全文获取类型
收费全文 | 992篇 |
免费 | 36篇 |
专业分类
化学 | 824篇 |
晶体学 | 4篇 |
力学 | 20篇 |
数学 | 71篇 |
物理学 | 109篇 |
出版年
2024年 | 3篇 |
2023年 | 10篇 |
2022年 | 64篇 |
2021年 | 53篇 |
2020年 | 36篇 |
2019年 | 61篇 |
2018年 | 44篇 |
2017年 | 37篇 |
2016年 | 41篇 |
2015年 | 43篇 |
2014年 | 30篇 |
2013年 | 65篇 |
2012年 | 64篇 |
2011年 | 67篇 |
2010年 | 52篇 |
2009年 | 36篇 |
2008年 | 59篇 |
2007年 | 40篇 |
2006年 | 41篇 |
2005年 | 34篇 |
2004年 | 16篇 |
2003年 | 29篇 |
2002年 | 15篇 |
2001年 | 13篇 |
2000年 | 9篇 |
1999年 | 5篇 |
1998年 | 4篇 |
1997年 | 4篇 |
1996年 | 3篇 |
1995年 | 4篇 |
1994年 | 4篇 |
1988年 | 2篇 |
1987年 | 2篇 |
1986年 | 2篇 |
1985年 | 2篇 |
1984年 | 2篇 |
1983年 | 3篇 |
1982年 | 2篇 |
1979年 | 1篇 |
1978年 | 4篇 |
1976年 | 1篇 |
1975年 | 4篇 |
1974年 | 1篇 |
1973年 | 3篇 |
1972年 | 3篇 |
1971年 | 1篇 |
1970年 | 1篇 |
1968年 | 1篇 |
1967年 | 1篇 |
1966年 | 2篇 |
排序方式: 共有1028条查询结果,搜索用时 15 毫秒
1.
In this paper experimental study and mathematical modelling of newly designed vibro-impact moling rig are presented. The design is based on electro-mechanical interactions of a conductor with an oscillating magnetic field. The rig consists of a metal bar placed within a solenoid which is connected to an RLC circuit, and an obstacle block positioned nearby. Both the solenoid and the block are attached to a base board. Externally supplied alternating voltage causes the bar to oscillate and hit the block resulting in the forward motion of the base board mimicking a mole penetration through the soil. By varying the excitation voltage and the capacitance in the circuit, a variety of system responses can be obtained.In the paper the rig design and experimental procedure are explained in detail, and the mathematical modelling of the rig is described. Then the obtained coupled electro-mechanical equations of motion are integrated numerically, and a comparison between experimental results and numerical predictions is presented. 相似文献
2.
N. S. Prostakov B. Kh. Sisimbina S. A. Soldatova V. P. Shalimov K. G. Montenegro N. I. Leonova L. A. Murugova 《Chemistry of Heterocyclic Compounds》1982,18(12):1290-1294
Isomeric (with respect to the position of the nitrogen atom) azafluorenes were cyanoethylated. The resulting 9,9-bis(-cyanoethyl) derivatives were converted to the corresponding dibasic acids and their diesters. The latter were subjected to the Dieckmann reaction to obtain spiro compounds with azafluorene and cyclohexene fragments. The analogous spirans with 1,3-dioxalane and 1,3-dioxane rings were obtained from 3-methyl-2-azafluorenone.Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 12, pp. 1668–1672, December, 1982. 相似文献
3.
Three new Ni(BDC)/2,2'-bipy compounds, Ni2(BDC)(HBDC)2(2,2'-bipy)2 (2), Ni3(BDC)3(2,2'-bipy)2 (3), and Ni(BDC)(2,2-bipy)2.2H2O (5), in addition to the previously reported Ni(BDC)(2,2'-bipy).0.75H2BDC (1) and Ni(BDC)(2,2'-bipy)(H2O) (4) [BDC = 1,4-benzenedicarboxylate; 2,2'-bipy = 2,2'-bipyridine], have been synthesized by hydrothermal reactions. A systematic investigation of the effect of the reaction temperature and pH resulted in a series of compounds with different compositions and dimensionality. The diverse product slate illustrates the marked sensitivity of the structural chemistry of polycarboxylate aromatic ligands to synthesis conditions. Compound 1, which has a channel structure containing guest H2BDC molecules, is formed at the lowest pH. The guest H2BDC molecules are connected by hydrogen bonds and form extended chains. At a slightly higher pH, a dimeric molecular compound 2 is formed with a lower number of protonated carboxylate groups per nickel atom and per BDC ligand. Reactions at higher temperature and the same pH lead to the transformation of 1 and 2 into the two-dimensional, layered trinuclear compound 3. As the pH is increased, a one-dimensional polymer 4 is formed with a water molecule coordinated to Ni2+. Bis-monodentate and bischelating BDC ligands alternate along the chain to give a crankshaft rather than a regular zigzag arrangement. A further increase of the pH leads to the one-dimensional chain compound 5, which has two chelating 2,2'-bipy ligands. Crystal data: 2, triclinic, space group P, a = 7.4896(9) angstroms, b = 9.912(1) angstroms, c = 13.508(2) angstroms, alpha = 86.390(2) degrees , beta = 75.825(2) degrees, gamma = 79.612(2) degrees, Z = 2; 3, orthorhombic, space group Pbca, a = 9.626(2) angstroms, b = 17.980(3) angstroms, c = 25.131(5) angstroms, Z = 4; 5, orthorhombic, space group Pbcn, a = 14.266(2) angstroms, b = 10.692(2) angstroms, c = 17.171(2) angstroms, Z = 8. 相似文献
4.
Mangos MM Min KL Viazovkina E Galarneau A Elzagheid MI Parniak MA Damha MJ 《Journal of the American Chemical Society》2003,125(3):654-661
The ability of modified antisense oligonucleotides (AONs) containing acyclic interresidue units to support RNase H-promoted cleavage of complementary RNA is described. Manipulation of the backbone and sugar geometries in these conformationally labile monomers shows great benefits in the enzymatic recognition of the nucleic acid hybrids, while highlighting the importance of local strand conformation on the hydrolytic efficiency of the enzyme more conclusively. Our results demonstrate that the duplexes support remarkably high levels of enzymatic degradation when treated with human RNase HII, making them efficient mimics of the native substrates. Furthermore, interesting linker-dependent modulation of enzymatic activity is observed during in vitro assays, suggesting a potential role for this AON class in an RNase H-dependent pathway of controlling RNA expression. Additionally, the butyl-modified 2'F-ANA AONs described in this work constitute the first examples of a nucleic acid species capable of eliciting high RNase H activity while possessing a highly flexible molecular architecture at predetermined sites along the AON. 相似文献
5.
The behavior of electrochemical cells Pt(sponge)/Na5TbSi412/Na0.65Co2(cell I) and Pt(sponge)/Na5TbSi412/Pt(sponge) (cell II) is studied by, respectively, potentiometric and impedance methods in oxygen and argon atmospheres at 50–300°C. Dependence of potential of cell I on the oxygen concentration is affected by the grain size of platinum sponge and the temperature. At 50–200°C the coarse-grained platinum electrode in contact with solid electrolyte Na5TbSi412 exhibits an oxygen function characterized by the potential-determining reaction 2(g) + 2 + 2 = –
2 + –. An impedance method shows the triple-phase boundary 2, Pt(sponge)/Na5TbSi412 to be reversible with respect to oxygen. The reversibility is realized by minority charge carriers in the solid electrolyte, i.e. by oxygen ions. 相似文献
6.
A.N. Nesmeyanov E.V. Leonova N.S. Kochetkova A.I. Malkova 《Journal of organometallic chemistry》1975,96(2):271-274
A method is described for the preparation of 1,2-diacetylferrocene, in which ferrocene is acetylated with acetyl chloride in the presence of AlCl3 in methylene chloride. Addition of the ferrocene to an excess of the acetylation mixture over a prolonged period was found to be most favourable. The 1,2-diacetylferrocene formed proved to be free of the 1,3-isomer. It was reduced with LiAlH4/AlCl3 to 1,2-diethylferrocene. 相似文献
7.
L.O. Atovmyan O.S. Filipenko V.I. Ponomarev L.S. Leonova E.A. Ukshe 《Solid State Ionics》1984,14(2):137-142
Conductivity measurements of the crystals of the N5RESi4O12 family, where RE=Sm→Lu, have been made. A reversible phase transition R32Rc has been established. The conductive channels have been determined using a high temperature X-ray structural analysis of the Na5RESi4O12 crystals, as well as the ion exchanged Ag phase. 相似文献
8.
Acylation of 4-α-furyl-4-N-benzylaminobut-1-enes with maleic anhydride gave 4-oxo-3-aza-10-oxatricyclo[5.2.1.01,5]dec-8-ene-6-carboxylic acid via amide formation followed by intramolecular Diels-Alder reaction of furan (IMDAF). The cycloaddition proceeded under mild reaction conditions (25 °C) and provided only the exo-adduct in quantitative yield. Treatment of this compound with PPA gave isoindolo[2,1-b][2]benzazepine derivatives via ring opening, aromatization and intramolecular electrophilic alkylation. In order to extend the scope of the reaction sequence, 7-oxo-5,11b,12,13-tetrahydro-7H-isoindolo[2,1-b][2]benzazepine-8-carboxylic acids were further transformed into useful synthetic intermediates. 相似文献
9.
Specific sorption sites for nitrogen, N2, in NaLSX and LiLSX zeolites were investigated using a DRIFT spectroscopic method. Sorption of molecular hydrogen, H2, by NaLSX or LiLSX zeolite at 77 K with DRIFT control of perturbation of sorbed molecules allowed to discriminate two or three different types of specific sorption sites in the respective zeolites. Their H–H stretching frequencies are 4077 and 4081 cm–1 for NaLSX, and 4061, 4084 and 4129 cm–1 for LiLSX. With reference to an independent investigation by methods of both sorption thermodynamics and molecular modeling for N2 sorption on LiLSX, the first two of the corresponding bands were ascribed to H2 sorption on lithium cations, Li+, localized in supercages of the faujasite, FAU, zeolite framework at sites SIII and SIII, while the latter band most likely belongs to H2 sorption on Li+ cations at sites SII, and on hydroxyl groups, OH. Sorption of N2 by Li+ cations at sites SIII and SIII is the strongest, resulting in a decrease of intensity of the corresponding DRIFT bands that stem from subsequent H2 sorption. Nitrogen sorption by Li+ cations at sites SII is much weaker. Sorption of N2 on Na+ cations at sites SIII in NaLSX zeolite is also stronger than by Na+ cations at sites SII. 相似文献
10.
Ekaterina Paliakov 《Tetrahedron letters》2004,45(21):4093-4095
The treatment of 2(or 4)-benzylamino substituted quinolines, 9-benzylaminoacridine, 2-benzylaminopyridine, a 4-benzyloxyquinoline, and an N-benzyloxyamidine with BBr3 yields the corresponding amino or hydroxy substituted compounds. The scope and limitations of this novel reaction are discussed. 相似文献