全文获取类型
收费全文 | 97499篇 |
免费 | 3877篇 |
国内免费 | 2706篇 |
专业分类
化学 | 38357篇 |
晶体学 | 1036篇 |
力学 | 7898篇 |
综合类 | 191篇 |
数学 | 33813篇 |
物理学 | 22787篇 |
出版年
2024年 | 76篇 |
2023年 | 472篇 |
2022年 | 679篇 |
2021年 | 737篇 |
2020年 | 833篇 |
2019年 | 799篇 |
2018年 | 10937篇 |
2017年 | 10733篇 |
2016年 | 6949篇 |
2015年 | 1811篇 |
2014年 | 1406篇 |
2013年 | 1762篇 |
2012年 | 5602篇 |
2011年 | 12266篇 |
2010年 | 6804篇 |
2009年 | 7087篇 |
2008年 | 7804篇 |
2007年 | 9928篇 |
2006年 | 1346篇 |
2005年 | 2290篇 |
2004年 | 2226篇 |
2003年 | 2571篇 |
2002年 | 1567篇 |
2001年 | 674篇 |
2000年 | 703篇 |
1999年 | 624篇 |
1998年 | 551篇 |
1997年 | 516篇 |
1996年 | 506篇 |
1995年 | 410篇 |
1994年 | 376篇 |
1993年 | 338篇 |
1992年 | 251篇 |
1991年 | 260篇 |
1990年 | 226篇 |
1989年 | 170篇 |
1988年 | 144篇 |
1987年 | 146篇 |
1986年 | 117篇 |
1985年 | 90篇 |
1984年 | 85篇 |
1983年 | 61篇 |
1982年 | 66篇 |
1981年 | 56篇 |
1980年 | 60篇 |
1979年 | 45篇 |
1914年 | 45篇 |
1912年 | 40篇 |
1909年 | 41篇 |
1908年 | 40篇 |
排序方式: 共有10000条查询结果,搜索用时 15 毫秒
991.
Jonathan Rosenhead 《The Journal of the Operational Research Society》1978,29(2):105-111
A case study is presented of the application of robustness analysis to the choice of examination subjects to be made by a 14-year-old girl. The analysis is conducted in terms of the desirable future career options which may be preserved by different combinations of subjects, and also of the balance with topics selected for their intrinsic interest. The approach, which employs very limited technical apparatus, is justified on a number of grounds-in particular, the crucial importance of uncertainty, and the need for understanding and acceptance by a "client" very unlike the corporate manager. Some tentative conclusions are reached on the extension of such methods to other cases of decision-makers with little, if any, resources to control except their own lives. 相似文献
992.
Helmut Schneider 《The Journal of the Operational Research Society》1978,29(12):1181-193
This paper deals with a periodic review inventory system. Methods are discussed for determining the re-order point s of an (s, S) order policy, when a certain service level is required. The results differ from those presented for a (Q, s) model which is usually considered in literature and implemented in practice. Methods are discussed for determining the re-order point of an (s, S) policy when demand is normal or gamma distributed. A numerical investigation demonstrates the applicability of the described methods. In particular, it is shown that these methods are superior to a formula that is implemented in many inventory control systems. 相似文献
993.
Ji-Lai Li Cai-Yun Geng Xu-Ri Huang Chia-Chung Sun 《Theoretical chemistry accounts》2007,117(3):417-429
The reaction of atomic radical F with propyne has been studied theoretically using ab initio quantum chemistry methods and
transition state theory. The potential energy surface was calculated at the CCSD(T)/aug-cc-pVDZ (single-point) level using
the UMP2/6-311++G(d,p) optimized structures. Two reaction mechanisms including the addition–isomerization–elimination reaction
mechanism and the directed hydrogen abstraction reaction mechanism are considered. For the hydrogen abstraction reactions,
i.e., the most probable evolution pathway in the title reaction, the HF formation occurs via direct abstraction mechanism
dominantly and the H atom picked up by the atomic radical F should come mostly from the methyl group of normal propyne. On
the other hand, for the addition–isomerization–elimination mechanism, the most feasible pathway should be the atomic radical
F attacking on the C≡C triple bond in propyne (CH3C≡CH) to form a weakly-bound adduct A1 with no barrier, followed by F addition to the C≡C triple bond to form the low-lying
intermediate isomer 5. Subsequently, isomer 5 directly dissociates to P3 H2CCCHF + H via transition state TS5/P3. The other reaction pathways on the doublet PES are less competitive due to thermodynamical or kinetic factors. Furthermore,
based on the analysis of the kinetics of all channels through which the addition and abstraction reaction proceed, we expect
that the competitive power of reaction channels may vary with experimental conditions for the title reaction. The present
work will provide useful information for understanding the processes of atomic radical F reaction with other unsaturated hydrocarbons.
This material is available from author via E-mail. 相似文献
994.
A 4-Amino-2-mercaptopyrimidine self-assembled monolayer (AMP SAMs/Au) modified gold electrode was prepared. The electrochemical
behavior of acetaminophen on the AMP SAMs/Au was studied in Britton-Robinson (BR) buffer solution. Compared to a bare gold
electrode, the modified electrode exhibits a significant enhancement in the oxidation current response for acetaminophen.
The modified electrode was used for the determination of acetaminophen by square wave voltammetry. The oxidation current increased
linearly with the concentration of acetaminophen in the range of 2.0 × 10−6−4.0 × 10−3 M. The modified electrode made it possible to eliminate the interference of dopamine (DA), brucine, epinephrine (EP), and
norepinephrine (NE). The practical analytical utility was illustrated by the determination of acetaminophen in a commercially
available drug.
The text was submitted by the authors in English. 相似文献
995.
A room-temperature ionic liquid (IL), 1-ethyl-3-methyl-imidazolium tetrafluoroborate (1E-3MI-TFB), used for the coating of
a silica capillary enables one to reduce or invert the electroosmotic flow (EOF) in capillary zone electrophoresis. Excellent
separations of amino acids and ary lalkanoic acids were obtained. Such separations could not be obtained in a naked capillary
in the presence of the cationic surfactants cetyltrimethylammonium bromide (CTAB) or polycationic polymer hexadimethrine bromide
(HDB). The results indicate that 1E-3MI-TFB not only modulates the EOF but also acts as a discriminator. Further experiments
indicate that the interaction between hydrogen at C-2 carbon of IL and acid drugs plays an important role in the separation.
The text was submitted by the authors in English. 相似文献
996.
The catalytic effect of chiral Lewis acids on the hetero-Diels-Alder reaction between aldehydes and Danishefsky's diene (1) has been investigated. A variety of combinations of different ligands and Lewis acids have been examined as catalysts for the hetero-Diels-Alder reaction between benzaldehyde and 1, and it has been found that the readily accessible Ti(IV)-H(8)-BINOL (TiHBOL) complex is a very effective catalyst for the reaction, leading to products with very high enantioselectivity (up to 99% ee) and yield (92%). The hetero-Diels-Alder reaction of other aldehydes with 1 under the catalysis of TiHBOL is a general reaction which proceeds well with very high enantioselectivity and isolated yield for various aldehydes at 0 degrees C to room temperature. Based on the experimental results, the proposed mechanism of the hetero-Diels-Alder reaction and the dihedral angle effects of ligands are discussed. 相似文献
997.
Reversed-phase liquid chromatography and argentation chromatography of the minor capsaicinoids 总被引:1,自引:0,他引:1
Thompson RQ Phinney KW Sander LC Welch MJ 《Analytical and bioanalytical chemistry》2005,381(7):1432-1440
An investigation of the liquid chromatography of the minor capsaicinoids in a commercial capsaicinoid mixture is reported. Twelve stationary phases including C8, C18, C30, phenyl, and cation-exchange chemistries were examined in combination with isocratic aqueous methanol and aqueous acetonitrile mobile phases. A phenyl stationary phase and aqueous acetonitrile mobile phase baseline-resolved 7 of 11 capsaicinoids, and selected ion chromatograms (LC–ESI-MS) demonstrated this was the most effective reversed-phase separation. Argentation chromatography with an alkyl or phenyl column and aqueous silver nitrate–methanol mobile phase revealed the presence of the 6-ene-8-methyl and 6-ene-9-methyl homocapsaicin isomers and the absence of 7-ene-9-methyl homocapsaicin. A mixed phenyl–cation-exchange stationary phase (charged with silver ion) enabled unique and useful separations of the capsaicinoids. 相似文献
998.
Intermolecular potential energy surface and spectra of He-HCl with generalization to other rare gas-hydrogen halide complexes 总被引:3,自引:0,他引:3
A two-dimensional (rigid monomer) intermolecular potential energy surface (PES) of the He-HCl complex has been obtained from ab initio calculations utilizing the symmetry-adapted perturbation theory (SAPT) and an spdfg basis set including midbond functions. The bond length in HCl was chosen to be equal to the expectation value in the ground vibrational state of isolated HCl. The rigid-monomer potential should be a very good approximation to the complete (three-dimensional) potential for H-Cl distances corresponding to the lowest vibrational levels of the monomer since the He-HCl interaction energy was found to be only weakly dependent on the HCl bond length in this region, at least as compared to systems such as Ar-HF. The calculated points were fitted using an analytic function with ab initio computed asymptotic coefficients. As expected, the complex is loosely bound, with the dispersion energy providing the majority of the attraction. Our SAPT PES agrees with the semiempirical PES of Willey et al. [J. Chem. Phys. 96, 898 (1992)], in finding that, atypically for rare gas-hydrogen halide complexes including the lighter halide atoms, the global minimum is on the Cl side (with intermonomer separation 3.35 A and depth of 32.8 cm(-1)), rather than on the H side, where there is only a local minimum (3.85 A, 30.8 cm(-1)). The ordering of the minima was confirmed by single-point calculations in larger basis sets and complete basis set extrapolations, and also using higher levels of theory. We show that the opposite findings in the recent calculations of Zhang and Shi [J. Mol. Struct: THEOCHEM 589, 89 (2002)] are due to the lack of midbond functions in their basis set. Despite the closeness in depth of the two linear minima, the existence of a relatively high barrier between them invalidates the assumption of isotropy, a feature of some literature potentials. The trends concerning the locations of minima within the family of rare gas-hydrogen halide complexes are rationalized in terms of the physical components of the intermolecular forces and related to monomer properties. The accuracy of the SAPT PES was tested by performing calculations of rovibrational levels. The transition frequencies obtained were found to be in excellent agreement (to within 0.02 cm(-1)) with the measurements of Lovejoy and Nesbitt [J. Chem. Phys. 93, 5387 (1990)]. The SAPT PES predicts a dissociation energy for the complex of 7.74 cm(-1) which is probably more accurate than the experimental value of 10.1+/-1.2 cm(-1). Our analysis of the ground-state rovibrational wave function shows that the He-HCl configuration is favored over the He-ClH configuration despite the ordering of minima. This is due to the greater volume of the well in the former case. We have also determined positions and widths of three low-lying resonance states through scattering calculations. These predictions are expected to be more accurate than values derived from experiment. 相似文献
999.
1000.
Nano-sized phosphine and pyridine ligands having tetraphenylphenyl-, m-terphenyl-, poly(benzylether) moieties were synthesized. These ligands showed a remarkable effect on homogeneous transition
metal catalyzed reactions. Pd(II) complexes with tetraphenylphenyl substituted pyridine ligands show high catalytic activities
for oxidation of ketones suppressing Pd black formation and maintains the catalytic activity for a long time. Rh(I) complex
catalysts with m-terphenyl substituted phosphine ligands showed remarkable rate acceleration in the hydrosilylation of ketones. In addition,
several phosphinocalixarene ligands were synthesized and their coordination studies with Pd(II), Pt(II), Ru(II), Ir(I), and
Rh(I) metals were documented. Ir(I) and Rh(I) cationic complexes with a 1,3,5-triphosphinocalix[6]arene ligand showed dynamic
behavior with size-selective molecular recognition. 相似文献