全文获取类型
收费全文 | 27789篇 |
免费 | 4574篇 |
国内免费 | 2861篇 |
专业分类
化学 | 18386篇 |
晶体学 | 267篇 |
力学 | 1920篇 |
综合类 | 217篇 |
数学 | 3413篇 |
物理学 | 11021篇 |
出版年
2024年 | 106篇 |
2023年 | 592篇 |
2022年 | 1067篇 |
2021年 | 1101篇 |
2020年 | 1101篇 |
2019年 | 1041篇 |
2018年 | 972篇 |
2017年 | 919篇 |
2016年 | 1345篇 |
2015年 | 1302篇 |
2014年 | 1538篇 |
2013年 | 2061篇 |
2012年 | 2426篇 |
2011年 | 2448篇 |
2010年 | 1638篇 |
2009年 | 1595篇 |
2008年 | 1740篇 |
2007年 | 1497篇 |
2006年 | 1371篇 |
2005年 | 1162篇 |
2004年 | 864篇 |
2003年 | 693篇 |
2002年 | 619篇 |
2001年 | 518篇 |
2000年 | 517篇 |
1999年 | 630篇 |
1998年 | 528篇 |
1997年 | 522篇 |
1996年 | 488篇 |
1995年 | 464篇 |
1994年 | 385篇 |
1993年 | 345篇 |
1992年 | 285篇 |
1991年 | 251篇 |
1990年 | 238篇 |
1989年 | 186篇 |
1988年 | 145篇 |
1987年 | 124篇 |
1986年 | 93篇 |
1985年 | 94篇 |
1984年 | 63篇 |
1983年 | 50篇 |
1982年 | 52篇 |
1981年 | 22篇 |
1980年 | 12篇 |
1979年 | 4篇 |
1976年 | 1篇 |
1959年 | 1篇 |
1957年 | 7篇 |
1936年 | 1篇 |
排序方式: 共有10000条查询结果,搜索用时 31 毫秒
61.
Studies of the electrochemical behavior of epinephrine at a homocysteine self-assembled electrode 总被引:6,自引:0,他引:6
The self-assembled electrode with the homocysteine monolayer (Hcy/Au) has been characterized by infrared spectroscopy and ac impedance spectroscopy in electrolyte. The Hcy/Au electrode is demonstrated to promote the electrochemical response of epinephrine (E) by cyclic voltammetry. A pair of well-defined redox waves was obtained and the calculated standard rate constant (ks) is 2.1×10−2 cm s−1 at the self-assembled electrode. The reduction peak of E can be used to determine the concentration of E in presence of ascorbic acid (AA) owing to the Hcy/Au also promoting the electrochemical oxidation of AA. 相似文献
62.
The direct reactions of (C5H5)2LnCl with LiN=C(NMe2)2 proceeded at room temperature in THF under pure nitrogen to yield the lanthanocene guanidinate complexes [(C5H5)2Ln(mu-eta1:eta2-N=C(NMe2)2)]2 (Ln = Gd (1), Er (2)). Treatment of phenyl isocyanate with complexes 1 and 2 results in monoinsertion of phenyl isocyanate into the Ln-N(mu-Gua) bond to yield the corresponding insertion products [(C5H5)2Ln(mu-eta1:eta2-OC(N=C(NMe2)2)NPh)]2 (Ln = Gd (3), Er (4)), presenting the first example of unsaturated organic small molecule insertion into the metal-guanidinate ligand bond. Further investigations indicate that N,N'-diisopropylcarbodiimide does not react with complexes 1 and 2 under the same conditions; however, it readily inserts into the lithium-guanidinate ligand bond of LiN=C(NMe2)2. As a synthon of the insertion product Li[(iPrN)2C(N=C(NMe2)2)], its reaction with (C5H5)2LnCl gives the novel organolanthanide complexes containing the guanidinoacetamidinate ligand, (C5H5)2Ln[(iPrN)2C(N=C(NMe2)2)] (Ln = Yb (5), Er (6), Dy (7)). All complexes were characterized by elemental analysis and spectroscopic properties. The structures of complexes 1, 3, 5 and 7 were determined through X-ray single-crystal diffraction analysis. 相似文献
63.
Jun Zhou Jie Yang Li Qi Xuan Shen Dunru Zhu Yan Xu You Song 《Transition Metal Chemistry》2007,32(6):711-715
A novel dinuclear nickel(II) complex, [Ni2(MOBPT)2Cl2(H2O)2]Cl2 · 7H2O (MOBPT = 4-(p-methoxyphenyl) −3,5-bis(pyridine-2-yl)-1,2,4-triazole), has been synthesized and characterized by elemental analysis, IR and single crystal X-ray
diffraction methods. The crystal structure determination shows that the dinuclear Ni2N8 unit is almost planer in which each NiII ion is coordinated by four nitrogen atoms from MOBPT equatorially and a water molecule and a chloride ion axially in a distorted
octahedral geometry. Magnetic measurements reveal a relatively weak antiferromagnetic exchange in the complex. 相似文献
64.
Li Shu-Min Miao Yan-Gang Zhou Zi-Fang Chen Ji Liu Yao-Yang 《Zeitschrift für Physik D Atoms, Molecules and Clusters》1997,39(1):29-34
The first Born approximation is used to study the laser-assisted electron capture by a fast proton from a hydrogen atom. The laser modification on differential cross section peaks sharply in the forward direction. With the impact energy increasing, the change in integral cross section becomes notable. The more intense the laser, the greater the cross section is; the lower the frequency, the greater the cross section. 相似文献
65.
Zhou S 《The journal of physical chemistry. B》2005,109(15):7522-7528
A recently proposed partitioned density functional (DF) approximation (Phys. Rev. E 2003, 68, 061201) and an adjustable parameter-free version of a Lagrangian theorem-based DF approximation (LTDFA: Phys. Lett. A 2003, 319, 279) are combined to propose a DF approximation for nonuniform Lennard-Jones (LJ) fluid. Predictions of the present DF approximation for local LJ solvent density inhomogeneity around a large LJ solute particle or hard core Yukawa particle are in good agreement with existing simulation data. An extensive investigation about the effect of solvent bath temperature, solvent-solute interaction range, solvent-solute interaction magnitude, and solute size on the local solvent density inhomogeneity is carried out with the present DF approximation. It is found that a plateau of solvent accumulation number as a function of solvent bath bulk density is due to a coupling between the solvent-solute interaction and solvent correlation whose mathematical expression is a convolution integral appearing in the density profile equation of the DF theory formalism. The coupling becomes stronger as the increasing of the whole solvent-solute interaction strength, solute size relative to solvent size, and the closeness to the critical density and temperature of the solvent bath. When the attractive solvent-solute interaction becomes large enough and the bulk state moves close enough to the critical temperature of the solvent bath, the maximum solvent accumulation number as a function of solvent bath bulk density appears near the solvent bath critical density; the appearance of this maximum is in contrast with a conclusion drawn by a previous investigation based on an inhomogeneous version of Ornstein-Zernike integral equation carried out only for a smaller parameter space than that in the present paper. Advantage of the DFT approach over the integral equation is discussed. 相似文献
66.
Dakoji S Li D Agnihotri G Zhou HQ Liu HW 《Journal of the American Chemical Society》2001,123(40):9749-9759
The inhibitory properties of (methylenecyclopropyl)formyl-CoA (MCPF-CoA), a metabolite derived from a natural amino acid, (methylenecyclopropyl)glycine, against bovine liver enoyl-CoA hydratase (ECH) were characterized. We have previously demonstrated that MCPF-CoA specifically targets ECHs, which catalyze the reversible hydration of alpha,beta-unsaturated enoyl-CoA substrates to the corresponding beta-hydroxyacyl-CoA products. Here, we synthesized (R)- and (S)-diastereomers of MCPF-CoA to examine the stereoselectivity of this inactivation. Both compounds were shown to be competent inhibitors for bovine liver ECH with nearly identical second-order inactivation rate constants (k(inact)/K(I)) and partition ratios (k(cat)/k(inact)), indicating that the inactivation is nonstereospecific with respect to ring cleavage. The inhibitor, upon incubation with bovine liver ECH, labels a tryptic peptide, ALGGGXEL, near the active site of the protein, where X is the amino acid that is covalently modified. Cloning and sequence analysis of bovine liver ECH gene revealed the identity of the amino acid residue entrapped by MCPF-CoA as Cys-114 (mature sequence numbering). On the basis of gHMQC (gradient heteronuclear multiple quantum coherence) analysis with [3-(13)C]-labeled MCPF-CoA, the ring cleavage is most likely induced by the nucleophilic attack at the terminal carbon of the exomethylene group (C(2)'). We propose a plausible inactivation mechanism that involves relief of ring strain and is consistent with examples found in the literature. In addition, these studies provide important clues for future design of more efficient and selective inhibitors to control and/or regulate fatty acid metabolism. 相似文献
67.
68.
Nan Zhou 《Mikrochimica acta》1991,105(4-6):159-162
Proposed in this paper is an improved method for removal of tin as the matrix element by volatilization in an anhydrous medium as mixed halides of different composition. Any one of them boils at a lower temperature than SnBr4. This ternary system enhances the eventual recombination of temporarily dissociated species to volatile ones, thus making the process quicker and more efficient. The presence of 2 mg of Pb(II) suffices to prevent Bi(III) from loss due to volatilization. 相似文献
69.
Zhixian Zhou Yuzhong Wang Jingchao Tao Yaoting Fan Yangjie Wu 《Journal of inclusion phenomena and macrocyclic chemistry》1998,32(1):69-80
A novel anion-selective electrode has been prepared by usingtetraazaporphyrinogen as the electroactive component and o-nitrophenyloctylether as the plasticizer. The electrode exhibits almost Nernstian responsecharacteristics for Pic-, ReO
4
-
,SCN-, ClO
4
-
and TPB-. The linearresponse ranges towards the above-mentioned anions are 10-6 10-2, 10-5 10-2,10-5 10-2, 10-5 10-1, and 10-5 10-2mol/Land the corresponding slopes are -56.8, -57.1, -56.3, -56.1, and -59.9mV/decade with correlation coefficients of -0.99978, -0.99987, -0.99999,-0.99998, and -0.99998, respectively. The electrode shows an anti-Hofmeisterselectivity sequence: Pic- > SCN- >ReO
4
-
> ClO
4
-
> I- >Br- > BF
4
-
> Sal->NO
3
-
> Cl-. The unusual responsemechanism of the novel anion-selective electrode was investigated byexperimental observations and calculation with the MNDO method. Theelectrode was used as a TPB- and a Pic-sensitiveelectrode, respectively, and applied to the assay of levamisolehydrochloride tablets by potentiometric titration and Gran's methods. Theresults obtained are in excellent agreement with that determined by thestandard pharmacopoeia method based on nonaqueous titration. 相似文献
70.