全文获取类型
收费全文 | 152110篇 |
免费 | 1585篇 |
国内免费 | 440篇 |
专业分类
化学 | 83756篇 |
晶体学 | 2428篇 |
力学 | 6200篇 |
综合类 | 4篇 |
数学 | 14318篇 |
物理学 | 47429篇 |
出版年
2021年 | 1069篇 |
2020年 | 1239篇 |
2019年 | 1312篇 |
2018年 | 1680篇 |
2017年 | 1738篇 |
2016年 | 2635篇 |
2015年 | 1662篇 |
2014年 | 2457篇 |
2013年 | 6308篇 |
2012年 | 5096篇 |
2011年 | 6294篇 |
2010年 | 4341篇 |
2009年 | 4344篇 |
2008年 | 6011篇 |
2007年 | 5820篇 |
2006年 | 5659篇 |
2005年 | 5227篇 |
2004年 | 4709篇 |
2003年 | 4319篇 |
2002年 | 4206篇 |
2001年 | 5610篇 |
2000年 | 4067篇 |
1999年 | 3140篇 |
1998年 | 2163篇 |
1997年 | 2271篇 |
1996年 | 2161篇 |
1995年 | 1977篇 |
1994年 | 1986篇 |
1993年 | 1803篇 |
1992年 | 2277篇 |
1991年 | 2366篇 |
1990年 | 2184篇 |
1989年 | 2138篇 |
1988年 | 2119篇 |
1987年 | 2117篇 |
1986年 | 1942篇 |
1985年 | 2436篇 |
1984年 | 2446篇 |
1983年 | 1953篇 |
1982年 | 1984篇 |
1981年 | 1815篇 |
1980年 | 1802篇 |
1979年 | 2094篇 |
1978年 | 2157篇 |
1977年 | 2098篇 |
1976年 | 2026篇 |
1975年 | 1906篇 |
1974年 | 1891篇 |
1973年 | 1912篇 |
1972年 | 1257篇 |
排序方式: 共有10000条查询结果,搜索用时 15 毫秒
971.
T. S. Martins J. R. Matos G. Vicentini P. C. Isolani 《Journal of Thermal Analysis and Calorimetry》2005,82(1):77-82
Summary Rare earth picrate (RE) complexes with L-lysine (Lys) were synthesized and characterized. Elemental analysis (CHN), EDTA titrations and thermogravimetry data suggest
a general formula RE(pic)3·2Lys·2H2O, where RE=La-Lu (without Pm) and Y, pic=picrate). IR spectra suggest that Lys is coordinated to the central ion through the nitrogen of the α-amino group. Parameters
obtained from the absorption spectrum of the Nd compound indicated that the metal-ligand bonds are essentially electrostatic.
Emission spectrum and biexponential behavior of the luminescence decay of the Eu compound suggest the existence of polymeric
species. Thermogravimetric/derivative thermogravimetric (TG/DTG) and differential scanning calorimetry (DSC) curves of all
complexes are very similar, with five events. The final products are the corresponding rare earth oxides and their X-ray diffraction
patterns are identical to the calcinated oxides.</o:p> 相似文献
972.
Photoconversion of lutetium diphthalocyanine and interpretation of its electronic absorption spectra
V. G. Maslov T. P. Prokof'eva A. N. Sidorov 《Theoretical and Experimental Chemistry》1990,25(5):564-568
When frozen solutions of lutetium diphthalocyanine (LuPC2) in a mixture of methylene chloride with trichloroethylene are irradiated by UV light, monocations of LuPC2 form. The photoreaction is slowed and ceases in an early stage apparently due to the reversibility of the photoconversion in this system. The reduced form of LuPC2 (its monoanions) are completely converted into the neutral form of LuPC2 during irradiation. When this photoconversion is carried out in a frozen solution, the electronic absorption bands in the spectrum of the LuPC2 formed are displaced in comparison to the bands of the original substance under the same conditions, posibly due to the difference between the structures of the solvation shells. An interpretation of the electronic absorption spectrum of LuPC2 in the 300–1600-nm region has been given on the basis of the scheme of the molecular orbitals of sandwich phthalocyanine dimer with one -electronic vacancy.Translated from Teoreticheskaya i Éksperimental'naya Khimiya, Vol. 25, No. 5, pp. 614–618, September–October, 1989.We express our thanks to P. N. Moskalev for supplying the preparations of MIIIPC2. 相似文献
973.
Condensation of aryl- and aroylhydrazines and thiosemicarbazide with 2-diphenylphosphinoyloxybenzaldehyde results in formation of the corresponding hydrazones and thiosemicarbazone. The products give rise to conformational equilibrium between rotational and Z,E isomers, which is strongly displaced toward the E,E',Z' isomer and is determined by the nature of substituent in the hydrazine fragment. 相似文献
974.
T. Katsuki 《Russian Chemical Bulletin》2004,53(9):1859-1870
The recent development of asymmetric Baeyer—Villiger oxidation of prochiral and racemic ketones is briefly summarized, focusing on the regio- and stereocontrol of the oxidation attained by regulating the stereoelectronic demand in the step of rearrangement of the Criegee intermediate.Based on the report presented at the International Conference Modern Trends in Organoelement and Polymer Chemistry dedicated to the 50th anniversary of the A. N. Nesmeyanov Institute of Organoelement Compounds of the Russian Academy of Sciences (Moscow, May 30–June 4, 2004).Published in Russian in Izvestiya Akademii Nauk. Seriya Khimicheskaya, No. 9, pp. 1784–1794, September, 2004. 相似文献
975.
Catalytic nitrobenzene oxidation of lignins 总被引:1,自引:0,他引:1
A. F. Gogotov N. A. Rybal'chenko T. I. Makovskaya V. A. Babkin 《Russian Chemical Bulletin》1996,45(12):2854-2857
Alkaline nitrobenzene oxidation of hardwood and softwood lignins in the presence of redox and phase-transfer catalysts was studied. The selectivity of oxidation of lignins increased by 1.7 to 1.9 times. A possible mechanism of catalysis is discussed.Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 12, pp. 3004–3007, December, 1996. 相似文献
976.
Enthalpies of solution have been measured from 5 to 85°C for aqueous tetraethyl- and tetrapropylammonium bromides, and the integral heat method is employed to evaluate
for these electrolytes over a wide temperature range. Data taken from the literature have been used to evaluate
for aqueous Bu4NBr over a similar temperature range. These data, along with similar data for Me4NBr, previously reported, have been used to evaluate absolute ionic heat capacities. While the absolute values agree only qualitatively with two other methods of division, the temperature dependences of the three methods essentially agree up to 65°C. Heat capacities due to structural effects on the solvent, obtained by subtracting the inherent heat capacities of the ions, are extraordinarily positive for all four tetraalkylammonium ions and have negative temperature coefficients, indicating that all four ions, including the tetramethylammonium ion, are structure-making ions. 相似文献
977.
Institute of the Chemistry of Plant Substances, Uzbekistan Academy of Sciences, Tashkent. Translated from Khimiya Prirodnykh
Soedinenii, No. 6, pp. 899–900, November–December, 1993. 相似文献
978.
Ya. S. Yakhyaev S. N. Khadzhiev T. M. Gairbekov S. E. Spiridonov 《Reaction Kinetics and Catalysis Letters》1986,30(2):263-268
The effect of hydrothermal treatment of decationized superhigh-silica zeolite on the mechanism of n-hexane conversion has been studied. It has been established that thermosteam modification sharply decreases the cracking activity and increases the selectivity to aromatization reactions. Zeolite acidity markedly decreases, but its crystal structure does not become amorphous.
-. . .相似文献
979.
Stephen G. Davies Ian A. Hunter Rebecca L. Nicholson Paul.M. Roberts Edward D. Savory Andrew D. Smith 《Tetrahedron》2004,60(35):7553-7577
α-Dibenzylamino- and α-benzyloxy- derivatives of N-acetyl-(S)-4-benzyl-5,5-dimethyloxazolidin-2-one readily undergo highly stereoselective boron mediated syn-aldol reactions with a range of aromatic and aliphatic aldehydes, generating the syn-aldol products in good to excellent yields as single diastereoisomers after purification. In the α-dibenzylamino series, deprotection of the functionalised aldol fragments to the corresponding α-amino-β-hydroxy methyl ester or α-amino-β-hydroxyaldehyde proved problematic, with a range of N- and O-protecting groups giving mixtures of products arising from endocyclic and exocyclic cleavage pathways. However, in the α-benzyloxy series, O-silyl protection of the aldol products, and subsequent DIBAL reduction gives stereoselectively the corresponding N-1′-hydroxyalkyloxazolidin-2-ones, which undergo base promoted fragmentation to the desired highly functionalised and differentially protected α,β-dihydroxyaldehydes in good yields and without loss of stereochemical integrity. 相似文献
980.