全文获取类型
收费全文 | 17407篇 |
免费 | 2656篇 |
国内免费 | 1914篇 |
专业分类
化学 | 12523篇 |
晶体学 | 186篇 |
力学 | 1192篇 |
综合类 | 135篇 |
数学 | 2019篇 |
物理学 | 5922篇 |
出版年
2024年 | 55篇 |
2023年 | 331篇 |
2022年 | 537篇 |
2021年 | 594篇 |
2020年 | 626篇 |
2019年 | 661篇 |
2018年 | 529篇 |
2017年 | 537篇 |
2016年 | 760篇 |
2015年 | 760篇 |
2014年 | 950篇 |
2013年 | 1166篇 |
2012年 | 1526篇 |
2011年 | 1538篇 |
2010年 | 1051篇 |
2009年 | 930篇 |
2008年 | 1081篇 |
2007年 | 975篇 |
2006年 | 973篇 |
2005年 | 789篇 |
2004年 | 599篇 |
2003年 | 543篇 |
2002年 | 543篇 |
2001年 | 458篇 |
2000年 | 343篇 |
1999年 | 360篇 |
1998年 | 288篇 |
1997年 | 268篇 |
1996年 | 297篇 |
1995年 | 234篇 |
1994年 | 203篇 |
1993年 | 159篇 |
1992年 | 169篇 |
1991年 | 173篇 |
1990年 | 128篇 |
1989年 | 123篇 |
1988年 | 81篇 |
1987年 | 70篇 |
1986年 | 80篇 |
1985年 | 60篇 |
1984年 | 54篇 |
1983年 | 44篇 |
1982年 | 32篇 |
1981年 | 31篇 |
1980年 | 29篇 |
1978年 | 24篇 |
1977年 | 25篇 |
1976年 | 23篇 |
1974年 | 20篇 |
1973年 | 26篇 |
排序方式: 共有10000条查询结果,搜索用时 15 毫秒
191.
本文介绍一种简单、快速、灵敏、直接分析酒中游离脂肪酸的测定方法。用涂有OV-17熔融石英毛细管柱。选择游离脂肪酸质谱图中的基峰离子m/z 60进行SIM检测。定量测定了茅台酒、珍酒及鸭溪窖酒中十二种游离脂肪酸。 相似文献
192.
Pengyuan Zhao Aolin Cheng Xinxu Wang Jiguo Ma Guoqing Zhao Yingkun Li Yi Zhang Baoguo Zhao 《中国化学》2020,38(6):565-569
By using a combination of a chiral N‐triflyl phosphoramide and TiCl4 as the catalyst, a new process for asymmetric intramolecular hydroalkoxylation of unactivated alkenes was developed, producing various chiral tetrahydrofuran derivatives in 51%—99% yields with 30%—71% ee's. 相似文献
193.
通过1-环庚烯基锂与6,6-二烷基富烯发生环外双键的加成反应形成的大取代茂锂试剂与MCl4(M=Ti,Zr)反应,合成了12个含或不含手性碳的大位阻取代茂金属有机化合物,并研究了它们的1HNMR,EIMS和IR. 相似文献
194.
铟(Ⅲ)-芦丁极谱络合吸附波的研究 总被引:3,自引:0,他引:3
在pH6.0的乙酸盐缓冲底液中,用单扫极谱法可获得高灵敏度的铟(Ⅲ)-芦丁的络合吸附波,其检测下限达3.0×10~(-10)mol/L。成功地用于纯金属锌中10~(-5)%铟的测定。测得吸附电活性络合物的组成为:In(Ⅲ):芦丁=1∶2,条件稳定常数为1.8×10~(10)。电极反应是吸附络合物中的In(Ⅲ)还原为In(Hg)。测得电极反应的转移系数α=0.51,表面电化学反应的标准速率常数k_s=0.43/s 相似文献
195.
196.
The charge transport properties of mer-tris(8-hydroxyquinolinato)aluminum(III) (mer-Alq), which is the most widely used electron transport material in OLED, were investigated by quantum chemistry calculations within the framework of the charge hopping model and Marcus electron transfer theory. Internal reorganization energies of 0.276 and 0.242 eV were calculated by the DFT-B3LYP method employing a 6-31 G* basis set for the electrons lambdai(e) and holes lambdai(h), respectively. The relative distances and orientations of Alq molecules in amorphous film were simulated by those in the beta-phase. The intermolecular charge-transfer integrals, Hda(h) and Hda(e), along all 14 hopping pathways were then calculated by the Koopmans Theorem in conjunction with the Hartree-Fock method employing a 6-31 G* basis set as well as by the direct coupling method. The results showed that there were some Hda(e) that were 1 order of magnitude larger than any Hda(h), because hopping pathways with effective overlaps of LUMOs can occur and, thus, large Hda(e). On the other hand, effective overlap of HOMO was absent in all pathways, resulting in a relatively small Hda(h). This difference in the magnitudes of Hda(e) and Hda(h) would predict a 2 orders of magnitude difference in the electron-transfer rate constants and account for the observed 2 orders of magnitude difference in the mobilities of electrons and holes. 相似文献
197.
The equilibrium geometries, electronic structures, as well as one- and two-photon absorption cross sections of a series of octupolar chromophores with Zn(2+) or Cu(+) as coordinate centers and 4,4'-bis(dibutylaminostyryl)-[2,2']-bis(bipyridyl) as ligands have been determined by using B3LYP/6-31G and ZINDO methods. These molecules are designed by controlled combination of two or three bipyridyl ligands with the metal centers. The results show that Zn(2+) is an effective template for the design of octupolar structures which enable it to form tetrahedral and octahedral coordinated complexes; while Cu(+) only exists in a tetrahedral coordinated complex, comparing the tetrahedral complex with Zn(2+) as the center with that of Cu(+) as the center, it is found that the complex with the Cu(+) center is a better two-photon absorption material than the former as far as the transparency/nonlinearity is concerned. Furthermore, for the same metal center of Zn(2+), both one- and two-photon absorptions of the tetrahedral complex are redshifted relative to those of the octahedral complex, is attributed to the spiroconjugation effect in the tetrahedral complex. Our theoretical findings are consistent with recent experimental observations and provide an important foundation for the design of improved transparency-nonlinearity two-photon absorption materials. 相似文献
198.
Aminonaphthalic anhydrides as red-emitting materials: electroluminescence, crystal structure, and photophysical properties 总被引:2,自引:0,他引:2
Islam A Cheng CC Chi SH Lee SJ Hela PG Chen IC Cheng CH 《The journal of physical chemistry. B》2005,109(12):5509-5517
The red and orange emitters (ANA-1-3) consisting of a 4-amino-1,8-naphthalic anhydride group were synthesized. The lowest absorption band of these ANA molecules centered at approximately 450 nm is assigned to be a charge-transfer transition with emission at 514-536 nm in nonpolar solvents such as n-hexane and at approximately 590-640 nm in polar solvents such as THF and CH(2)Cl(2) and in the solid states. Emission lifetimes are measured with time-correlated single photon counting. Shorter lifetimes are observed for the ANA molecules when dissolved in polar solvents compared with those in nonpolar solvents. Strong dipole-dipole interaction of ANA molecules with solvents is indicated. At high concentrations the measured emission lifetimes, generally shortened from self-quenching, are found to remain about the same order of magnitude in ANAs. This implies that the exciton states of aggregates are formed and they exhibit a relatively long lifetime. Crystallographic data of 4-(phenyl antracen-9-yl) (ANA-2) and 4-(phenyl-2-naphthyl) amino-1,8-naphthalic anhydrides (ANA-3) show that the molecules exist as dimeric structures with antiparallel head-to-tail stacking of naphthalic anhydride planes in addition to other pi-pi stacking. The strong dipole-dipole interactions and the pi-pi stacking account for the observed red-shifted emissions of ANAs in the powders. For films prepared from vacuum sublimation, a structure similar to that in the crystal but with less crystalline order is expected based on the emission wavelength. Several electroluminescent devices based on these ANAs are reported here; they emit orange-red light at 602-628 nm with high brightness and steady external quantum efficiency. 相似文献
199.
A chiral stationary phase (CSP) has been prepared by chemically bonding a chiral pseudo-18-crown-6 type host having a 1-phenyl-1,2-cyclohexanediol unit to 3-aminopropyl silica gel. The chiral column was prepared by the slurry-packing method in a stainless steel HPLC column. Normal mobile phases can be used with this CSP in contrast to conventional dynamic coating type CSPs. Enantiomers of 20 out of 30 amino compounds, including 20 amino acids, 2 amino acid methyl esters, 6 amino alcohols, and 2 lipophilic amines, were efficiently separated on columns with this CSP. It is noteworthy that 15 amino compounds out of 30 were separated with better separation factors and shorter retention times compared to the corresponding CSP having pseudo-18-crown-6 with 1-phenyl-1,2-ethanediol as a chiral unit. In view of the correlation between the enantiomer selectivities observed in chromatography and those obtained in gas phase FABMS-EL methods and solution phase titrations, chiral recognition in the host-guest interaction likely contributes to enantiomer separation. 相似文献
200.
From the hexane extractive of the wood of Pinus luchuensis Mayer, α-pinene, β-pinene, camphene, camphor, 4-terpineol, α-terpineol, carvacrol, tetracosanol, hexacosanol, octacosanol, β-sitosterol, stigmasterol, methyl dehydroabietate, pinosylvin monomethylether, pimaric acid, dehydroabietic acid and straight chain hydrocarbons C23-C35 were isolated. 相似文献