全文获取类型
收费全文 | 16040篇 |
免费 | 1189篇 |
国内免费 | 749篇 |
专业分类
化学 | 15944篇 |
晶体学 | 331篇 |
力学 | 18篇 |
综合类 | 14篇 |
数学 | 4篇 |
物理学 | 1667篇 |
出版年
2024年 | 15篇 |
2023年 | 169篇 |
2022年 | 554篇 |
2021年 | 483篇 |
2020年 | 498篇 |
2019年 | 371篇 |
2018年 | 299篇 |
2017年 | 282篇 |
2016年 | 557篇 |
2015年 | 560篇 |
2014年 | 603篇 |
2013年 | 1171篇 |
2012年 | 738篇 |
2011年 | 678篇 |
2010年 | 765篇 |
2009年 | 765篇 |
2008年 | 791篇 |
2007年 | 812篇 |
2006年 | 771篇 |
2005年 | 722篇 |
2004年 | 797篇 |
2003年 | 705篇 |
2002年 | 1419篇 |
2001年 | 385篇 |
2000年 | 324篇 |
1999年 | 323篇 |
1998年 | 306篇 |
1997年 | 227篇 |
1996年 | 426篇 |
1995年 | 402篇 |
1994年 | 144篇 |
1993年 | 113篇 |
1992年 | 136篇 |
1991年 | 83篇 |
1990年 | 54篇 |
1989年 | 68篇 |
1988年 | 68篇 |
1987年 | 37篇 |
1986年 | 44篇 |
1985年 | 55篇 |
1984年 | 39篇 |
1983年 | 26篇 |
1982年 | 21篇 |
1981年 | 19篇 |
1980年 | 14篇 |
1979年 | 11篇 |
1978年 | 13篇 |
1975年 | 8篇 |
1971年 | 48篇 |
1970年 | 25篇 |
排序方式: 共有10000条查询结果,搜索用时 15 毫秒
181.
182.
A small amount (≤ 10−6 mol fraction) of four alkaline earth metals, tin and yttrium were introduced into five, premixed, fuel-rich, H2–O2–N2 flames at atmospheric pressure in the temperature range 1820–2400 K. Aqueous salt solutions of the metals were sprayed into the premixed flame gas as an aerosol using an atomizer technique. Ions in a flame were observed by sampling flame gas through a nozzle into a mass spectrometer. The concentrations of the major neutral metallic species present in the flame were calculated from thermodynamic data currently available. The principal metallic ions observed were AOH+ (A = Mg, Ca, Sr, Ba, Sn) and A(OH)2+ (A = Y), formed initially by proton transfer to AO and OAOH from H3O+, a natural flame ion. Except for Mg, the ions were also produced by chemi-ionization processes. By adjusting the concentration(s) of the salt solution in the atomizer, it was found that a pair of ions could be brought into equilibrium within the time scale of the flame; the pairs included H3O+ with a metal ion or two metallic ions. Because water is a major product of combustion, a very large difference in proton affinity PA0(AO) − PA0(H2O) ≤ 490 kJ mol−1 (117 kcal mol−1) could be attempted for the proton transfer equilibrium. Using PA0(H2O) = 691.0 kJ mol−1 (165.2 kcal mol−1) as a reference base to anchor the proton affinity scale, ion ratio measurements led to proton affinity PA0 values of 766, 912, 1004, 1184, 1201, and 1222 kJ mol−1 (183, 218, 240, 283, 287, and 292 kcal mol−1) corrected to 298 K for OYOH, SnO, MgO, CaO, SrO, and BaO, respectively; of these, only the value for OYOH has not been reported previously. If it is assumed that the neutral thermodynamic data are correct (although some appear to be in error), the uncertainties in the PA results reported here are ± 21 kJ mol−1 (5 kcal mol−1). The realization that these equilibria can be achieved in flames provides a new approach to consolidate and build the high end of the proton affinity ladder, primarily of metallic species which are not accessible at lower temperatures. 相似文献
183.
184.
The reaction of acetone-4-chlorophenylhydrazone (6) with bromine in the presence of acetamide yields 2-bromo-2-(4-chlorophenylazo)-propane (7) and 2,2-bis(4-chlorophenylazo)propane (8). The unstable heteroallylic bromide7 was subjected without isolation to nucleophilic displacements with a series of heteronucleophiles thereby affording the corresponding 2-(4-chlorophenylazo)-2-propane derivatives9 with the azo- and heteroelement-functions in a geminal position to each other.
Herrn Prof. Dr. Dr. h. c.K. Kratzl mit den besten Wünschen zum 70. Geburtstag gewidmet. 相似文献
185.
Céline Jousse-KarinthiFatima Zouhiri Jacqueline MahuteauDidier Desmaële 《Tetrahedron》2003,59(12):2093-2099
The palladium-catalyzed condensation of a variety of active methylene compounds with methyl 6-acetoxymethyl-hepta-2,6-dienoate was investigated. The six-membered adducts resulting from a η3 palladium complex alkylation-Michael addition sequence were obtained with moderate to good yields. In some cases, further evolution of the primary adduct was observed. The process has been expanded to access nitrogen heterocycles by using sodium p-toluenesulfonamide as the nucleophilic partner. 相似文献
186.
本文报道了一类新型全硫冠醚聚合物的合成,即由聚环硫氯丙烷与二巯基化合物反应,生成具有冠醚环结构单元的交联型聚合物。并研究了这些聚合物的对金属离子的络合性能。 相似文献
187.
Chemo- and regioselectivity in the reactions between highly electrophilic fluorine containing dicarbonyl compounds (ethyl 4,4,4-trifluoroacetoacetate, 3,3,3-trifluoropyruvate and 1,1,1,5,5,5-hexafluoropentane-2,4-dione) and various benzylamines were systematically studied. The results obtained lead to the development of a generalized and practical method for large-scale synthesis of the corresponding imines/enamines, useful starting materials for preparation fluorinated amines and amino acid. 相似文献
188.
Valentine G Nenajdenko Georgy N Varseev Alexey V Shastin 《Journal of fluorine chemistry》2003,124(1):115-118
A novel catalytic approach to (2,2-difluorovinyl)benzenes has been developed. It was found that hydrazones of aromatic aldehydes generated in situ could be converted to the corresponding (2,2-difluorovinyl)benzenes by catalytic olefination reaction (COR) with dibromodifluoromethane in the presence of CuCl. 相似文献
189.
Tetra-Schiff base macrocyclic compound containing benzo-12-crown-4 was synthesized via condensation of 2,6-diformyl-4-methyl-phenol with 4′,5′-diaminobenzo-12-C-4 promoted by proton. The compound was characterized by MS,IR ^1HNMR spectroscopy and elemental analysis. 相似文献
190.
CuO/γ-Al2O3 catalysts were prepared by plasma treatment and conventional impregnation methods. The catalytic combustion of two kinds of volatile organic compounds (VOCs), toluene and benzene, were carried out over these CuO/γ-Al2O3 catalysts. The surface properties of these catalysts were characterized by X-ray Diffraction (XRD) and Scanning Electron Microscopy (SEM). The experimental results showed that in catalytic combustion the activity of the CuO/γ-Al2O3 catalyst prepared via plasma was much higher than that of the CuO/γ-Al2O3 catalyst prepared by conventional impregnation method. XRD results showed that an enhanced dispersion had been achieved with the plasma treatment. SEM results indicated that the size became much smaller and the surface became more uniform with the plasma treatment. 相似文献