全文获取类型
收费全文 | 5012篇 |
免费 | 381篇 |
国内免费 | 303篇 |
专业分类
化学 | 3625篇 |
晶体学 | 70篇 |
力学 | 202篇 |
综合类 | 15篇 |
数学 | 628篇 |
物理学 | 1156篇 |
出版年
2023年 | 40篇 |
2022年 | 86篇 |
2021年 | 127篇 |
2020年 | 114篇 |
2019年 | 138篇 |
2018年 | 114篇 |
2017年 | 98篇 |
2016年 | 180篇 |
2015年 | 186篇 |
2014年 | 226篇 |
2013年 | 324篇 |
2012年 | 376篇 |
2011年 | 349篇 |
2010年 | 249篇 |
2009年 | 263篇 |
2008年 | 318篇 |
2007年 | 299篇 |
2006年 | 268篇 |
2005年 | 247篇 |
2004年 | 190篇 |
2003年 | 165篇 |
2002年 | 155篇 |
2001年 | 98篇 |
2000年 | 68篇 |
1999年 | 67篇 |
1998年 | 58篇 |
1997年 | 48篇 |
1996年 | 59篇 |
1995年 | 52篇 |
1994年 | 51篇 |
1993年 | 38篇 |
1992年 | 38篇 |
1991年 | 35篇 |
1990年 | 37篇 |
1989年 | 26篇 |
1988年 | 22篇 |
1987年 | 26篇 |
1986年 | 22篇 |
1985年 | 34篇 |
1984年 | 27篇 |
1983年 | 18篇 |
1982年 | 29篇 |
1981年 | 15篇 |
1980年 | 40篇 |
1979年 | 12篇 |
1978年 | 36篇 |
1977年 | 66篇 |
1976年 | 28篇 |
1975年 | 24篇 |
1974年 | 19篇 |
排序方式: 共有5696条查询结果,搜索用时 15 毫秒
41.
Tritium exchange at C-8 of xanthosine, theobromine, 1-, 3- and 7-methylxanthine in water has been studied. The rates of detritiation of these compounds have been determined over a pH range at constant temperature. Several mechanisms of exchange involving various ionic forms of substrate operating at different pH have been suggested. 相似文献
42.
Takashi Kato Ju Kumanotani 《Journal of polymer science. Part A, Polymer chemistry》1969,7(6):1455-1465
Previously, the formation of urushiol quinone from urushiol was demonstrated in the laccase-catalyzed oxidation process of the sap of the Japanese lacquer tree (Rhus vernicifera D.C.) or of lacquer formed from it. This paper presents the results of the investigation on the participation of urushiol quinone in the oxidative polymerization and crosslinking of the sap or the lacquer. The polymeric urushiol was obtained by the fractionation of the mildly oxidized sap (Japanese lacquer), and a specific dimeric urushiol was isolated from it by thin-layer chromatography (TLC). Structural analysis of the dimer illustrated that it has a conjugated triene structure and may be formed by a coupling reaction between urushiol quinone and a triolefinic component of urushiol. Further support for this was given by the spectroscopic study of the reaction between 4-tert-butyl-o-quinone and the triolefinic component of dimethylurushiol, and by the isolation and identification of the coupling product between them. 相似文献
43.
Jerzy Lange Elzbieta Pytlewska Jan Plenkiewicz Tomasz Kulinski Janina Karolak-Wojciechowska Slawomir Rump 《Journal of heterocyclic chemistry》1997,34(2):389-396
Ethoxycarbonylalkylidene derivatives 2 and 6 of the title hydrazones were obtained in the reaction with ethyl pyruvate or ethyl aroylformate and ethyl acetoacetate, respectively, in methanol. Both compounds were mixtures of geometric isomers with high predominance of one of them. Nmr spectroscopy revealed an unexpected magnetic non-equivalence of the CH2 protons in the ester ethyl group of the major isomer of 6 . On heating (?200°) in an inert medium or on refluxing in ethanolic sodium ethoxide 2 cyclized to the corresponding pyridazino[6,1-c]-triazines 4 , whereas 6 formed pyrazolylpyridazines 7 . The structure of the latter was unambigously established by X-ray analysis. Alkylation of 4a with benzyl bromide in the presence of tetrabutylammonium bromide occurred selectively on the pyridazine N atom. 相似文献
44.
Rode MF Roszak S Szymczak JJ Sadlej J Leszczynski J 《The Journal of chemical physics》2004,121(13):6277-6281
The results of the theoretical study of ground state potential energy surfaces for the chlorine-acetonitrile anion and its photodetachment product are presented. The shallow potential surfaces allow for the nondefinitive position of the chlorine within the complex. The dissociation energy of the neutral complex, estimated through the thermodynamic cycle, indicates significant structural changes due to the photodetachment process. The excess negative charge is localized mostly on the chlorine atom, and the electron detachment proceeds as an electron is removed from chlorine. The process leads to drastic changes in the electrostatic interactions within the complex. The first electronic excited state corresponds to the excess electron transfer from chlorine to acetonitrile fragment. This state is a precursor of the observed charge-transfer-to-solvent state. 相似文献
45.
R. Ramanauskas L. Gudavičiūtė A. Kaliničenko R. Juškėnas 《Journal of Solid State Electrochemistry》2005,9(12):900-908
The influence of pulse plating parameters on the surface morphology, grain size, lattice imperfection and corrosion properties
of Zn–Ni alloy has been studied. The coatings were electrodeposited in an alkaline cyanide-free solution. AFM was applied
for surface morphology examination, XRD measurements were carried out for phase composition and texture analysis, electron
probe microanalysis was used for alloy chemical composition studies, while electrochemical techniques were applied for corrosion
performance evaluation. The pulse plated Zn–Ni coatings appeared to consist of the γ-Zn21Ni5 phase and the composition of the alloy depended on the plating parameters. The grain size, lattice imperfection and homogeneity
of grain distribution were established to be the main factors determining corrosion behaviour of the coating.
Presented at the 4th Baltic Conference on Electrochemistry, Greifswald, March 13–16, 2005 相似文献
46.
"Click chemistry" 1,3-dipolar cycloaddition between alkynyl 6-carboxyfluorescein (FAM) and azido-labeled single-stranded (ss) DNA was carried out under aqueous conditions to produce FAM-labeled ssDNA in quantitative yield. The FAM-labeled ssDNA was successfully used as a primer to produce DNA sequencing products with single-base resolution in a capillary electrophoresis DNA sequencer with laser-induced fluorescence detection. 相似文献
47.
Lukin O Müller WM Müller U Kaufmann A Schmidt C Leszczynski J Vögtle F 《Chemistry (Weinheim an der Bergstrasse, Germany)》2003,9(15):3507-3517
The readily available in gram quantities tris(allyloxy)knot of the amide-type 5 (knotane) can be completely and partially deprotected with nBu(3)SnH in the presence of a palladium catalyst resulting in hydroxyknotanes 7-9. These, in turn, react with diethylchlorophosphate giving rise to knotanes equipped with between one and three phosphoryl groups. Sulfonylation of bis(allyloxy)monohydroxyknotane 8 with p-toluenesulfonyl chloride and, following removal of one or two allyl groups from the intermediate monosulfonate 13, give rise to sulfonyloxy-allyloxy-hydroxy- and sulfonyloxy-dihydroxy-knotanes 15 and 14, respectively. This provides a convenient method for the preparation of knotanes with any substitution pattern. All new knotanes have been isolated in preparative amounts and as highly pure substances with an exception of allyloxy-dihydroxyknotane 9. This compound could only be obtained as a mixture with the corresponding monohydroxy-derivative 8. The structures of all synthesized compounds were established by means of FAB and MALDI TOF mass spectrometry, (1)H and (31)P NMR spectroscopy. The triphosphorylated knotane 10 exhibits high solubility in alcohols, allowing its complete enantiomeric resolution with a commercially available chiral HPLC column. (1)H,(1)H DQF-COSY correlation spectroscopy along with H/D exchange experiments and ab initio calculations provided the first detailed (1)H NMR signal assignments of knotanes in [D(6)]DMSO solution. The combination of variable temperature (1)H and (31)P NMR spectroscopy and molecular modeling has been applied to study the conformational behavior of the new knotanes in different solvents. It has been shown that in DMSO solution at room temperature knotanes exist in a relatively rigid nonsymmetrical conformation similar to that found in the solid state while faster conformational exchange leading to the average D(3) symmetrical structure was detected in a number of other solvents. 相似文献
48.
The repression of glucose oxidase (GOD) biosynthesis by catabolites during fermentation can be alleviated through membrane dialysis fermentation (MDF). The results show that the volumetric enzyme productivity of MDF was two times higher than that of the control (fermentation without dialysis), and its total enzyme activity was increased by 30–50%. The operation conditions of MDF, such as pore size of the membrane, initiating time for membrane dialysis, and volume of dialysate used, were optimized. The content of amino acids and organic acids in the fermentation broth and the dialysate in the reservoir were assessed by amino acid analyzer and ionic chromatography, respectively. The relationship among the contents of pyruvic acid, gluconic acid, and enzyme activity during fermentation was analyzed quantitatively. Furthermore, the effect of membrane dialysis technology applied to the low-yield strain was found to be more effective than that applied to the high-yield strain. 相似文献
49.
Wieczorek-Ciurowa K. Gamrat K. Shirokov Ju. G. 《Journal of Thermal Analysis and Calorimetry》2003,72(1):323-328
A catalytic action of the mechanochemical products of copper hydroxocarbonate with calcium carbonate was investigated in n-butyl
alcohol oxidation tests. The solid products of high-energy milling were identified using thermogravimetry supplemented by
X-ray diffraction method. It was shown that the mechanical activation induces more effective tested catalyst because it promotes
the alcohol conversion at lower temperatures than that unmilled one.
This revised version was published online in July 2006 with corrections to the Cover Date. 相似文献
50.
We present an analytical expression of the Wigner distribution function (WDF) for the bound eigenstates of the rotating Morse oscillator (RMO). The effect of rotational excitation on the WDF on the quantum phase space has been demonstrated. This effect has been visualized by a series of contour diagrams for given rovibrational quantum states. Rotations of the molecule have been proved to qualitatively and quantitatively change the Wigner function. As a result, the most probable distance between atoms in a rotating molecule changes, and depends on the parity of the vibrational quantum number. © 2005 Wiley Periodicals, Inc. Int J Quantum Chem, 2005 相似文献