全文获取类型
收费全文 | 36797篇 |
免费 | 5051篇 |
国内免费 | 4941篇 |
专业分类
化学 | 28596篇 |
晶体学 | 574篇 |
力学 | 1753篇 |
综合类 | 448篇 |
数学 | 3853篇 |
物理学 | 11565篇 |
出版年
2024年 | 42篇 |
2023年 | 414篇 |
2022年 | 808篇 |
2021年 | 984篇 |
2020年 | 1108篇 |
2019年 | 1166篇 |
2018年 | 927篇 |
2017年 | 906篇 |
2016年 | 1533篇 |
2015年 | 1535篇 |
2014年 | 1881篇 |
2013年 | 2626篇 |
2012年 | 3130篇 |
2011年 | 3251篇 |
2010年 | 2395篇 |
2009年 | 2199篇 |
2008年 | 2663篇 |
2007年 | 2345篇 |
2006年 | 2245篇 |
2005年 | 1967篇 |
2004年 | 1709篇 |
2003年 | 1524篇 |
2002年 | 1690篇 |
2001年 | 1240篇 |
2000年 | 1019篇 |
1999年 | 845篇 |
1998年 | 574篇 |
1997年 | 552篇 |
1996年 | 511篇 |
1995年 | 449篇 |
1994年 | 388篇 |
1993年 | 356篇 |
1992年 | 326篇 |
1991年 | 259篇 |
1990年 | 230篇 |
1989年 | 188篇 |
1988年 | 142篇 |
1987年 | 116篇 |
1986年 | 103篇 |
1985年 | 107篇 |
1984年 | 62篇 |
1983年 | 54篇 |
1982年 | 41篇 |
1981年 | 41篇 |
1980年 | 26篇 |
1979年 | 14篇 |
1978年 | 16篇 |
1977年 | 14篇 |
1976年 | 13篇 |
1974年 | 12篇 |
排序方式: 共有10000条查询结果,搜索用时 0 毫秒
991.
Reaction of 2-adamantyl chloroformate under a variety of solvolytic conditions leads to 2-adamantyl chloride accompanied by solvolysis products, some with and some without retention of the CO(2) unit. For example, in 100% ethanol, only 4.8% 2-adamantyl chloride is formed with the mixed carbonate (88%) being the dominant product, and in 100% 2,2,2-trifluoroethanol, the products are both formed with loss of CO(2), 59% of the chloride and 41% of the ether. With exclusion of the specific rates in 100% and 90% ethanol and methanol, a good Grunwald-Winstein plot against Y(Cl) values (solvent ionizing power) is obtained, with a slope of 0.47 +/- 0.03. The results are compared with those reported earlier for 1-adamantyl chloroformate and isopropyl chloroformate and mechanistic conclusions are drawn. 相似文献
992.
Solid-state synthesis of a conducting polythiophene via an unprecedented heterocyclic coupling reaction 总被引:2,自引:0,他引:2
Meng H Perepichka DF Bendikov M Wudl F Pan GZ Yu W Dong W Brown S 《Journal of the American Chemical Society》2003,125(49):15151-15162
Prolonged storage ( approximately 2 years) or gentle heating (50-80 degrees C) of crystalline 2,5-dibromo-3,4-ethylenedioxythiophene (DBEDOT) affords a highly conducting, bromine-doped poly(3,4-ethylenedioxythiophene) (PEDOT), as confirmed by solid-state NMR, FTIR, CV, and vis-NIR spectroscopies. The novel solid-state polymerization (SSP) does not occur for 2,5-dichloro-3,4-ethylenedioxythiophene (DCEDOT), and requires a much higher temperature (>130 degrees C) for 2,5-diiodo-3,4-ethylenedioxythiophene (DIEDOT). X-ray structural analysis of the above dihalothiophenes reveals short Hal.Hal distances between adjacent molecules in DBEDOT and DIEDOT, but not in DCEDOT. The polymerization may also occur in the melt but is significantly slower and leads to poorly conductive material. Detailed studies of the reaction were performed using ESR, DSC, microscopy, and gravimetric analyses. SSP starts on crystal defect sites; it is exothermic by 14 kcal/mol and requires activation energy of approximately 26 kcal/mol (for DBEDOT). The temperature dependence of the conductivity of SSP-PEDOT (sigma(rt) = 20-80 S/cm) reveals a slight thermal activation. It can be further increased by a factor of 2 by doping with iodine. Using this approach, thin films of PEDOT with conductivity as high as 20 S/cm were fabricated on insulating flexible plastic surfaces. 相似文献
993.
CrystalStructuresofLanthanumComplexeswithNitrobenzoicAcids¥MaJian-Fang;JinZhong-Sheng;NiJia-Zuan(LaboratoryofRareEarthChemist... 相似文献
994.
MINDO/3 method has been used to study the mechanism of the consecutive addition ofHCN to aminoacetonitrile.The results obtained for the first three steps show that the reaction isexothermic,and step I is the rate determining step. 相似文献
995.
用晶内形成法制备了Ni_xB/沸石催化剂,用饱和氢化学吸附法结合TEM方法考察了负载金属的分散性,并研究了其己环烷脱氢反应性。结果表明,Ni_xB/沸石样品上负载金属的分散性高,金属粒径分布也相对集中;金属负载量、载体结构和性质以及Ni_xB的制备条件对负载金属的分散性有明显影响。Ni_xB/沸石样品呈现较好的环己烷脱氢反应性。 相似文献
996.
微量稀土对超导稳定化基体铜材的性能和组织的影响 总被引:4,自引:0,他引:4
研究了微量稀土元素对铜的机械性能、导电性和组织的影响,在铜中加入微量钇、钕、镝、铒和富铈混合稀土后,使铜的抗拉强度有所提高,并保持良好的塑性和导电性。 相似文献
997.
998.
YuYingFENG XiaoTianGU JiaHongZHOU JianChunBAO GangLI TianHongLU 《中国化学快报》2004,15(12):1505-1508
New Ge/SiO2 glasses have been synthesized by heating the GeO2/SiO2 dry gels under H2 gas at 700℃. The resulting fluorescence spectra show that this kind of Ge/SiO2 glasses emit strong photoluminescence at 392 nm (3.12 eV), medium strong photoluminescence at 600 nm (2.05 eV) and weak photoluminescence at 770 nm (1.60 eV) respectively. Possible photoluminescence mechanisms are also discussed based on the results of X-ray diffraction (XRD) and X-ray photoelectron spectra (XPS). 相似文献
999.
Lanying?Yang Yi?Zhang Qingqi?Chen Jin Shi?MaEmail author 《Monatshefte für Chemie / Chemical Monthly》2004,135(2):223-229
Summary. 1-(Dipyrrin-2-yl)-1-(dipyrrin-3-yl)methane, the N-confused analog of biladiene-ac, is prepared by condensation of 2,3-dipyrromethane with two molecules of 2-formylpyrrole in dichloromethane in the presence of hydrogen bromide. Self-assembly of the ligand with Zn(II) in dichloromethane and methanol offers a dinuclear dimeric complex with a ligand:metal ratio of 2:2. X-Ray crystal structure analysis reveals two ligands bound through a head-to-tail pattern to two zinc centers to form a severely distorted helical conformation, which has the shape of a rectangle. 相似文献
1000.
YueMingLIU FengMeiZHANG HaiHongWU HaiJiaoZHANG JianGuoYANG XingTianSHU MingYuanHE 《中国化学快报》2004,15(10):1258-1260
A SAPO-11 silicoaluminophosphate molecular sieve with stable crystal structure was synthesized for the first time. After removing template by calcination, its crystal space group still retains Icm2 which the as-synthesized has. The catalyst deriving from the present SAPO-I 1 materials shows higher isomerization selectivity and higher paraffin hydroisomerization yield than those reported elsewhere. 相似文献