全文获取类型
收费全文 | 35035篇 |
免费 | 1002篇 |
国内免费 | 216篇 |
专业分类
化学 | 23627篇 |
晶体学 | 294篇 |
力学 | 930篇 |
综合类 | 1篇 |
数学 | 5200篇 |
物理学 | 6201篇 |
出版年
2021年 | 395篇 |
2020年 | 390篇 |
2019年 | 456篇 |
2018年 | 401篇 |
2017年 | 348篇 |
2016年 | 734篇 |
2015年 | 611篇 |
2014年 | 805篇 |
2013年 | 1916篇 |
2012年 | 1929篇 |
2011年 | 2323篇 |
2010年 | 1246篇 |
2009年 | 1007篇 |
2008年 | 1970篇 |
2007年 | 1981篇 |
2006年 | 1907篇 |
2005年 | 1875篇 |
2004年 | 1645篇 |
2003年 | 1363篇 |
2002年 | 1341篇 |
2001年 | 584篇 |
2000年 | 471篇 |
1999年 | 373篇 |
1998年 | 352篇 |
1997年 | 391篇 |
1996年 | 487篇 |
1995年 | 375篇 |
1994年 | 357篇 |
1993年 | 344篇 |
1992年 | 332篇 |
1991年 | 285篇 |
1990年 | 275篇 |
1989年 | 274篇 |
1988年 | 294篇 |
1987年 | 261篇 |
1986年 | 250篇 |
1985年 | 409篇 |
1984年 | 453篇 |
1983年 | 337篇 |
1982年 | 443篇 |
1981年 | 417篇 |
1980年 | 347篇 |
1979年 | 337篇 |
1978年 | 362篇 |
1977年 | 340篇 |
1976年 | 287篇 |
1975年 | 280篇 |
1974年 | 263篇 |
1973年 | 248篇 |
1972年 | 151篇 |
排序方式: 共有10000条查询结果,搜索用时 15 毫秒
991.
Nichkova M Park EK Koivunen ME Kamita SG Gee SJ Chuang J Emon JM Hammock BD 《Talanta》2004,63(5):1213-1223
Polychlorinated dibenzo-p-dioxins (PCDDs) and polychlorinated dibenzofurans (PCDFs) are considered highly toxic contaminants and the environmental and biological monitoring of these compounds is of great concern. Immunoassays may be used as screening methods to satisfy the growing demand for rapid and low cost analysis. In this work, we describe the application of an immunoassay that uses 2,3,7-trichloro-8-methyldibenzo-p-dioxin (TMDD) as a surrogate standard for 2,3,7,8-tetrachlorodibenzo-p-dioxin (TCDD) to sediment and human serum samples. Sample extraction and preparation methods were developed with the aim to establish the simplest, cost-effective and efficient removal of the matrix interferences in the enzyme-linked immunosorbent assay (ELISA). The overall method for sediments is based on a hexane extraction; clean up by a multilayered silica gel column and an activated carbon column; an organic solvent exchange with DMSO–Triton X-100 and ELISA measurement. The gas chromatography–high resolution mass spectrometry (GC–HRMS) validation studies (n = 13) revealed that the method is suitable for the toxic equivalents (TEQ) screening of dioxin in sediments with a method detection limit of about 100 pg g−1 dry sediment with a precision of 13–33% R.S.D. The analysis of a large number of samples originating from different sources would be required to establish more precisely the screening level, as well as the number of false positives and negatives of dioxin TEQ by the immunoassay for sediments. The immunoassay method for sediment analysis offers improvement in speed, sample throughput, and cost in comparison to GC–HRMS. Dioxins were determined in serum samples after a simple liquid–liquid extraction and solvent exchange into DMSO–Triton X-100 without further dilution. The current method (approximate method LOQ of 200 pg ml−1 serum) is not sufficiently sensitive for the determination of dioxins in serum to measure acceptable exposure limit. 相似文献
992.
Various approaches to the syntheses of 5-substituted-3-carbomethoxy-2,5-dihydrothiophenes and their product sulfolenes, required as synthetic precursors for tangutorine, are described. An efficient route to 3,5-disubstituted-4,5-dihydrothiophenes and hence 3,5-disubstituted-2-sulfolenes by radical chemistry is also described. 相似文献
993.
Kimberly A. Carter-Fenk Kevin Carter-Fenk Michelle E. Fiamingo Heather C. Allen John M. Herbert 《Chemical science》2021,12(24):8320
Surface-sensitive vibrational spectroscopy is a common tool for measuring molecular organization and intermolecular interactions at interfaces. Peak intensity ratios are typically used to extract molecular information from one-dimensional spectra but vibrational coupling between surfactant molecules can manifest as signal depletion in one-dimensional spectra. Through a combination of experiment and theory, we demonstrate the emergence of vibrational exciton delocalization in infrared reflection–absorption spectra of soluble and insoluble surfactants at the air/water interface. Vibrational coupling causes a significant decrease in peak intensities corresponding to C–F vibrational modes of perfluorooctanoic acid molecules. Vibrational excitons also form between arachidic acid surfactants within a compressed monolayer, manifesting as signal reduction of C–H stretching modes. Ionic composition of the aqueous phase impacts surfactant intermolecular distance, thereby modulating vibrational coupling strength between surfactants. Our results serve as a cautionary tale against employing alkyl and fluoroalkyl vibrational peak intensities as proxies for concentration, although such analysis is ubiquitous in interface science.Coupling between surfactant molecules at the air/water interface bleeds intensity into a diffuse background, such that single-wavelength vibrational intensity is effectively depleted at high surface coverage. 相似文献
994.
Reaction of Cu(ClO(4))(2) x 6H(2)O with a racemic mixture of the novel chiral ligand N-(1,2-bis(2-pyridyl)ethyl)pyridine-2-carboxamide (PEAH) affords only the homochiral dimeric copper(II) complexes [Cu(2)((R)()PEA)(2)](ClO(4))(2) and [Cu(2)((S)()PEA)(2)](ClO(4))(2) in a 1:1 ratio. The phenomenon of molecular self-recognition is also observed when a racemic mixture of the monomeric copper(II) complex [Cu((R(S))()PEA)(Cl)(H(2)O)] is converted into the homochiral dimeric species [Cu(2)((R(S))()PEA)(2)](ClO(4))(2) via reaction with Ag(+) ion. This is the first report of direct conversion of a racemic mixture of a chiral monomeric copper(II) complex to a mixture of the homochiral dimers. 相似文献
995.
Pyrazines and quinoxalines bearing 2-substituents that direct ortho metalation reacted with lithium 2,2,6,6-tetramethylpiperidide to produce 2-substituted-3-lithiopyrazines and quinoxalines. These lithio reagents reacted with N-methoxy-N-methylbenzamide to give good to moderate yields of 3-substituted pyrazinyl or quinoxalinylphenylmethanones. The 3-methylthio substituents of some ketone products were oxidized to methylsulfonyl groups that were susceptible to nucleophilic displacement. 相似文献
996.
A numerical model for calculating the electrostatic interaction between two particles of arbitrary shape and topology is described. A key feature of the model is a generalized discretization program, capable of simulating any desired analytical shape as a set of flat, triangular elements. The relative sizes of the elements are adjusted using a density function to better match the desired shape and the spatial variation of the electrical surface properties on each particle. The distribution of either surface potential or surface charge density is then calculated using a boundary element approach to solve the linearized Poisson-Boltzmann equation. Example interaction energy profiles are calculated for three different types of roughness-bumps, pits, and surface waves. It is found that the interaction energy between rough particles remains different from that between two equivalent smooth spheres at all separations, even for gap widths much larger than either the solution Debye length or the characteristic roughness size. This behavior at large gap widths arises from the nature of the decay of the electric potential away from each particle. In addition, the magnitude of the roughness effect is found to depend greatly on the size and shape of the nonuniformity as well as the electrostatic boundary conditions. For example, for a sphere containing asperities of height equal to 0.2 times the particle radius, the interaction energy can be as much as 50% greater than that between two equivalent spheres under the condition of constant surface potential. At constant surface charge density, the ratio of the interaction energies between rough and smooth spheres was found to either diverge or become zero as contact between the two particles is approached, depending on the nature of the roughness. Changes of this magnitude could clearly have a substantial impact on the stability behavior of a dispersion of such particles. Copyright 2001 Academic Press. 相似文献
997.
John R. Reeher Gerald D. Flesch Harry J. Svec 《Journal of mass spectrometry : JMS》1976,11(2):154-166
A mass spectrometer equipped with a dual ionization chamber ion source has been used to characterize directly the neutral species produced in the dissociative ionization of gases by electron impact. Neutral fragment mass spectra have been obtained for the electron ionization and fragmentation of benzene, toluene, o-xylene, m-xylene, p-xylene, mesitylene and isotopically labeled toluene. The neutral fragment mass spectra correlate well with the structures of the molecules. The abundant species in the neutral fragment mass spectra also correlate reasonably well with the abundant complementary positive ions of the normal mass spectra. Ionization potentials have been determined for the abundant neutral species produced. Where comparisons with values reported elsewhere are possible, the agreement is usually within ±0.2 eV or less. 相似文献
998.
Evert J. Ditzel Xavier L. R. Fontaine Norman N. Greenwood John D. Kennedy Mark Thornton-Pett 《无机化学与普通化学杂志》1992,616(10):79-85
The action of SMe2 on the ten-vertex nido-ruthenaborane [6-(η6-C6Me6)RuB9Hl3] ( 1 ) provides a high-yield route to the unsubstituted isocloso-ruthenaborane [1-(η6-C6Me6)RuB9H9] (2). The benzene analogue [1-(η6-C6Me6)RuB9H9] is prepared similarly. By contrast, reaction of (1) with PhNH2 gives a variety of B-phenylamino isocloso derivatives, including orange crystals of [1-(η6-C6Me6)-2-(PhNH)-isocloso-1-RuB 9 H8] ( 3 ), red-orange [1-(η6-C6Me6)-2,3-(PhNH)2-isocloso-1-RuB9H7] ( 4 ) and dark-red [1-(η6-C6Me6)-5,6,7-(PhNH)3-isocloso-1-RuB9H6] ( 5 ). Detailed 1H and 11B nmr properties of these various compounds are described. The structure of ( 3 ) has been established by a single-crystal X-ray diffraction study of the solvate [1-(η6-C6Me6)-2-(PhNH)-isocloso-1-RuB9H8] · 1/2 CH2Cl2; the crystals were monoclinic, space group C2/c, with a = 1895.1(3), b = 1556.6(3), c = 1716.4(3) pm, β = 104.37(1)° and z = 8. 相似文献
999.
Solvent extraction methods involving toluene, chloroform, 4-methyl-2-pentanone and pentyl acetate were studied for palladium and rhodium chelates. The palladiurn-salicylaldoxime chelate was extracted quantitatively into 4-methyl-2-pentanone at pH 3. The rhodium-diethyldithiocarbamate chelate was completely extracted into 4-methyl-2-pentanone at pH 8. The optimum combustion conditions for each of the organic extracts were then studied. The position of maximum emission intensity in the flame mantle was determined for each chelate and solvent system ; readings were taken at 363.5 mμ for palladium, and 369.2 mμ for rhodium. For palla-dium, when 4-methyl-2-pentanone was used instead of water as solvent, the emission intensity increased 21-fold. For rhodium, this kctone increased the sensitivity 27 times compared with water. A method is suggested for the separation and determination of palladium and rhodium in the same sample. 相似文献
1000.
John P. Chupp 《Journal of heterocyclic chemistry》1971,8(4):565-570
Alkyl (1-cyclohexen-1-yl)carbamoyl chlorides ( 1 ) react with thiocyanate ion to form enecarbamoyl thiocyanates ( 2 ). In pyridine solution 2 readily isomerizes to the isothiocyanate 4 , which however is not isolated, but immediately transformed in good yields to tetrahydro-4-thio-2,4(lH,3H)quinazolinediones ( 3 ). Various transformations of 3 , including conversion to tetra-hydro-2,4(2H,4H)quinazolinedione ( 5 ), dithione ( 6 ), alkylation products ( 8 and 9 ), sodium salts 11 and Raney nickel degradation to 4,4a,5,6,7,8,8a-octahydro-l-methyl-2(1H)quinazolinone ( 7 ), were carried out to investigate their chemistry and substantiate structural assignments. 相似文献