate the structure and relative stabilities of the suggested tautomeric forms of the ligand and its corresponding copper(II) complex. 相似文献
7.
采用全电子相对论密度泛函理论探索多种六聚吡咯大环锕酰基配合物(nAn;n=1~3;An=U,Np and Pu)的电子结构本质、成键规律和化学反应特性。结构优化发现大环配体空穴大小与锕酰离子尺寸相当时,配合物锕酰基采用性对规则的六角双锥结构,而当空穴尺寸相对大时,配合物则采取扭曲结构以降低体系能量。当配体相同时,随着铀、镎、钚变化,An=O伸缩振动频率逐渐变小,这与优化的键长和键级变化规律相一致。QTAIM(quantum theory of atoms in molecule)拓扑分析显示An-N为弱共价单键特征,具有较大离子性成分。依据不同铀源,得到与大环配体的反应自由能均小于146 kJ·mol~(-1),与实验合成配合物的反应能计算数值相当。对含铀配合物电子吸收光谱计算显示,低能(近红外和可见光区)的吸收带具有全部或较大的配体→金属电荷转移性质贡献。 相似文献
8.
《Journal of Coordination Chemistry》2012,65(10):885-893
A new series of square-pyramidal coordination compounds L·Zn(acac)2 (acac = acetylacetonate; L is a variety of substituted phenylthioureas: p-N,N ′-dimethylaminophenylthiourea 1, p-methoxy-phenylthiourea 2, p-nitrophenylthiourea 3, p-acetylphenylthiourea 4) have been synthesized and characterized by 1H NMR and IR spectra and elemental analysis. Most of these compounds exhibit wide transparent ranges in the visible region. Their electronic spectra have been studied experimentally, and theoretically by ZINDO/S calculation. The MOPAC software package has been used to evaluate their first-order molecular hyperpolarizabilities (β). All β values of the four coordination compounds are greater than or equal to those of p-nitroaniline, and are larger than β values of their corresponding substituted phenthylthiourea ligands. 相似文献
9.
《Physics and Chemistry of Liquids》2012,50(4):430-434
The mechanical stability of two immiscible liquid drops of water and mercury resting on a polypropylene solid substrate was attained. It is found that the mechanical stability and the complete encapsulation of mercury drop, by a Millipore water drop, depends severely on the volume of the droplets. The merging of four phases along a single contact line as claimed by Mahadevan et al. [L. Mahadevan, M. Adda-Bedia, and Y. Pomeau, J. Fluid Mech. 451, 411 (2002)] is experimentally shown to be invalid. 相似文献
10.
Yu. K. Grishin I. P. Gloriozov S. M. Gerdov V. A. Roznyatovsky L. L. Frolova A. V. Kuchin Yu. A. Ustynyuk 《Russian Chemical Bulletin》2008,57(8):1689-1696
The selectivity of deuterium distribution between the nonequivalent positions in 3-carene (1), 4-α-acetyl-2-carene (2), and 4-(1-hydroxyethyl)-2-carene (3) has been measured by 2H-{1H} NMR spectroscopy at the natural abundance of deuterium. These “H/D-isotope portraits” were shown to be typical of terpenes
and terpenoids produced in plants via the biosynthetic DXP pathway. The mechanism of acylation of 1 was studied by the density functional theory method (PBE functional, TZ2p basis set). The six-membered ring in compound 1 is planar. However, the endo attack of electrophiles on this ring is more favorable both kinetically and thermodynamically. It was shown both experimentally
and theoretically that the elimination of a hydrogen atom in the second reaction step proceeds stereoselectively at the C(2)
atom from the anti position with respect to the three-membered ring and occurs with pronounced nucleophilic assistance from the carbonyl group.
For Part 2, see Ref. 1.
Published in Russian in Izvestiya Akademii Nauk. Seriya Khimicheskaya, No. 8, pp. 1657–1664, August, 2008. 相似文献
11.
《Physics and Chemistry of Liquids》2012,50(3):285-295
Abstract We suggest that the growth of molecular aggregates is the rate-controlling step in the crystallization of lysozyme from pH buffered aqueous solutions of strong electrolytes. We propose that the aggregation reaction passes through a charged transition state whose rate of formation is accelerated by Debye-Huckel screening and whose charge is stabilized by ion exchange with the solution. Applying the theory of the “primary kinetic salt effect”, we predict that the half-life for decay of the lysozyme concentration in solution in contact with a growing crystal should decrease linearly with the square root of the ionic strength. This prediction is confirmed experimentally in the case of lysozyme crystals precipitating at 4°C from pH buffered aqueous solutions of sodium chloride. 相似文献
12.
《液相色谱法及相关技术杂志》2012,35(5):807-817
Abstract The mathematical relationship between the gel permeation chromatography calibration curves of polystyrene and linear polyethylene has been determined in 1,2,4-trichlorobenzene at 130, 135 and 140°C. The experimentally determined relationship is in good agreement with that predicted from application of the principles of the universal calibration technique and published Mark-Houwink coefficients. Definition of this relationship enables the use of polystyrene as a secondary standard for gel permeation chromatographic determination of linear polyethylene molecular weight determinations. 相似文献
13.
Taibi Ben Hadda Fatim Z. Khardli Mostafa Mimouni Maria Daoudi Abdelali Kerbal Héctor Salgado-Zamora 《Phosphorus, sulfur, and silicon and the related elements》2013,188(6):753-761
AbstractA series of four different armed heterocyclic candidates; 1-(2-methyl-2,3-dihydro-1,3-benzothiazol-2-yl)acetone (2), 1-(3-methyl-4H-1,4-benzothiazin-2-yl)ethanone (3), 2-[(2-aminophenyl)dithio]aniline (4), and 3-hydroxy-3-methyl-4-(3-methyl-2-quinoxalinyl)-2-butanone (5) have been prepared and their microbial activities were evaluated. A correlation of the structure and activities relationships of these compounds with respect to molecular modeling, Lipinski Rule of Five, drug likeness, toxicity profiles, and other physico-chemical properties of drugs are described and verified experimentally. 相似文献
14.
《Analytical letters》2012,45(1):175-179
Abstract A discussion on using the phase shifts of the photoacoustic signal of a monophase sample for resolving its overlapping absorption peaks is presented. It is experimentally shown that the method is simple and useful. And the time delay which includes the nonradiative relaxation time, the thermal-diffusion time and the time of generating the acoustic signal is calculated. This is demonstrated using L-Tryptophan compounds. 相似文献
15.
V. A. Balandin S. V. Pasechnik V. I. Prokopjev O. Ya. Shmelyoff 《Liquid crystals》2013,40(10):1319-1325
Abstract The results of a low frequency ultrasonic study of 4-n-butyloxybenzylidene-4'-n-butylaniline (BBBA) in the vicinity of the smectic A-nematic transition are presented. The frequency and temperature dependence of the parameters describing the anisotropic ultrasound absorption are determined experimentally and compared with the predictions of fluctuation and relaxation theories of the smectic A-nematic transition. It is shown that no single theory could explain all of the experimental data. 相似文献
16.
Yu. A. Borisov N. D. Chkanikov A. F. Kolomiets A. V. Fokin 《Russian Chemical Bulletin》1993,42(11):1797-1799
Quantum chemical AM1 calculations with full geometry optimization are carried out forN-methylaniline (2), tetrahydroquinoline (3), indoline (4) molecules, as well as for the products and reaction intermediates of their C-hydroxyalkylation with hexafluoroacetone (1). Enthalpies of formation, frontier orbital energies, and atomic charge distributions are determined for all systems examined. These values are used to estimate the relative stabilities of adducts formed by donor-acceptor interaction between amino- and carbonyl groups using the Klopman perturbation theory. The complexes of1 with2 and1 with4 are concluded to have the longest and shortest lifetimes, respectively. The results of the theoretical study allow one to explain the experimentally observed increase in the propensity forortho-C-hydroxyalkylation in the series2<3<4. The reduction of the ability of methyl trifluoropyruvate to undergoortho-C-hydroxyalkylation is shown to be a consequence of the greater stabilities of its arylamine complexes.Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 11, pp. 1883–1886, November, 1993. 相似文献
17.
《液相色谱法及相关技术杂志》2012,35(14):2665-2677
Abstract The very important aspect of effect of the magnitude of specific surface area on RM values obtained by using TLC method is presented. In experiments were performed on 4 adsorbents of different specific surface areas 50 – 500 m2/g and with mixed binary mobile phases. It is shown that RM values of chromatographed substances aromatic hydrocarbons are lineary dependente upon the specific surface area of adsorbents for each composition of mobile phase. This relationship can be described by a straight line, with the parameters a and b that can be tabularized. These lines can be used to calculate the RM values of chromatographed substances for any adsorbent if is specific surface area is known. The illustrational comparison of experimentally obtained and theoretically predicted RM values for different chromatographic system are presented. 相似文献
18.
Chun-Hong Jiang Li-Fang Song Cheng-Li Jiao Jian Zhang Li-Xian Sun Fen Xu Huan-Zhi Zhang Qing-Yang Xu Zelimir Gabelica 《Journal of Thermal Analysis and Calorimetry》2011,103(3):1095-1103
Two metal-organic frameworks, Ca(2,6-NDC)(DMF) (1) and Mn3(2,6-NDC)3(DMF)4 (2) (where 2,6-NDC = 2,6-naphthalene dicarboxylate and DMF = N,N′-dimethylformamide) have been solvothermally synthesized under optimized conditions and characterized by X-ray powder diffraction,
elemental analysis, FT-IR spectroscopy, and TG analysis. The thermal decomposition characteristics were investigated under
air atmosphere from 300 to 1,170 K (for 1) and from 300 to 971 K (for 2). The molar heat capacities were measured from 198 to 548 K (for 1) and from 198 to 448 K (for 2) by temperature modulated differential scanning calorimetry (TMDSC) for the first time. The fundamental thermodynamic parameters
such as entropy and enthalpy variations with temperature were calculated based on the experimentally determined molar heat
capacities. 相似文献
19.
Synthesis of Schiff's bases in aqueous medium: a green alternative approach with effective mass yield and high reaction rates 总被引:1,自引:0,他引:1
《Green Chemistry Letters and Reviews》2013,6(3):217-223
Abstract Schiff's bases constitute a class of pharmaceutical and medicinally important molecules. The conventional methods for the synthesis of Schiff's bases require long reaction times and use of organic solvents. We report a novel and eco-friendly condensation reaction method permitting the “green synthesis” of various Schiff's bases by stirring 1,2-diaminobenzene with various aromatic aldehydes in water as solvent. This method is experimentally simple, clean, high yielding, green, and with reduced reaction times. The product is purified by simple filtration followed by washing with water and drying processes. 相似文献
20.
Yi-hong Ding Ze-sheng Li Yu-guo Tao Xu-ri Huang Chia-chung Sun 《Theoretical chemistry accounts》2002,107(5):253-265
The structures and isomerization pathways of various HC2P isomers in both singlet and triplet states are investigated at the B3LYP/6-311G(d,p), QCISD/6-311G(d,p) (for isomers only)
and single-point CCSD(T)/6-311G(d,p)//B3LYP/6-311G(d,p) levels. At the CCSD(T)/6-311G(d,p)//B3LYP/6-311G(d,p) level, the lowest-lying
isomer is a linear HCCP structure
3
1 in the 3∑− state. The second low-lying isomer has a CPC ring with exocyclic CH bonding
1
5 in a singlet state at 10.5 kcal/mol. The following third and fourth low-lying isomers are a singlet bent HCCP structure
1
1 at 20.9 kcal/mol and a bent singlet HPCC structure
1
3 at 35.8 kcal/mol, respectively. Investigation of the HC2P potential-energy surface indicates that in addition to the experimentally known isomer
3
1, the other isomers
1
1,
1
3 and
1
5 also have considerable kinetic stability and may thus be observable. However, the singlet and triplet bent isomers HCPC
1
2 and
3
2 as well as the triplet bent isomer HPCC
3
3 are not only high-lying but are also kinetically unstable, in sharp contrast to the situation of the analogous HCNC and HNCC
species that are both kinetically stable and that have been observed experimentally. Furthermore, the reactivity of various
HC2P isomers towards oxygen atoms is briefly discussed. The results presented here may be useful for future identification of
the completely unknown yet kinetically stable HC2P isomers
1
1,
1
3 and
1
5 either in the laboratory or in interstellar space.
Received: 5 November 2000 / Accepted: 25 November 2001 / Published online: 8 April 2002 相似文献