全文获取类型
收费全文 | 52451篇 |
免费 | 6682篇 |
国内免费 | 5133篇 |
专业分类
化学 | 11590篇 |
晶体学 | 992篇 |
力学 | 12221篇 |
综合类 | 785篇 |
数学 | 22704篇 |
物理学 | 15974篇 |
出版年
2024年 | 113篇 |
2023年 | 587篇 |
2022年 | 1017篇 |
2021年 | 1158篇 |
2020年 | 1490篇 |
2019年 | 1321篇 |
2018年 | 1379篇 |
2017年 | 1861篇 |
2016年 | 2064篇 |
2015年 | 1596篇 |
2014年 | 2633篇 |
2013年 | 4017篇 |
2012年 | 3036篇 |
2011年 | 3502篇 |
2010年 | 2977篇 |
2009年 | 3323篇 |
2008年 | 3240篇 |
2007年 | 3317篇 |
2006年 | 3023篇 |
2005年 | 2830篇 |
2004年 | 2446篇 |
2003年 | 2229篇 |
2002年 | 2028篇 |
2001年 | 1715篇 |
2000年 | 1632篇 |
1999年 | 1486篇 |
1998年 | 1356篇 |
1997年 | 1120篇 |
1996年 | 916篇 |
1995年 | 756篇 |
1994年 | 696篇 |
1993年 | 522篇 |
1992年 | 561篇 |
1991年 | 439篇 |
1990年 | 343篇 |
1989年 | 256篇 |
1988年 | 205篇 |
1987年 | 168篇 |
1986年 | 121篇 |
1985年 | 164篇 |
1984年 | 134篇 |
1983年 | 83篇 |
1982年 | 80篇 |
1981年 | 68篇 |
1980年 | 39篇 |
1979年 | 55篇 |
1978年 | 37篇 |
1977年 | 47篇 |
1976年 | 17篇 |
1957年 | 12篇 |
排序方式: 共有10000条查询结果,搜索用时 15 毫秒
891.
T. A. Isaev N. S. Mosyagin A. V. Titov A. B. Alekseyev R. J. Buenker 《International journal of quantum chemistry》2002,88(5):687-690
The correlation calculation of the electronic structure of PbH is carried out with the generalized relativistic effective core potential (GRECP) and multireference single‐ and double‐excitation configuration interaction (MRD‐CI) methods. The 22‐electron GRECP for Pb is used and the outer core 5s, 5p, and 5d pseudospinors are frozen using the level‐shift technique, so only five external electrons of PbH are correlated. A new configuration selection scheme with respect to the relativistic multireference states is employed in the framework of the MRD‐CI method. The [6, 4, 3, 2] correlation spin–orbit basis set is optimized in the coupled cluster calculations on the Pb atom using a recently proposed procedure, in which functions in the spin–orbital basis set are generated from calculations of different ionic states of the Pb atom and those functions are considered optimal that provide the stationary point for some energy functional. Spectroscopic constants for the two lowest‐lying electronic states of PbH (2Π1/2, 2Π3/2) are found to be in good agreement with the experimental data. © 2002 Wiley Periodicals, Inc. Int J Quantum Chem, 2002 相似文献
892.
Petra A W Van Den Berg Koert Grever Arie Van Hoek Willem J H Van Berkel Antonie J W G Visser 《Journal of Chemical Sciences》2007,119(2):123-133
Conformational heterogeneity of the FAD cofactor in p-hydroxybenzoate hydroxylase (PHBH) was investigated with time-resolved polarized flavin fluorescence. For binary enzyme/substrate
(analogue) complexes of wild-type PHBH and Tyr222 mutants, crystallographic studies have revealed two distinct flavin conformations;
the ‘in’ conformation with the isoalloxazine ring located in the active site, and the ‘out’ conformation with the isoalloxazine
ring disposed towards the protein surface. Fluorescence-lifetime analysis of these complexes revealed similar lifetime distributions
for the ‘in’ and ‘out’ conformations. The reason for this is twofold. First, the active site of PHBH contains various potential
fluorescence-quenching sites close to the flavin. Fluorescence analysis of uncomplexed PHBH Y222V and Y222A showed that Tyr222
is responsible for picosecond fluorescence quenching free enzyme. In addition, other potential quenching sites, including
a tryptophan and two tyrosines involved in substrate binding, are located nearby. Since the shortest distance between these
quenching sites and the isoalloxazine ring differs only little on average, these aromatic residues are likely to contribute
to fluorescence quenching. Second, the effect of flavin conformation on the fluorescence lifetime distribution is blurred
by binding of the aromatic substrates: saturation with aromatic substrates induces highly efficient fluorescence quenching.
The flavin conformation is therefore only reflected in the small relative contributions of the longer lifetimes. 相似文献
893.
Arrhenius parameters values, in non-isothermal kinetic vaporisation processes for a series of compounds with related structures,
have been calculated. This was made using a method of calculation that allows to find the most probable vaporisation mechanisms.
According to this method DTG curves were compared with some theoretical ones reported in literature, whose shape results to
be only a function of the mechanisms. In this way the choice of the mathematical functions which can be inserted in the kinetic
equations, was influenced by the shape of the DTG plots and other thermal analysis signals thus allowing to choose the most
probable mechanisms.
The kinetic parameters derived from these mechanisms were compared, using statistical analysis, with those obtained from another
method of calculation based on ‘a priori’ vaporisation mechanism chosen for the investigated liquid–gas transition.
The standard deviations of the slope and of the intercept, together with the standard deviation and the square correlation
coefficient (r
2) of the linear regression equations related to the mechanisms of the two methods were calculated. Student t-test, Fisher F-test, confidence intervals (c.i.) and residuals valueswere also given.
Statistical analysis shows that the mechanisms obtained with the former method (diffusive and geometrical models) and the
related Arrhenius parameters result to be more significant (in terms of probability) than the corresponding quantities of
the latter for which a first-order model was chosen.
This revised version was published online in August 2006 with corrections to the Cover Date. 相似文献
894.
The molecular intrinsic characteristic contour (MICC) is defined based on the classical turning point of electron movement in a molecule. Three typical organic molecules, I.e. Methane, methanol and formic acid, were employed as examples for detailed introduction of our method. Investigations on the cross-sections of MICC provide important information about atomic size changing in the process of forming molecules. The electron density distributions on the MICCs of these molecules were calculated and shown for the first time. Results showed that the electron density distribution on the MICC correlates closely with molecular chemical properties, and it provides a new insight into molecular boundary. 相似文献
895.
Anand Pal Singh P. Ramos Cabrer E. Alvarez-Parrilla F. Meijide J. Vázquez Tato 《Journal of inclusion phenomena and macrocyclic chemistry》1999,35(1-2):335-348
In order to study its guest binding and the inclusion phenomena, 6-deoxy-6-(aminoethyl)amino--cyclodextrin (CDN) was synthesised and its binding properties examined. The complexation phenomena of sodium cholate (NaC) and sodium deoxycholate (NaDC) with CDN has been monitored by the NMR method using 13C chemical shift data. The method of continuous variation Job's method has been used to determine the stoichiometry of these supramolecular complexes. The Job's plot confirms the 1 : 1 supramolecular complex for NaC: CDN and the 1 : 2 supramolecular complex for NaDC: CDN. The interaction of NaC and NaDC with CDN has been obtained through two-dimensional Rotational Nuclear Overhauser Effect Spectroscopy (ROESY) NMR. Equilibrium constants were also obtained from 13C chemical shift data (C-1, C-3 & C-4) at different pH values (7, 9, & 11). 相似文献
896.
Summary The Multiple Copy Simultaneous Search methodology has been used to construct functionality maps for an extended region of human thrombin, including the active site. This method allows the determination of energetically favorable positions and orientations for functional groups defined by the user on the three-dimensional surface of a protein. The positions of 10 functional group sites are compared with those of corresponding groups of four thrombin-inhibitor complexes. Many, but not all features, of known thrombin inhibitors are reproduced by the method. The results indicate that certain aspects of the binding modes of these inhibitors are not optimal. In addition, suggestions are made for improving binding by interaction with functional group sites on the thrombin surface that are not used by the thrombin inhibitors.
Abbreviations: MCSS, multiple copy simultaneous search; PPACK, d-phenylalanyl-l-propyl-l-arginine chloromethane; NAPAP, N
-(2-naphthylsulfonylglycyl)-d-para-amidinophenylalanylpiperidine; argatroban, (2R,4R)-4-methyl-1-[N
-(3-methyl-1,2,3,4-tetrahydro-8-quinolinylsulfonyl)-l-arginyl]-2-piperidine carboxylic acid; rms, root mean square. The thrombin residues are numbered according to the chymotrypsin-based numbering by Bode et al. [8]. P1, P2, P3, etc., denote the peptide inhibitor residues on the amino-terminal side of the scissile peptide bond, and S1, S2, S3, etc., the corresponding subsites of thrombin 相似文献
897.
FRICTIONAL DISSIPATION AND NONLINEAR BAROTROPIC INSTABILITY 总被引:1,自引:0,他引:1
陆维松 《中国科学B辑(英文版)》1990,(6)
Based on the nonlinear quasi-geostrophic barotropic vorticity equation with Ekman friction, the criteria for nonlinear barotropic stability of the zonal basic flows are derived using Serrin-Joseph energy approach and through total energy, total enstrophy and their linear combination, separately, in terms of variational principle. Since the new transformation for Euler equation is utilized, the estimation of eigenvalue is more accurate, and the previous results of the author are improved very well. 相似文献
898.
Castellano PM Vignaduzzo SE Maggio RM Kaufman TS 《Analytical and bioanalytical chemistry》2005,382(7):1711-1714
A new, repeatable, and rapid method has been developed for resolution of binary mixtures of acetaminophen and diclofenac with minimum sample pretreatment and without separation of the analytes. The method, based on the PLS1 processing of absorbance data in the UV region, was successfully used for quantification of the drug content of three tablet preparations. The results obtained were in good agreement with HPLC recovery data. The method also enabled determination of drug-dissolution profiles of these commercial tablets, by simultaneous determination of both analytes during the dissolution test. 相似文献
899.
随着杂原子分子筛研究领域的开拓与发展,近年来,对钛硅沸石的研究逐渐增多.Ti-ZSM-11(TS-2)型分子筛是由Reddy,Ratanasarny等[1]首先合成的.钛硅沸石的表征与其它杂原子分子筛相比较为复杂,对杂原子Ti是否进入了骨架还没有一个直接的证据,且争议较多.在红外光谱的研究中,对960cm-1-980cm-1区间的特征吸收的归属也存在着很大的分歧[2-4].钛硅沸石在H2O2对有机化合物的选择氧化领域有极其优良的催化性能[1],因此,对它的开发有广泛的应用前景.本文以动态和静态相结合的水热晶化法合成了Ti-ZSM-11型分子筛.IR光… 相似文献
900.
Moses Salci Evgeny Yarevsky Sergey B. Levin Nils Elander 《International journal of quantum chemistry》2007,107(2):464-468
A three‐dimensional finite element method is applied to the ground states of the symmetric and asymmetric atomic helium trimers 4He3 and 4He2–3He. Three different He–He interaction potentials of hard‐core nature were studied. Two extrapolation procedures based on the convergence properties of the finite element method are investigated. © 2006 Wiley Periodicals, Inc. Int J Quantum Chem, 2007 相似文献