全文获取类型
收费全文 | 241篇 |
免费 | 6篇 |
国内免费 | 4篇 |
专业分类
化学 | 166篇 |
晶体学 | 2篇 |
力学 | 1篇 |
数学 | 20篇 |
物理学 | 62篇 |
出版年
2022年 | 1篇 |
2021年 | 5篇 |
2020年 | 3篇 |
2019年 | 6篇 |
2018年 | 2篇 |
2017年 | 3篇 |
2016年 | 4篇 |
2015年 | 5篇 |
2014年 | 9篇 |
2013年 | 14篇 |
2012年 | 11篇 |
2011年 | 24篇 |
2010年 | 10篇 |
2009年 | 13篇 |
2008年 | 10篇 |
2007年 | 15篇 |
2006年 | 11篇 |
2005年 | 12篇 |
2004年 | 5篇 |
2003年 | 8篇 |
2002年 | 13篇 |
2001年 | 2篇 |
2000年 | 3篇 |
1997年 | 3篇 |
1996年 | 1篇 |
1992年 | 12篇 |
1991年 | 4篇 |
1990年 | 1篇 |
1989年 | 2篇 |
1988年 | 3篇 |
1987年 | 3篇 |
1986年 | 1篇 |
1985年 | 2篇 |
1984年 | 6篇 |
1983年 | 5篇 |
1982年 | 2篇 |
1981年 | 5篇 |
1980年 | 3篇 |
1977年 | 1篇 |
1976年 | 1篇 |
1974年 | 1篇 |
1973年 | 2篇 |
1972年 | 1篇 |
1967年 | 2篇 |
1965年 | 1篇 |
排序方式: 共有251条查询结果,搜索用时 15 毫秒
1.
2.
Datta S Kumar K 《Spectrochimica acta. Part A, Molecular and biomolecular spectroscopy》2005,62(1-3):473-477
The isotropic component of Raman band for C=O stretching mode of acetophenone in solution was analyzed by estimating the correlation coefficient with reference to Lorentzian lineshape. In the intermediate region of solute/solvent concentration there is a sharp decrease in the correlation coefficient and there appears to be a transition from non-Lorentzian to Lorentzian lineshape. The vibrational relaxation rates have been estimated from the isotropic component of Raman band in different solvents. The rate is shown to be dependent on several macroscopic as well as microscopic properties of the solute-solvent system and intermolecular interactions. The hydrodynamic and dispersion forces appear to play a major role in determining the vibrational relaxation rate and the broadening of the bands. 相似文献
3.
Ashis Kumar Pondit Asim Kumar Das Soma Gangopadhyay Debabrata Banerjea 《Transition Metal Chemistry》1988,13(6):437-439
Summary Acid catalysed dissociation of the copper(II) and nickel(II) complexes (ML2+ of the quadridentate macrocyclic ligand 1, 5, 9, 13-tetraaza-2, 4, 4, 10, 12, 12-hexamethyl-cyclohexadecane-1, 9-diene (L) has been studied spectrophotometrically. Both complexes dissociate quite slowly with the observed pseudo-first order rate constants (kobs) showing acid dependence; for the nickel(II) complex (kobs)=kO+kH[H+], the ko path is however absent with the copper(II) complex. At 60°C (I=0.1M) the kH values areca 10–4 M–1 s–1 for both complexes; k
H
Cu
/k
H
Ni
=ca. 3.9, comparable to some other square-planar complexes of these metal ions. The rate difference is primarily due to H values [copper(II) complex, 29.4±0.5 kJ mol–1; nickel(II) complex, 35.6±1.5 kJ mol–1] with highly negative S values [for copper(II), –215.5 ±6.1 JK–1 mol–1 and for nickel(II), –208.1 ±5.6 JK–1 mol–1] which are much higher than the entropy of solvation of Ni2+ (ca. –160 JK–1 mol–1) and Cu2+ (ca. –99 JK–1 mol–1) ions; significant solvation of the released metal ions and the ligand is indicated. 相似文献
4.
A series of novel monoazo disperse dyes derived from the coupling of diazotized 2-aminobenzo[b]thiophene derivatives with N-arylmaleimides is described. The monoazo disperse dyes applied to nylon fabric and their dyeing performance has been assessed. These dyes have been found to give light yellow to reddish pink color shades with very good depth and levelness on nylon fabric. The dyed fabric shows moderate light fastness and excellent washing, rubbing, perspiration, and sublimation fastness. The percentage dyebath exhaustion on nylon fabric has been found to be good and acceptable. 相似文献
5.
The properties of precipitate-based copper sulphide electrodes are investigated. Solid-phase studies wre done by x-ray photoelectron spectroscopy and solution-phase studies by combined potentiometric and atomic absorptioni spectrometric techniques. The predominant valence state of copper in the copper sulphide samples is shown to be Cu(I), but Cu(II) can also be identified at the surfaces. The oxidation of the membrane surface results in dissolution of copper ion and a decrease in the Cu/S ratio in the solid phase; reduction of the surface causes sulphide dissolution and an increase in the Cu/S ratio. Application of anodic or cathodic curents was used to study the redox behaviour of the copper suphide memebrane. 相似文献
6.
Anna Rabe Julia Büker Dr. Soma Salamon Adarsh Koul Dr. Ulrich Hagemann Dr. Joachim Landers Dr. Klaus Friedel Ortega Dr. Baoxiang Peng Prof. Dr. Martin Muhler Prof. Dr. Heiko Wende Prof. Dr. Wolfgang Schuhmann Prof. Dr. Malte Behrens 《Chemistry (Weinheim an der Bergstrasse, Germany)》2021,27(68):17038-17048
By using the crystalline precursor decomposition approach and direct co-precipitation the composition and mesostructure of cobalt-based spinels can be controlled. A systematic substitution of cobalt with redox-active iron and redox-inactive magnesium and aluminum in a cobalt spinel with anisotropic particle morphology with a preferred 111 surface termination is presented, resulting in a substitution series including Co3O4, MgCo2O4, Co2FeO4, Co2AlO4 and CoFe2O4. The role of redox pairs in the spinels is investigated in chemical water oxidation by using ceric ammonium nitrate (CAN test), electrochemical oxygen evolution reaction (OER) and H2O2 decomposition. Studying the effect of dominant surface termination, isotropic Co3O4 and CoFe2O4 catalysts with more or less spherical particles are compared to their anisotropic analogues. For CAN-test and OER, Co3+ plays the major role for high activity. In H2O2 decomposition, Co2+ reveals itself to be of major importance. Redox active cations in the structure enhance the catalytic activity in all reactions. A benefit of a predominant 111 surface termination depends on the cobalt oxidation state in the as-prepared catalysts and the investigated reaction. 相似文献
7.
Self‐Assembly of DNA–Oligo(p‐phenylene‐ethynylene) Hybrid Amphiphiles into Surface‐Engineered Vesicles with Enhanced Emission 下载免费PDF全文
Shine K. Albert Hari Veera Prasad Thelu Murali Golla Nithiyanandan Krishnan Soma Chaudhary Dr. Reji Varghese 《Angewandte Chemie (International ed. in English)》2014,53(32):8352-8357
Surface‐addressable nanostructures of linearly π‐conjugated molecules play a crucial role in the emerging field of nanoelectronics. Herein, by using DNA as the hydrophilic segment, we demonstrate a solid‐phase “click” chemistry approach for the synthesis of a series of DNA–chromophore hybrid amphiphiles and report their reversible self‐assembly into surface‐engineered vesicles with enhanced emission. DNA‐directed surface addressability of the vesicles was demonstrated through the integration of gold nanoparticles onto the surface of the vesicles by sequence‐specific DNA hybridization. This system could be converted to a supramolecular light‐harvesting antenna by integrating suitable FRET acceptors onto the surface of the nanostructures. The general nature of the synthesis, surface addressability, and biocompatibility of the resulting nanostructures offer great promises for nanoelectronics, energy, and biomedical applications. 相似文献
8.
E.S.R. experiments have been performed on the lowest triplet state of free base porphin (H2P) in a n-octane single crystal at 1·3 K. The results demonstrate that the large majority of guest molecules occur in two orientations. While the molecules in these two orientations are coplanar, they have their N-H H-N axes at right angles. The fine structure results show that the two molecular orientations have zero-field splittings that differ by a few per cent in magnitude. Further, the 65 cm-1 doublet separation which appears in the fluorescence spectrum of H2P is related to the occurrence of these two orientations. Resolved hyperfine structure is obtained for the two in-plane canonical orientations of the magnetic field and also when the field bisects the angle between these two directions. From an analysis of the fine structure and hyperfine structure results it is established that the zero-field splitting pattern is described by the parameters (average over the two orientations) the x axis is taken along the N-H H-N direction and z is the out-of-plane axis. From a computer simulation of the hyperfine structure it further follows that this structure is dominated by a high spin density at the methine carbons; with the coupling constants of the C-H fragment proposed by Hirota et al. the methine density is found to be ρm = 0·163. In order to interpret the experimental results the zero-field splitting parameters and spin density distribution have been calculated for the lower triplet states of H2P on the basis of a set of PPP-SCF-MO-CI calculations. From these calculations it follows that the lowest triplet state must correspond to the excitation eg ←a 2u in Gouterman's four-orbital model. In terms of the D 2h symmetry of the H2P molecule the assignment is 3 B 2u (b 3g ←b 1u ). For this assignment the calculations yield . 相似文献
9.
Baryon inhomogeneities generated during the quark-hadron transition may alter the abundances of light elements if they persist
up to the time of nucleosynthesis. These inhomogeneities survive up to the nucleosynthesis epoch if they are separated by
a distance of at least a few metres. In this work we present a model where large sheets of these inhomogeneities separated
by a distance of a few km are formed by cosmic string wakes during the quark-hadron transition. The effect of these sheets
on nucleosynthesis will also put constraints on the various cosmic string parameters. 相似文献
10.
Soma Bahmany Lucia E.A. de Wit Dennis A. Hesselink Teun van Gelder Nauras M. Shuker Carla Baan Bart C.H. van der Nagel Birgit C.P. Koch Brenda C.M. de Winter 《Biomedical chromatography : BMC》2019,33(1)
After solid organ transplantation, tacrolimus is given to prevent rejection. Therapeutic drug monitoring is used to reach target concentrations of tacrolimus in whole blood. Because the site of action of tacrolimus is the lymphocyte, and tacrolimus binds ~80% to erythrocytes, the intracellular tacrolimus concentration in lymphocytes is possibly more relevant. For this purpose, we aimed to develop, improve and validate a UPLC–MS/MS method to measure tacrolimus concentrations in isolated peripheral blood mononuclear cells (PBMCs). PBMCs were isolated using a Ficoll separation technique, followed by a washing step using red blood cell lysis. A cell suspension of 50 μL containing 1 million PBMCs was used in combination with MagSiMUS‐TDMPREP. To each sample we added 30 μL lysis buffer, 20 μL reconstitution buffer containing 13C2H4‐tacrolimus as internal standard, 40 μL MagSiMUS‐TDMPREP Type I Particle Mix and 175 μL Organic Precipitation Reagent VI for methanol‐based protein precipitation. A 10 μL aliquot of the supernatant was injected into the UPLC–MS/MS system. The method was validated, resulting in high sensitivity and specificity. The method was linear (r2 = 0.997) over the range 5.0–1250 pg/1 × 106 PBMCs. The inaccuracy was <5% and the imprecision was <15%. The washing steps following Ficoll isolation could be performed at either room temperature or on ice, with no effect of the temperature on the results. A method for the analysis of tacrolimus concentrations in PBMCs was developed and successfully validated. Further research will be performed to investigate the correlation between concentrations in PBMCs and clinical outcome. 相似文献