全文获取类型
收费全文 | 11423篇 |
免费 | 400篇 |
国内免费 | 40篇 |
专业分类
化学 | 7133篇 |
晶体学 | 128篇 |
力学 | 378篇 |
综合类 | 4篇 |
数学 | 1953篇 |
物理学 | 2267篇 |
出版年
2023年 | 82篇 |
2022年 | 169篇 |
2021年 | 320篇 |
2020年 | 268篇 |
2019年 | 294篇 |
2018年 | 340篇 |
2017年 | 296篇 |
2016年 | 518篇 |
2015年 | 368篇 |
2014年 | 461篇 |
2013年 | 926篇 |
2012年 | 765篇 |
2011年 | 805篇 |
2010年 | 649篇 |
2009年 | 581篇 |
2008年 | 728篇 |
2007年 | 692篇 |
2006年 | 502篇 |
2005年 | 423篇 |
2004年 | 366篇 |
2003年 | 353篇 |
2002年 | 272篇 |
2001年 | 215篇 |
2000年 | 171篇 |
1999年 | 112篇 |
1998年 | 110篇 |
1997年 | 89篇 |
1996年 | 95篇 |
1995年 | 70篇 |
1994年 | 60篇 |
1993年 | 58篇 |
1992年 | 53篇 |
1991年 | 50篇 |
1990年 | 45篇 |
1989年 | 34篇 |
1988年 | 41篇 |
1987年 | 25篇 |
1986年 | 32篇 |
1985年 | 52篇 |
1984年 | 47篇 |
1983年 | 28篇 |
1982年 | 30篇 |
1981年 | 25篇 |
1980年 | 37篇 |
1979年 | 20篇 |
1978年 | 33篇 |
1976年 | 21篇 |
1975年 | 20篇 |
1974年 | 19篇 |
1973年 | 19篇 |
排序方式: 共有10000条查询结果,搜索用时 62 毫秒
131.
The binary and mixed-ligand complexes formed between ligands (histidine (His), histamine (Him) and glycine (Gly)) and some transition metals (Cu(II), Ni(II) and Zn(II)) were studied potentiometrically in aqueous solution at (25.0 ± 0.1) C and I = 0.10 M KCl in order to determine the protonation constants of the free ligands and stability constants of binary and ternary complexes. The complexation model for each system has been established by the software program BEST from the potentiometric data. The most probable binding mode for each binary species of histidine and for all mixed species was also discussed based upon derived equilibrium constants and stability constants related to the binary species. The ambidentate nature of the histidine ligand, i.e. the ability to coordinate histamine-like, imidazolepropionic acid-like and glycine-like modes was indicated from the results obtained. The stability of ternary complexes was quantitatively compared with their corresponding binary complexes in terms of the parameters, log K, log X and 1110. The concentration distributions of various species formed in solution were also evaluated. In terms of the nature of metal ion, the complex stability follows the trend Cu(II) > Ni(II) > Zn(II), which is in agreement with the Irving-Williams order of metal ions. Thus, the results obtained were compared and evaluated with those in the literature. 相似文献
132.
The main features of transition structures associated with eight-electron electrocyclic reactions have been studied with Density Functional Theory. It is found that conrotatory electrocyclization reaction of (3Z,5Z)-octa-1,3,5,7-tetraenes takes place via M?bius aromatic transition structures of helical conformation. The reaction is completely periselective. In general, transition structures having outward substituents are preferred with respect to the inward transition structures, irrespective of the pi-donor or pi-acceptor character of the substituent. In contrast with four-electron thermal conrotatory electrocyclic reactions, there is no satisfactory correlation between the difference in energy of activation between inward and outward substituents and the Taft resonance sigma(R) parameter. 相似文献
133.
AurelioG. Cskÿ Rocío Medel M.Carmen Murcia Joaquín Plumet 《Helvetica chimica acta》2005,88(6):1387-1396
A new method for the synthesis of spiro‐β‐lactams tethered to tetrahydrofuran rings is described. The procedure is based on Ru‐catalyzed metathesis sequences with oxanorbornene precursors easily obtained by the Staudinger [2+2] cycloaddition of related imines. 相似文献
134.
Immobilization of protein on ferromagnetic Dacron 总被引:1,自引:0,他引:1
A. M. A. Carneiro LeÃo E. A. Oliveira L. B. Carvalho 《Applied biochemistry and biotechnology》1991,31(1):53-58
Ferromagnetic Dacron (polyethyleneterephthalate) is proposed as a matrix to immobilize proteins covalently. Dacron in powder was magnetized by reacting ferrous (Fe+2) and ferric (Fe+3) ions with its hydrazide form at pH 8.3. Ferromagnetic hydrazide Dacron was converted to ferromagnetic azide Dacron and amyloglucosidase (E.C. 3.2.1.3) was covalently bound through the latter group. The catalytic property of the enzyme was preserved (8% of the specific activity estimated for the soluble enzyme) and all the magnetic amyloglucosidase Dacron derivative was recovered by using a magnetic field. No activity was detected in the supernatant. 相似文献
135.
2-Amino-4-[3-methyl-3-(5,6,7,8-tetrahydro-2-naphthyl)cyclobutyl]thiazole was synthesized by reaction of 1-methyl-1-(5,6,7,8-tetrahydro-2-naphthyl)-3-chloroacetylcyclobutane with thiourea in ethanol, and its subsequent transformations afforded new derivatives which were tested in vitro for antibacterial activity against some bacteria using the disk diffusion technique.__________From Zhurnal Organicheskoi Khimii, Vol. 40, No. 12, 2004, pp. 1861–1865.Original English Text Copyright © 2004 by Koparr, Cansz, Ahmedzade.The original article was submitted in English. 相似文献
136.
Removal of methyl violet from aqueous solution by perlite 总被引:2,自引:0,他引:2
The use of perlite for the removal of methyl violet from aqueous solutions at different concentration, pH, and temperature has been investigated. Adsorption equilibrium is reached within 1 h. The capacity of perlite samples for the adsorption of methyl violet was found to increase with increasing pH and temperature and decrease with expansion and increasing acid-activation. The adsorption isotherms are described by means of the Langmuir and Freundlich isotherms. The adsorption isotherm was measured experimentally at different conditions and the experimental data were correlated reasonably well by the adsorption isotherm of Langmuir. The order of heat of adsorption corresponds to a physical reaction. It is concluded that the methyl violet is physically adsorbed onto the perlite. The removal efficiency (P) and dimensionless separation factor (R) have shown that perlite can be used for removal of methyl violet from aqueous solutions, but unexpanded perlite is more effective. 相似文献
137.
Jo?o?Pedro?Ferreira Jo?o?Alexandre?Rodrigues Inês?Teodora?Elias?da?FonsecaEmail author 《Journal of Solid State Electrochemistry》2004,8(4):260-271
The electrochemical behaviour of copper in neutral buffered and non-buffered synthetic seawater and in pure chloride solutions has been studied by cyclic voltammetry, weight loss measurements, open circuit potential and scanning electron microscopy (SEM). Values of the repassivation potentials of Cu in non-buffered and buffered synthetic seawater, at 50 mV s–1, were 0.12 and 0.46 V vs. SCE, respectively. The sharpness, heights and location of the different peaks as well as their charges were shown to be influenced by the composition of the solution, buffering conditions, deoxygenation, polarization potential and time. High chloride concentrations lead to higher oxidation charges. The anodic and the cathodic charges were shown to increase as the chloride concentration increases. The open circuit potential transients of copper in non-deoxygenated, non-buffered synthetic seawater indicate pitting from the beginning of the exposure, while in buffered solutions the pitting appeared only after a quite long exposure period, i.e. after 40 days. Corrosion rates of Cu samples after 3 months of immersion were higher in solutions of pure chloride (0.5 M) than in synthetic seawater. After six months the differences were even more noticeable. SEM images have showed a somewhat higher density of pits on copper samples immersed in the chloride solution (0.5 M), in comparison with those in synthetic seawater. 相似文献
138.
del Río JC Gutiérrez A Martínez AT 《Rapid communications in mass spectrometry : RCM》2004,18(11):1181-1185
A series of non-wood plant fibers, namely kenaf, jute, sisal and abaca, have been analyzed upon pyrolysis-gas chromatography/mass spectrometry (Py-GC/MS) of the whole material. The pyrolysis products mainly arise from the carbohydrate and lignin moieties of the fibers. The lignin-derived phenols belonged to the p-hydroxyphenylpropanoid (H), guaiacylpropanoid (G) and syringylpropanoid (S) structures, and showed a high S/G ratio of between 2.0 and 5.4, the highest corresponding to kenaf. Among the lignin-derived phenols released, small amounts of sinapyl and coniferyl acetates (in both cis- and trans-forms) were identified for the first time upon Py-GC/MS of lignocellulosic materials. Acetylation of the sinapyl and coniferyl alcohols was at the gamma-position of the side chain. The release of these alcohols derived from intact acetylated lignin units upon pyrolysis seems to indicate that the native lignin in the fibers selected for this study is at least partially acetylated. Sinapyl (and coniferyl) acetates have recently been suggested to be authentic lignin precursors involved in the polymerization of lignin along with the normal sinapyl and coniferyl alcohols. Py-GC/MS will offer a convenient and rapid tool for analyzing naturally acetylated lignins, as well as to screen plant materials for the presence of acetylated units in lignin. 相似文献
139.
The first example of an organic reduction with boranes catalyzed by a high valent oxo-complex is reported. The systems catecholborane/MoO2Cl2(H2O)2 (5 mol %) and BH3·THF/MoO2Cl2 (5 mol %) proved to be very efficient for the reduction of sulfoxides to the corresponding sulfides in excellent yields. 相似文献
140.
Abstract— Although the lex gene has been described until recently as being required for lysogenic induction, both our work and the work of others have reported Λ prophage induction in some lexA mutants. However, the characteristics of the process were not defined. We describe UV induction of prophage in a lexA1 mutant at a slightly lower level and requiring 2 times longer than the wild type. As demonstrated in some work, in cells treated with low levels of rifampicin (RIF) no new synthesis of RecA protein is needed for the prophage induction although the onset of lysis is delayed. We suggest that the lysogenic induction in lexA cells is due to the same mechanism that induces prophage in the wild type cells treated with RIF. That is, the induction is due to the cleavage of Λ represser by the basal RecA protease in the DNA-single-strand gap, since RecA protease and monomer represser both have high affinity for this type of DNA. So, LexA protein need not be cleaved for the prophage induction.
No Weigle-reactivation (WR) was detected in the lex mutant even after a long post-irradiation incubation, suggesting that unlike prophage induction, WR requires LexA protein cleavage. 相似文献
No Weigle-reactivation (WR) was detected in the lex mutant even after a long post-irradiation incubation, suggesting that unlike prophage induction, WR requires LexA protein cleavage. 相似文献