全文获取类型
收费全文 | 7680篇 |
免费 | 421篇 |
国内免费 | 204篇 |
专业分类
化学 | 4692篇 |
晶体学 | 80篇 |
力学 | 316篇 |
综合类 | 25篇 |
数学 | 1230篇 |
物理学 | 1962篇 |
出版年
2023年 | 69篇 |
2022年 | 117篇 |
2021年 | 199篇 |
2020年 | 220篇 |
2019年 | 213篇 |
2018年 | 195篇 |
2017年 | 168篇 |
2016年 | 249篇 |
2015年 | 237篇 |
2014年 | 269篇 |
2013年 | 536篇 |
2012年 | 480篇 |
2011年 | 548篇 |
2010年 | 349篇 |
2009年 | 306篇 |
2008年 | 410篇 |
2007年 | 339篇 |
2006年 | 338篇 |
2005年 | 288篇 |
2004年 | 213篇 |
2003年 | 218篇 |
2002年 | 189篇 |
2001年 | 167篇 |
2000年 | 144篇 |
1999年 | 111篇 |
1998年 | 74篇 |
1997年 | 69篇 |
1996年 | 81篇 |
1995年 | 58篇 |
1994年 | 98篇 |
1993年 | 69篇 |
1992年 | 83篇 |
1991年 | 66篇 |
1990年 | 61篇 |
1989年 | 47篇 |
1988年 | 46篇 |
1987年 | 46篇 |
1986年 | 50篇 |
1985年 | 69篇 |
1984年 | 65篇 |
1983年 | 38篇 |
1982年 | 66篇 |
1981年 | 57篇 |
1980年 | 61篇 |
1979年 | 57篇 |
1978年 | 61篇 |
1977年 | 54篇 |
1976年 | 50篇 |
1975年 | 44篇 |
1973年 | 42篇 |
排序方式: 共有8305条查询结果,搜索用时 15 毫秒
81.
Machuca F de León SG Centeno A Fierro JL 《Journal of colloid and interface science》2001,237(2):290-293
The equilibrium parameters for the adsorption of Mo(VI) on gamma-Al(2)O(3) and of Co(II) and Pt(IV) on MoO(3)/gamma-Al(2)O(3) were determined. The adsorption isotherms were performed from aqueous solutions of the corresponding precursors on two different alumina supports. According to the classification given by Giles, L-type-shaped, subgroup 2, adsorption curves were found for the system Mo on gamma-Al(2)O(3), L-type, subgroup 1, for the Pt on MoO(3)/gamma-Al(2)O(3), and S-type for Co on the MoO(3)/gamma-Al(2)O(3) system. Numerical calculations were carried out for all the isotherms to find the equilibrium parameters. These constants are being used to model the development of Pt, Co, and Mo profiles on MoO(3)/gamma-Al(2)O(3) or gamma-Al(2)O(3) extrudates, respectively, which belong to the new generation of noble-metal-MoO(3)/gamma-Al(2)O(3)-supported catalysts to be used in oil-refining processes. Copyright 2001 Academic Press. 相似文献
82.
Pham-Tran NN Bouchoux G Delaere D Nguyen MT 《The journal of physical chemistry. A》2005,109(12):2957-2963
We have investigated the basicity of phosphinine (C5H5P, phosphabenzene) in reevaluating its proton affinity (PA) and gas-phase basicity (GB) and the pK(a) value of its protonated form. As a necessary step, we have first determined its gas-phase proton affinity. Using both mass spectrometric and quantum chemical methods, we have obtained the values PA(C5H5P) = 195.8 +/- 1.0 kcal mol(-1) and GB(298)(C5H5P) = 188.1 +/- 1.0 kcal mol(-1), in good agreement with previous results. We then derived a value of pK(a)(C5H6P+) = -16.1 +/- 1.0 in aqueous solution using three different approaches: the latter markedly differs from the currently available value of -10. The reason for such a discrepancy in the pK(a) of protonated phosphinine in solution is discussed. In the theoretical determination of PAs, evaluation of the basis set superposition error (BSSE) showed that this effect is quite small, being 0.1-0.2 kcal mol(-1) for phosphinine, when a density functional theory (DFT) method in conjunction with a large basis set were used. 相似文献
83.
The cellular mechanism based on P-glycoprotein (PGP) for its drug pump function has become very important in multidrug resistance (MDR) research. A method has been established to characterize PGP on single K562 cell by coupling capillary electrophoresis with laser induced fluorescence detection. A permeable intact cell after the immunoassay binding with fluorescence labeling antibody was injected into the capillary and directly separated without lysis. It was found that once 5-10 optional cells were detected in batch, the PGP amount on this cell line could be outlined and calculated clearly. The PGP amount on K562 MDR cell line is 3.88 times higher than that on K562 sensitive cell line. These two cell lines with immunoassay binding were also analyzed by injection of multi-cells in order to improve the throughput. A resistance factor so called multidrug resistance multiple (MRM) was introduced to evaluate the MDR difference between cell lines. The MRM values of the cell line K562 measured by single cell analysis are well correlated with those by flow cytometry, which also prove the validity of our method in single cell analysis for the possibility of cancer diagnosis, pharmacokinetics and drug screening in future. 相似文献
84.
The association of a C3v-symmetrical calix[6]tris-amine with different concave tris-carboxylic acids of various degrees of flexibility has been explored by 1H NMR spectroscopy. In all cases, self-assembled structures directed by the selective inclusion of a neutral guest molecule were obtained, the more preorganized being stable in protic solvents. With a rigid C3-symmetrical cap, chiral guest recognition in the calixarene cavity resulted. A large tris-acidic partner gave a unique molecular ditopic receptor that is able to simultaneously accommodate two neutral molecules in two distinct hydrophobic cavities with different binding processes. 相似文献
85.
Perfluoromethyl Element Ligands. XXIX. Preparation and Spectroscopic Investigation of M(CO)4L2 Complexes (M ? Cr, Mo, W; L ? Me2PSMe, Me2PSeMe, (CF3)2PSMe, (CF3)2PSMe) The complexes M(CO)4L2 (see Inhaltsübersicht) have been prepared by the reaction of tetracarbonyl norbornadiene metal compounds M(CO)4NBD with L at room temperature or 35°C, respectively. The cis-complexes formed in the first step undergo rearrangement to trans-isomers at higher temperatures. New compounds have been characterized by analytical and spectroscopic (IR, NMR, MS) methods. 相似文献
86.
This review covers our extensive research activities in the area of fluorine containing phospha- and arsaalkenes as well as selenocarbonyls, which differ considerably in their properties and reactivities from their alkyl and aryl counterparts and thus contribute in a gratifying manner to the still growing field of unsaturated element-carbon compounds of 3rd and 4th row main group elements E. Of particular interest is the influence of the fluorine substituents and other small groups (OR, NR2) with either inductive and/or mesomeric effects on the polarity and reactivity of the EC bond. Addition reactions of proton acidic and hydridic polar HX reactants as well as [2+2], [3+2] and [4+2] cycloadditions have been thoroughly studied. The results obtained allow a classification of the EC systems within five different types, A to E, and prove a change from “normal” to “inverse” heteroalkenes in this sequence. The ligand properties of some derivatives have also been investigated in some detail. 相似文献
87.
A 'bottom-up' approach for the expression of results obtained from analytical methods that include analytical steps with recovery inherently different from 100% [mass transfer steps (MTS): extraction, evaporation, clean-up procedures, digestion, etc.] is presented. The estimation of the combination of all MTS uncertainty involves the comparison of the experimental dispersion of replicated analyses of spiked samples with the estimation of the uncertainty obtained for the combination of all uncertainty sources except MTS ones ('incomplete' estimation). The estimation of MTS uncertainty by difference is performed after evaluating the statistical difference between the 'incomplete' estimation and the experimental dispersion (F-test). When the two estimations are statistically equivalent, the MTS uncertainty is considered to be negligible in relation to the other sources budget. The assumption of constancy of MTS performance within the analytical range is tested through single analyses at several concentration levels and is evaluated by the inclusion of the expected values at the intervals resulting from the combination of the MTS uncertainty estimation performed at one concentration level and the 'incomplete' estimation. The developed methodology can also be useful for method optimisation and validation and for the detection of small trends in results. The determination of pesticides in sweet peppers by GC-NPD was used to explore the above concepts. 相似文献
88.
89.
Thierry Le Borgne Pierre Thury Michel Ephritikhine 《Acta Crystallographica. Section C, Structural Chemistry》2002,58(1):m8-m9
The ligand 1,2,3,4‐tetramethyl‐5‐(2‐pyridyl)cyclopentadiene (cp*py) forms a dinuclear complex with UIV, i.e. di‐μ‐oxo‐bis{chloro(diethyl ether‐κO)[(η5,κN)‐1,2,3,4‐tetramethyl‐5‐(2‐pyridyl)cyclopentadienyl]uranium(IV)}, [U2Cl2O2(C14H16N)2(C4H10O)2], in which cp*py acts as a chelating ligand, being bound to the metal atom by the cyclopentadienyl unit and also by the N atom of the pyridyl ring. 相似文献
90.
Syntheses of new sulfinylcinnolines, quinoxalines, quinazolines and phtalazines have been investigated starting from the appropriate halogenobenzodiazine derivatives. The latter were converted in one step to the corresponding sulfanyl benzodiazines which upon oxidation with m-CPBA led to the corresponding sulfoxide derivatives of benzodiazines in moderate to good yields. In parallel to this study, an improved method for the synthesis of 2-methylsulfinylquinoxaline starting from 2-sulfanylquinoxaline is also described and in the quinazoline series a synthetic route has been developed to prepare 2-tert-butyl-5-phenylsulfinylquinazoline with satisfactory yield as well as 2-tert-butyl-5-tert-butylsulfinyl-4(3H)-quinazolinone and 2-tert-butyl-8-tert-butylsulfinyl-4(3H)-quinazolinone. 相似文献