全文获取类型
收费全文 | 67567篇 |
免费 | 12767篇 |
国内免费 | 3102篇 |
专业分类
化学 | 64369篇 |
晶体学 | 1164篇 |
力学 | 1852篇 |
综合类 | 124篇 |
数学 | 8161篇 |
物理学 | 7766篇 |
出版年
2024年 | 16篇 |
2023年 | 72篇 |
2022年 | 321篇 |
2021年 | 539篇 |
2020年 | 858篇 |
2019年 | 2628篇 |
2018年 | 2483篇 |
2017年 | 3023篇 |
2016年 | 3334篇 |
2015年 | 5583篇 |
2014年 | 5465篇 |
2013年 | 7534篇 |
2012年 | 6003篇 |
2011年 | 5642篇 |
2010年 | 4684篇 |
2009年 | 4492篇 |
2008年 | 4843篇 |
2007年 | 4184篇 |
2006年 | 3816篇 |
2005年 | 3570篇 |
2004年 | 2966篇 |
2003年 | 2696篇 |
2002年 | 3282篇 |
2001年 | 1774篇 |
2000年 | 1580篇 |
1999年 | 777篇 |
1998年 | 167篇 |
1997年 | 179篇 |
1996年 | 181篇 |
1995年 | 131篇 |
1994年 | 94篇 |
1993年 | 96篇 |
1992年 | 94篇 |
1991年 | 76篇 |
1990年 | 30篇 |
1989年 | 35篇 |
1988年 | 31篇 |
1987年 | 27篇 |
1986年 | 20篇 |
1985年 | 22篇 |
1984年 | 10篇 |
1983年 | 12篇 |
1982年 | 22篇 |
1981年 | 7篇 |
1980年 | 6篇 |
1979年 | 8篇 |
1978年 | 7篇 |
1977年 | 3篇 |
1973年 | 8篇 |
1972年 | 2篇 |
排序方式: 共有10000条查询结果,搜索用时 46 毫秒
931.
Grimme S 《Journal of computational chemistry》2003,24(13):1529-1537
Based on a partitioning of the total correlation energy into contributions from parallel‐ and antiparallel‐spin pairs of electrons, a modified third‐order Møller–Plesset (MP) perturbation theory is developed. The method, termed SCS–MP3 (SCS for spin‐component‐scaled) continues previous work on an improved version of MP2 (S. Grimme, J Chem Phys 2003, 118, 9095). A benchmark set of 32 isogyric reaction energies, 11 atomization energies, and 11 stretched geometries is used to assess to performance of the model in comparison to the standard quantum chemical approaches MP2, MP3, and QCISD(T). It is found, that the new method performs significantly better than usual MP2/MP3 and even outperforms the more costly QCISD method. Opposite to the usual MP series, the SCS third‐order correction uniformly improves the results. Dramatic enhancements are especially observed for the more difficult atomization energies, some of the stretched geometries, and reaction and ionization energies involving transition metal compounds where the method seems to be competitive or even superior to the widely used density functional approaches. Further tests performed for other complex systems (biradicals, C20 isomers, transition states) demonstrate that the SCS–MP3 model yields often results of QCISD(T) accuracy. The uniformity with which the new approach improves for very different correlation problems indicates significant robustness, and suggests it as a valuable quantum chemical method of general use. © 2003 Wiley Periodicals, Inc. J Comput Chem 24: 1529–1537, 2003 相似文献
932.
Macrocyclic Schiff‐base ligand, bisacetylaceton‐ethylenediimine (BAE) and its transition metal complexes M(BAE) (M = Cu2+, Ni2+) were synthesized. The complexes having characteristics of aromatic systems and well‐defined one‐dimensional structures, reacted with p‐phthaloyl chloride, to obtain polymer complexes. The complexes were characterized by elemental analysis, inductively coupled plasma (ICP), FT‐IR, and thermal analysis and show good thermal stability. ESR spectra analysis discovered that there are free radicals in the chain of polymers, indicating that a weak magnetic spin‐exchange interaction operates between the metal ions and free radicals. It is found that, as the bridging p‐phthaloyl group is able to propagate the magnetic exchange interaction, the polymer complexes show paramagnetic properties by measurement of temperature dependence of the magnetic property, and obey Curie–Weiss law. Copyright © 2001 John Wiley & Sons, Ltd. 相似文献
933.
Yoshitaka Uenoyama Takahide Fukuyama Keisuke Morimoto Osamu Nobuta Hidefumi Nagai Ilhyong Ryu 《Helvetica chimica acta》2006,89(10):2483-2494
The carbonylation of alkanes 1 under radical‐reaction conditions was examined by using ethynyl triflone A as the unimolecular chain‐transfer (UMCT) reagent. Good to moderate yields of ethynyl ketones 2 were prepared by means of this three‐component coupling reaction. Higher CO pressures as well as lower concentrations of triflone A improved the efficiency of the reaction over the direct addition, the latter leading to alkylated ethynes 3 . In contrast to the reaction with A , the reaction of cyclohexane ( 1a ) with allyl triflone B (= ethyl 2‐methylene‐3‐[(trifluoromethyl)sulfonyl]propanoate) in the presence of CO gave a mixture of carbonylation products, including 8a formed from two molecules each of cyclohexane, CO, and allyl triflone B . 相似文献
934.
The stabilization modification of the halogen end groups of polystyrene prepared by atom transfer radical polymerization (ATRP) has been attempted. The reaction mechanism adopted is radical chain transfer reaction, and iso-propylbenzene is employed as not only the chain transfer agent but also the solvent. Moreover, Cu0 is used as the acceptor of the transformed halogen atom in some experiments. As evidenced by 1H NMR analysis of the modified products, the halogen end group can really be converted into the much more stable carbon-hydrogen structure. When Cu0 is not used, the conversion of the halogen end groups rises rapidly during the early stage and the increase rate slows down after about 8 h reaction. In view of the influence of reaction temperature on the modification, the conversion increases almost exponentially with temperature in the range of 80-100 °C, and the increase rate slows down at higher temperature. 1H NMR and SEC analyses prove that the modification reaction does not destroy the polymer backbone and the molecular weights remain almost the same as those of the unmodified samples. When Cu0 is introduced, the modification reaction proceeds much rapidly, the conversion of the halogen end groups rises almost linearly at the early stage and the nearly complete (>95%) dehalogenation of the polymeric chains is observed after only 12 h reaction. However, the molecular weights rise and the polydispersities become wider after the modification, which implies that the modification is accompanied with the couple termination of the polystyrene radicals besides chain transfer reaction. Furthermore, the couple termination can be restrained at some lower catalyst concentration. Indeed, the modified polymers show improved thermal stability, the initial weight loss temperatures is increased from 196 °C to 378 °C for the linear polystyrene and from 203 °C to 261 °C for the hyperbranched polystyrene. 相似文献
935.
《Electroanalysis》2003,15(19):1567-1570
Application of thin colloidal Au multilayers on glass substrates as optically transparent electrodes is reported herein. Evaluation of the electrode by scanning electron microscopy and as an optically transparent thin layer electrode (OTTLE) illustrate its use for spectroelectrochemical applications. A spectroelectrochemical Nernst plot acquired for the oxidation of o‐tolidine yielded a value of E°=0.605 V (vs. Ag/AgCl) and n=1.88. Both of these values are in excellent agreement with previously published values obtained using a traditional Au minigrid OTTLE. The colloidal Au multilayer electrode is expected to offer many advantages over the minigrid OTTLE in specific applications. These advantages include direct control over microscopic surface topography, large electrochemical surface area, applicability to many different electrode geometries, and increased microscopic surface roughness for SERS and SPR applications. 相似文献
936.
Qing‐Xiang Liu Feng‐Bo Xu Qing‐Shan Li Xian‐Shun Zeng Xue‐Bing Leng Zheng‐Zhi Zhang 《中国化学》2002,20(9):878-883
Dinuclear silver (I) six‐membered ring complex [Ag2 (bta)2 ‐(hmbta)2] (ClO4)2 (3) has been synthesized by the reaction of benzotriazole (bta) (1) and 1‐hydroxymethyl benzotriazole (hmbta) (2) with Ag (CH3CN)4ClO4. The structures of compound 2 and Complex 3 have been studied by single crystal X‐ray diffraction analysis. The change of luminescent intensity of 1, 2 and 3 was reported. Compound 2 crystallizes in the monoclinic system with space group P2 (1)/c, a = 0.7655 (10) nm, b = 1.0126 (14) nm, c =0.9502 (13) nm, β = 95.07 (2)°, V = 0.7337 (17) nm3 and Z = 4. Complex 3 crystallizes in the triclinic system with space group P1, a = 0.73611 (18) nm, b = 0.9152 (2) nm, c = 1.2277 (3) nm, β = 87.170 (5)°, V = 0.8221 (3) nm3 and Z = 1. The main structural feature of complex 3 is a symmetric dinuclear six‐membered ring formed by two silver (I) atoms and four N‐atoms from two benzotriazoles. The second structural feature of complex 3 is the τ‐τ stacking interaction between two adjacent molecular planes, which forms the two‐dimentional layer structure. Besides, compared with 2, the luminescent intensity of complex 3 shows a remarkable enhancement. 相似文献
937.
The intergrowth of 1,10-decanedicarboxylic acid and urea give infinite hydrogen-bonded chains of the guest included in the hexagonal urea host. A deuterium high-resolution solid-state NMR study of the selectively deuterated intergrowth compound 1,10-decanedicarboxylic acid/hydrogenated urea at variable temperature in the range 90 < or = T < or = 300 K was performed on a single crystal. The analysis of the second moment as a function of temperature is shown to be compatible with the known phase transition occurring near T(c) = 203 K. Moreover, the spectra indicate that the orientational disorder is strong, and is compared to an axial uniform disorder. For this purpose, the general equation for the second moment of a system with uniform two-dimensional axial orientational disorder is given, and a method to take into account the non-uniform excitation of the pulse sequence is proposed. 相似文献
938.
Enkhtsetseg Dashjav Guido Kreiner Walter Schnelle Frank R. Wagner Rüdiger Kniep 《无机化学与普通化学杂志》2004,630(5):689-696
Carbometalates: Complex Anions equation/tex2gif-stack-4.gif [MoC4/26—] in the Crystal Structure of Pr equation/tex2gif-stack-5.gif [MoIIC2] Criteria for the existence of carbometalates are established and discussed in a broader context. The concept is then applied to the novel compound Pr2[MoC2], which is characterized by chemical analyses, X‐ray diffraction and metallography. The crystal structure (tetragonal, P42/mnm, Z = 4, a = 581.29(8) pm, c = 1032.53(14) pm) consists of layered polyanions equation/tex2gif-stack-6.gif[MoC4/26—] of distorted vertex and edge sharing MoC4 tetrahedra. Praseodymium is also in a distorted tetrahedral coordination by carbon. The physical properties show “bad metal” behaviour and localized magnetic 4f‐moments in agreement with the existence of Pr3+‐species. A detailed bonding analysis using both the electron localization function ELF and the COHP method justifies the interpretation of the title compound as a carbomolybdate(II). 相似文献
939.
Quantitative analysis of docetaxel in human plasma using liquid chromatography coupled with tandem mass spectrometry 总被引:2,自引:0,他引:2
Kuppens IE van Maanen MJ Rosing H Schellens JH Beijnen JH 《Biomedical chromatography : BMC》2005,19(5):355-361
An assay for the quantitative determination of docetaxel in human plasma is described. Docetaxel was extracted from the matrix using liquid-liquid extraction with ter-butylmethylether, followed by high-performance liquid chromatographic analysis using an alkaline eluent. Paclitaxel was used as internal standard. Positive ionization electrospray tandem mass spectrometry was performed for selective and sensitive detection. The method was validated according to the FDA guidelines on bioanalytical method validation. The validated range for docetaxel was from 0.25--1000 ng/mL using 200 microL plasma aliquots. The method requires only a limited volume (200 microL) of human plasma and the method can be applied in studies requiring a low lower limit of quantitation of 0.25 ng/mL. The assay was applied successfully in several clinical and pharmacological studies with docetaxel. 相似文献
940.
A number of aldehydes and ketones were prepared by oxidation of alcohol by N,N‐dichloro‐4‐methylbenzenesulfonamide under mild and neutral conditions in good to high yield in dichloromethane at room temperature. 相似文献