全文获取类型
收费全文 | 10347篇 |
免费 | 1062篇 |
国内免费 | 202篇 |
专业分类
化学 | 8789篇 |
晶体学 | 12篇 |
力学 | 30篇 |
综合类 | 5篇 |
数学 | 27篇 |
物理学 | 2748篇 |
出版年
2023年 | 74篇 |
2022年 | 143篇 |
2021年 | 202篇 |
2020年 | 338篇 |
2019年 | 265篇 |
2018年 | 239篇 |
2017年 | 178篇 |
2016年 | 361篇 |
2015年 | 343篇 |
2014年 | 443篇 |
2013年 | 675篇 |
2012年 | 410篇 |
2011年 | 485篇 |
2010年 | 385篇 |
2009年 | 453篇 |
2008年 | 437篇 |
2007年 | 492篇 |
2006年 | 436篇 |
2005年 | 372篇 |
2004年 | 327篇 |
2003年 | 342篇 |
2002年 | 1213篇 |
2001年 | 199篇 |
2000年 | 151篇 |
1999年 | 164篇 |
1998年 | 160篇 |
1997年 | 94篇 |
1996年 | 103篇 |
1995年 | 116篇 |
1994年 | 56篇 |
1993年 | 54篇 |
1992年 | 42篇 |
1991年 | 41篇 |
1990年 | 29篇 |
1988年 | 24篇 |
1987年 | 24篇 |
1985年 | 92篇 |
1984年 | 117篇 |
1983年 | 106篇 |
1982年 | 149篇 |
1981年 | 113篇 |
1980年 | 97篇 |
1979年 | 100篇 |
1978年 | 106篇 |
1977年 | 144篇 |
1976年 | 118篇 |
1975年 | 129篇 |
1974年 | 165篇 |
1973年 | 133篇 |
1972年 | 82篇 |
排序方式: 共有10000条查询结果,搜索用时 15 毫秒
71.
Radiation-chemical transformations of chloride solutions in the presence of iodide additives were studied by pulse radiolysis.
Radical anion Cl2
⋅− oxidize I− ion, while in the secondary reactions Cl2 reacts with I− to form a mixed trihalide ion ICl2
−. A reaction model that satisfactorily describes the experimental data was proposed.
Published in Russian in Izvestiya Akademii Nauk. Seriya Khimicheskaya, No. 6, pp. 1336–1340, June, 2005. 相似文献
72.
Fabiano Molinos de Andrade Clovis Peppe Werner Uhl 《Journal of organometallic chemistry》2005,690(5):1294-1299
The reaction of bromomethyl-dibromo-indium(III), Br2InCH2Br with dialkylselenides, R1SeR2 (R1 = CH3, R2 = CH2C6H5; R1 = C2H5, R2 = CH2C6H5; R1 = R2 = CH2C6H5) afforded the corresponding dialkylselenonium methylide complexes of indium tribromide, Br3InCH2SeR1R2, which were fully characterized by NMR spectroscopy and single crystal X-ray diffraction studies. 相似文献
73.
Theodor H. G. Hehenkamp 《Mikrochimica acta》1992,107(3-6):273-277
In order to optimize the physical properties of HTSC small single crystals grown from a melt for basic studies of their physical properties the influence of the environment on their impurity content was investigated by EPMA. This requires quantitative analysis of all elements being present in the crystals. The accuracy of results was affected by problems with the choice and quality of standards, by contamination but also by malfunction of microprobe electronics. The HTSC materials were found to react with mills, milling balls, crucibles and the atmosphere. These problems are being discussed and some reactions being studied for Y1Ba2Cu3O6+x (0 < x < 1) HTSC in A12O3 and ZrO2 crucibles. The crystals grown contain reproducible amounts of impurities depending on boundary conditions and exhibit a zone structure in composition particularly for Y and Ba within their range of homogeneity. 相似文献
74.
75.
Matthias Westerhausen Alexander N. Kneifel Peter Mayer Heinrich Nth 《无机化学与普通化学杂志》2004,630(12):2013-2021
Synthesis and Molekular Structures of N‐substituted Diethylgallium‐2‐pyridylmethylamides (2‐Pyridylmethyl)(tert‐butyldimethylsilyl)amine ( 1a ) and (2‐pyridylmethyl)‐di(tert‐butyl)silylamine ( 1b ) form with triethylgallane the corresponding red adducts 2a and 2b via an additional nitrogen‐gallium bond. These oily compounds decompose during distillation. Heating under reflux in toluene leads to the elimination of ethane and the formation of the red oils of [(2‐pyridylmethyl)(tert‐butyldimethylsilyl)amido]diethylgallane ( 3a ) and [(2‐pyridylmethyl)‐di(tert‐butyl)silylamido]diethylgallane ( 3b ). In order to investigate the thermal stability solvent‐free 3a is heated up to 400 °C. The elimination of ethane is observed again and the C‐C coupling product N, N′‐Bis(diethylgallyl)‐1, 2‐dipyridyl‐1, 2‐bis(tert‐butyldimethylsilyl)amido]ethan ( 4 ) is found in the residue. Substitution of the silyl substituents by another 2‐pyridylmethyl group and the reaction of this bis(2‐pyridylmethyl)amine with GaEt3 yield triethylgallane‐diethylgallium‐bis(2‐pyridylmethyl)amide ( 5 ). The metalation product adds immediately another equivalent of triethylgallane regardless of the stoichiometry. The reaction of GaEt3 with 2‐pyridylmethanol gives quantitatively colorless 2‐pyridylmethanolato diethylgallane ( 6 ). 相似文献
76.
ValeryN. Kalinin IgorV. Shishkov SergeyK. Moiseev ElviraE. Shults GenrikhA. Tolstikov NataliaI. Sosnina PavelV. Petrovskii KonstantinA. Lyssenko Helmut Schmidhammer 《Helvetica chimica acta》2006,89(5):861-869
In a search for starting materials for the preparation of 7,8‐fused morphine alkaloid derivatives, 8‐[(1E‐2‐phenylethenyl]codeinone dimethyl ketal ( 4 ) and 8‐[(1E‐2‐phenylethenyl]codeine ( 5 ) were prepared. These dienes were used as substrates in the Diels–Alder reactions. Compound 5 formed the ‘normal’ adduct 12 with N‐phenylmaleimide, while compound 4 behaved in reactions with dienophiles as the ‘masked’ diene 11 , a 8‐[(1E)‐2‐phenylethenyl]‐substituted thebaine, yielding the corresponding 19‐substituted 6,14‐endo‐etheno‐6,7,8,14‐tetrahydrothebaines. Specifically, reaction of 4 with methyl vinyl ketone gave rise to 19‐[(1E)‐phenylethenyl]thevinone ( 14 ) whose structure was elucidated by an X‐ray diffraction analysis. The thebaine derivative 11 was also prepared from 4 . 相似文献
77.
H. Surya Prakash Rao S. Senthilkumar K. Gopu Shaik Rafi 《Chemistry of Heterocyclic Compounds》2007,43(3):292-297
The microwave-mediated reaction of 4-aryl-4-oxobutanoic acids with benzylamines furnished 1-arylmethyl-3-[(E)-1-arylmethylidene]-5-phenyl-2,3-dihydro-1H-pyrrolones.
This result is in contract to the earlier report on this reaction conducted under neat conditions. Structures for the products
were assigned on the basis of spectral data and confirmed by independent synthesis.
__________
Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 3, pp. 368–373, March, 2007. 相似文献
78.
Antonio García Martínez Santiago de la Moya Cerero Beatriz Lora Maroto 《Tetrahedron》2005,61(12):3055-3064
An empiric first approach to the knowledge about the structural factors influencing the catalytic behavior of conformationally flexible δ-amino-alcohol-based ligands, for the enantioselective addition of dialkylzincs to prochiral carbonyl groups, has been applied using the 1-(2-aminoethyl)norbornan-2-ol moiety as the model chiral system, and the asymmetrically catalyzed addition of diethylzinc to benzaldehyde as the test reaction. For this purpose, a selected small library of seven norbornane-based chiral ligands, bearing well-defined structural variations to allow a comparative study, that is, variation of the relative configuration and steric hindrance at the C(2), C(3) and/or C(7) norbornane positions, has been synthesized and probed in the mentioned test reaction. The experimental results obtained have been rationalized empirically using diastereomeric Noyori-like transition states, demonstrating that the conformational flexibility of the δ-amino-alcohol ligands, contrary to the more studied and rigid β-amino-alcohols, plays a crucial role on the catalytic behavior of such ligands (stereochemical sense and degree of the stereodifferentiation in the asymmetric process), which makes such structural factors, important for the improved design of new related chiral catalysts. In this sense, a robust crude empirical model for the prediction of the catalytic behavior of such δ-amino-alcohol-based ligands is proposed. 相似文献
79.
This paper deals with synthesis and assessment of the hydraulicity of C4A3Cr, analog phase C4A3S to , relevant to the phase chemistry and properties of sulfoaluminate cements. C4A3Cr, synthesized at 1250 °C is well crystallized phase, latently hydraulic, with hydration accelerated in the presence of C4A3S, or CS. Calorimetric curves show reciprocal influence of sulfate and chromate phase in hydration of C4A3S-C4A3Cr system. The total heat expressed at hydration is nearly the same for all specimens, but the rate of heat evolution depends
on the ratio of C4A3S/C4A3Cr phases. X-ray diffraction pattern and DTA curves showed that, increasing content of C4A3Cr in hydrating mixture results in a coexistence of two types of ettringite (chromate and sulfate ettringite) hydrogarnet,
gibbsite and monosulfate.
This revised version was published online in July 2006 with corrections to the Cover Date. 相似文献
80.
J. M. Launay 《Theoretical chemistry accounts》1991,79(3-4):183-190
Summary A quantum mechanical calculation of cross sections for the reaction F+H2(v=0,j=0) FH(vj)+H has been performed on the T5A semiempirical potential surface using hyperspherical coordinates. State-to-state integral and differential cross sections converge rapidly with the number of components of the total angular momentum projection onto the axis of least inertia. Thev=3 differential cross section has a forward peak whose magnitude increases with energy whereas thev=2 differential cross section has a backward maximum, in qualitative agreement with cross-beam experiments. Thev=2 andv=3 rotational distributions are in rather good agreement with experiment, but not the vibrational branching ratios. 相似文献