全文获取类型
收费全文 | 1707篇 |
免费 | 48篇 |
国内免费 | 5篇 |
专业分类
化学 | 1257篇 |
晶体学 | 9篇 |
力学 | 38篇 |
综合类 | 1篇 |
数学 | 222篇 |
物理学 | 233篇 |
出版年
2023年 | 13篇 |
2022年 | 32篇 |
2021年 | 50篇 |
2020年 | 46篇 |
2019年 | 38篇 |
2018年 | 31篇 |
2017年 | 36篇 |
2016年 | 57篇 |
2015年 | 39篇 |
2014年 | 59篇 |
2013年 | 93篇 |
2012年 | 96篇 |
2011年 | 109篇 |
2010年 | 70篇 |
2009年 | 64篇 |
2008年 | 97篇 |
2007年 | 99篇 |
2006年 | 77篇 |
2005年 | 79篇 |
2004年 | 71篇 |
2003年 | 48篇 |
2002年 | 60篇 |
2001年 | 18篇 |
2000年 | 19篇 |
1999年 | 15篇 |
1998年 | 13篇 |
1997年 | 14篇 |
1996年 | 19篇 |
1995年 | 20篇 |
1994年 | 13篇 |
1993年 | 24篇 |
1992年 | 15篇 |
1991年 | 11篇 |
1990年 | 11篇 |
1989年 | 12篇 |
1988年 | 11篇 |
1987年 | 15篇 |
1986年 | 7篇 |
1984年 | 6篇 |
1983年 | 19篇 |
1982年 | 17篇 |
1981年 | 9篇 |
1980年 | 12篇 |
1979年 | 7篇 |
1978年 | 13篇 |
1977年 | 7篇 |
1976年 | 10篇 |
1975年 | 5篇 |
1974年 | 9篇 |
1967年 | 4篇 |
排序方式: 共有1760条查询结果,搜索用时 15 毫秒
31.
Dillmore WS Yousaf MN Mrksich M 《Langmuir : the ACS journal of surfaces and colloids》2004,20(17):7223-7231
This work describes a chemically well defined method for patterning ligands to self-assembled monolayers (SAMs) of alkanethiolates on gold. This method begins with monolayers presenting a nitroveratryloxycarbonyl (NVOC)-protected hydroquinone which is photochemically irradiated to reveal a hydroquinone group. The resulting hydroquinone is then oxidized to the corresponding benzoquinone, providing a site for the Diels-Alder mediated immobilization of ligands. The rate constant for the photochemical deprotection is 0.032 s(-1) (with an intensity of approximately 100 mW/cm(2) between 355 and 375 nm), corresponding to a half-life of 21 s. The hydroquinone is oxidized to the benzoquinone using either electrochemical or chemical oxidation and then functionalized by reaction with a cyclopentadiene-tagged ligand. Two methods for patterning the immobilization of ligands are described. In the first, the substrate is illuminated through a mask to generate a pattern of hydroquinone groups, which are elaborated with ligands. In the second method, an optical microscope fit with a programmable translational stage is used to write patterns of deprotection which are then again elaborated with ligands. This technique is characterized by the use of well-defined chemical reactions to control the regions and densities of ligand immobilization and will be important for a range of applications that require patterned ligands for biospecific interactions. 相似文献
32.
Nada Majkić-Singh Milan Konjović Marina Stojanov Slavisa Spasić Ivan Berkeš 《Analytica chimica acta》1981,130(2):419-423
Hydrogen peroxide, the product of diamine oxidase-catalyzed putrescine or cadaverine oxidation, formed in proportion to the enzyme activity, is measured spectrophotometrically by using the above sulfonate (ABTS) and peroxidase. Only one reagent solution containing 3 mmol of putrescine or 10 mmol of cadaverine, 4 mmol of ABTS and 3000 U of peroxidase per litre of 0.2 mol l-1 Tris—0.1 mol l-1 HCl buffer pH 7.5 is needed. Absorbance changes are measured at 410 nm over the first 3 min of the reaction. This initial oxidation rate of the chromogen enables diamine oxidase activity up to 230 U l-1 to be determined. 相似文献
33.
Gutman I Vukicević D Graovac A Randić M 《Journal of chemical information and computer sciences》2004,44(2):296-299
An algebraic Kekulé structure of a benzenoid hydrocarbon is obtained from an ordinary Kekulé structure by inscribing into each hexagon the number of pi-electrons which (according to this Kekulé structure) belong to this hexagon. We show that in the case of catafusenes, there is a one-to-one correspondence between ordinary and algebraic Kekulé structures. On the other hand, in the case of perifusenes, one algebraic Kekulé structure may correspond to several ordinary Kekulé structures. 相似文献
34.
35.
Glass capillary columns have been prepared without acidic additive in the stationary phase, from which free organic acids elute as sharp and symmetrical peaks. The required surface in the borosilicate glass capillary was generated by a combination of leaching with aqueous HCl and deposition of colloidal silica particles; it can be coated with stationary phases have a broad range of polarity. Aqueous samples containing free organic acids can also be analyzed in such columns in an isothermal mode. 相似文献
36.
The formation and composition of highly fluorescent zinc phosphates in the presence of traces of uranium were investigated and a direct fluorimetric determination of uranium in aqueous media was developed, based on the formation of finely dispersed and stabilized fluorescent precipitates. The standard deviation for 20 μg of uranium, in 25 ml is 5% ; with the fluorimeter described, 10-2 μg of uranium per ml can be determined with an error of 50%. The method is very selective and can be employed for analysis of uranium in ores; it is less sensitive than conventional fluorimetry of fused alkali fluorides but is much simpler and faster. Interferences can often be eliminated by suitable masking reactions. 相似文献
37.
Milan Trsic Kim Wagstaff William G. Laidlaw 《International journal of quantum chemistry》1982,22(5):903-910
An ab initio version of the Hartree–Fock–Slater method is applied to obtain molecular orbitals and eigenvalues for S5N6. The electronic structure, bonding, stability, and electronic spectrum are discussed. 相似文献
38.
Peter Segl'a Martina Palicov Dusan Miklos Marian Koman Milan Melník Maria Korabik Jerzy Mrozinski Tadeusz Glowiak Markku R. Sundberg Peter Lnnecke 《无机化学与普通化学杂志》2004,630(3):470-478
Synthesis and characterization of seven new complexes [Cu(2‐MeSnic)2(CH3OH)]2 (where 2‐MeSnic is 2‐methylthionicotinate), [Cu(2‐MeSnic)2L2]2 (where L is pyridine — py, ethylnicotinate — Etnic and butylnicotinate — Bunic), [Cu(2‐MeSnic)2L2(H2O)2] (where L is py and nicotinamide — nia) and [Cu(2‐MeSnic)2(N‐Menia)2(H2O)2]·2H2O (where N‐Menia is N‐methylnicotinamide) are reported. The characterization were based on elemental analysis, infrared, electronic and EPR spectra, and magnetic susceptibility measurements over a temperature range of 1.8 — 300 K or 70 — 300 K. Three complexes of different type were studied by X‐ray analysis. The molecule of [Cu(2‐MeSnic)2(CH3OH)]2 has dimeric paddle‐wheel cage structure with a tetragonal pyramidal arrangement around CuII. The dimer results from the fact that carboxyl groups of four 2‐MeSnic anions function as bridging in a syn‐syn arrangement. On the other hand [Cu(2‐MeSnic)2(py)2]2 forms dimers with hexacoordinated CuII atoms in highly distorted coordination octahedra, each with two oxygen atoms of bridging carboxyl groups in an anti‐anti arrangement of two 2‐MeSnic anions, with two oxygen atoms of one asymmetrically chelating 2‐MeSnic anion and with two nitrogen atoms of two pyridine ligands. The temperature independent EPR spectrum for this complex exhibits an axial signal which corresponds to almost isolated S = 1/2 magnetic ions. Magnetic data for the dimer show a weak antiferromagnetic interaction between the two metal ions with J = —0.65 cm—1. The CuII atom in complex [Cu(2‐MeSnic)2(py)2(H2O)2] is hexacoordinated in an elongated centrosymmetrical tetragonal‐bipyramidal arrangement (4 + 2). Based on the molecular structure the electronic, infrared, electron paramagnetic resonance spectra and magnetic properties are discussed and stereochemistry as well as the mode of ligand coordination in new solid complexes under study have been determined. 相似文献
39.
Frantiek Hrabk Vlasta Hynkov Milan Bezdk 《Journal of polymer science. Part A, Polymer chemistry》1969,7(4):1111-1113
Some simple equations for the emulsion polymerization system were derived on the basis of the Smith-Ewart theory. These are used in calculating the molar monomer concentration and rate of polymerization in units of moles per liter per second for the zero-order region with respect to the monomer as well as in calculating the rate constant of the growth reaction. 相似文献
40.
Kyselová Z Kysel'ová Z Krizanová L Soltés L Stefek M 《Journal of chromatography. A》2005,1084(1-2):95-100
Sodium dodecyl sulfate-polyacrylamide gel electrophoresis (SDS-PAGE) profiles of eye lens proteins showed that both progression of diabetic cataract in rats in vivo and precipitation of soluble eye lens proteins stressed by free radicals in vitro were accompanied by significant protein cross-linking. There was a noticeable contribution of disulfide bridges to protein cross-linking in diabetic eye lens in vivo. In contrast, under conditions in vitro, when eye lens proteins were exposed to hydroxyl or peroxyl radicals, we showed that the participation of reducible disulfide linkages in the formation of high molecular mass products was markedly lower. These in vivo--in vitro differences indicate that the generally accepted role of reactive oxygen species in diabetic cataractogenesis may be overestimated in connection with the processes of protein cross-linking. 相似文献