全文获取类型
收费全文 | 106507篇 |
免费 | 5013篇 |
国内免费 | 3712篇 |
专业分类
化学 | 44558篇 |
晶体学 | 1218篇 |
力学 | 8410篇 |
综合类 | 299篇 |
数学 | 34643篇 |
物理学 | 26104篇 |
出版年
2024年 | 102篇 |
2023年 | 590篇 |
2022年 | 1044篇 |
2021年 | 1148篇 |
2020年 | 1271篇 |
2019年 | 1209篇 |
2018年 | 11237篇 |
2017年 | 11075篇 |
2016年 | 7370篇 |
2015年 | 2348篇 |
2014年 | 1974篇 |
2013年 | 2574篇 |
2012年 | 6273篇 |
2011年 | 13007篇 |
2010年 | 7319篇 |
2009年 | 7622篇 |
2008年 | 8376篇 |
2007年 | 10360篇 |
2006年 | 1712篇 |
2005年 | 2530篇 |
2004年 | 2492篇 |
2003年 | 2766篇 |
2002年 | 1796篇 |
2001年 | 841篇 |
2000年 | 822篇 |
1999年 | 702篇 |
1998年 | 666篇 |
1997年 | 605篇 |
1996年 | 694篇 |
1995年 | 497篇 |
1994年 | 479篇 |
1993年 | 389篇 |
1992年 | 333篇 |
1991年 | 313篇 |
1990年 | 237篇 |
1989年 | 204篇 |
1988年 | 190篇 |
1987年 | 163篇 |
1986年 | 165篇 |
1985年 | 146篇 |
1984年 | 114篇 |
1983年 | 104篇 |
1982年 | 91篇 |
1981年 | 82篇 |
1980年 | 89篇 |
1979年 | 77篇 |
1978年 | 54篇 |
1914年 | 45篇 |
1909年 | 41篇 |
1908年 | 40篇 |
排序方式: 共有10000条查询结果,搜索用时 62 毫秒
991.
The influence of Stokes shift in optosensing was discussed. Then, the current status of large Stokes shift-based optosensing was reviewed here. 相似文献
992.
993.
18-冠-6与Eu(fod)3+在CCl4中的化学平衡及其配合物的结构 总被引:1,自引:0,他引:1
在室温下测定了CCl_4溶液中,18-冠-6的亚甲基、Eu(fod)的t—丁基质子的PMR化学位移与溶液组成的相互关系。提出了生成配合物RS,R_2S,R_2,R_3(S为18-冠-6,R为Eu(fod)_3)的模式。求得了平衡常数值(升/摩):K_1=[RS]/([R][S])=2.O×10~5,K_2=[R_2S]/([R][RS])=1.0×10~3,Q_1=[R_2]/[R]~2=4.2×10~2,Q_2=[R_3]/([R_2][R])=4.0×10~1。并测得在配合物RS,R_2S中18-冠-6质子的平均化学位移分别为4.90,10.84(ppm,相对于纯18-冠-6); 在配合物R,R_2,R_3,RS,R_2中t-丁基质子平均化学位移分别为1.53,2.33,0.54,1.02,2.42(ppm,相对于TMS)。 根据配合物的化学位移值,并考虑分子及分子轨道的对称性、位阻等因素提出了配合物R_2,RS,R_2S的可能的结构模型。 相似文献
994.
Chen YW Liu YC Lu SX Xu CS Shao CL Wang C Zhang JY Lu YM Shen DZ Fan XW 《The Journal of chemical physics》2005,123(13):134701
Self-assembled zinc oxide (ZnO) and indium-doping zinc oxide (ZnO:In) nanorod thin films were synthesized on quartz substrates without catalyst in aqueous solution by sol-gel method. The samples were characterized by x-ray diffraction (XRD), scanning electron microscope (SEM), Raman-scattering spectroscopy, room-temperature photoluminescence (PL) spectra, and temperature-dependent PL spectra measurements. XRD and Raman spectra illustrated that there were no single In2O3 phase in ZnO lattice after indium doping. The PL spectra of ZnO showed a strong UV emission band located at 394 nm and a very weak visible emission associated with deep-level defects. Indium incorporation induced the shift of optical band gap, quenching of the near-band-edge photoluminescence and enhanced LO mode multiphonon resonant Raman scattering in ZnO crystals at different temperatures. Abnormal temperature dependence of UV emission integrated intensity of ZnO and ZnO:In samples is observed. The local state emission peak of ZnO:In samples at 3.37 eV is observed in low-temperature PL spectra. The near-band-edge emission peak at room temperature was a mixture of excitons and impurity-related transitions for both of two samples. 相似文献
995.
A pressure-filter-template approach was employed to prepare polyelectrolyte nanotubes through layer-by-layer deposition in the alumina template. With the thicker wall, the ordered polymer nanotubes possess a high flexibility. The results demonstrate that the electrostatic interactions of polyelectrolytes play a key role in fabricating water-soluble charged polymer nanotubes. The structure of the polyelectrolyte nanotube was confirmed by SEM, TEM, and UV, respectively. 相似文献
996.
Capillary electrochromatography (CEC) has been performed with a series of C14, methlyacrylamide based monolithic columns. These monoliths with different porosities were prepared by in-situ copolymerization in fused-silica capillaries. The porous properties of monoliths were further observed using scanning electron micrographs (SEM) and measured using a mercury porosimeter. The effect of various alcohols as porogens on porous structural properties and chromatographic behaviors were also investigated. The effects of organic additive, pH value and ionic strength in mobile phase on electroosmosis flow (EOF) and separation were further discussed. Meanwhile, the baseline separation of 6 neutral compounds can be well obtained. In addition, the monolithic column demonstrates the high column efficiency and satisfactory reproducibility.Acknowledgements We gratefully acknowledge the support of the National Natural Science Foundation of China. 相似文献
997.
Ya-Guang Chen Fan-Xia Meng Hai-Jun Pang Dong-Mei Shi Yu Sun 《Journal of Cluster Science》2007,18(2):396-405
A novel uranyl complex with dimeric lacunary polyoxoanion like open-mouthed clam, Na5[(A-α-SiW9O33H3)2K{UO2(H2O)}2], was prepared and characterized by elemental analysis, infrared and ultraviolet–visible spectroscopy and single crystal
X-ray diffraction. In the anion, two A-α-SiW9O3410− groups share two terminal oxygen atoms Od′ derived from removal of three corner-shared W atoms from saturated α-Keggin anion, forming a dimeric anion with an open
mouth in which potassium ion and uranyl ions are coordinated. Uranium atom adopts a pentagonal bipyramidal geometry. The coordinating
anions are linked by sodium ions via coordination of terminal or bridging oxygen atoms, forming two-dimensional layer arrangement.
Between the layers are the hydrogen bonds from which a supramolecular architecture is created. UV–VIS spectrum gives W–O and
U–O charge transfer transitions at 230–265 and 432 nm, showing the change of geometry of the polyanion and weakening of the
U–O bonds of the uranyl cation.
Electronic supplementary material The online version of this article () contains supplementary material, which is available to authorized users. 相似文献
998.
Yan Xiao Jian Wang Wang Xia Guang Feng Huai You Wang 《Journal of Analytical Chemistry》2007,62(5):438-443
The maximum emission wavelength of dopamine is 317 nm with excitation at 290 nm. The relative fluorescence intensity of dopamine
decreased in the presence of enoxacin, which showed that fluorescence quenching occurred. The Stern-Volmer (S-V) plot showed
a nonlinear relationship between the relative fluorescence intensity of dopamine and the concentration of enoxain. The quenching
mechanism was studied and the results suggested that both dynamic and static quenching processes were responsible for the
observed positive deviation in the S-V plot. When the S-V plot was modified by logarithm, the linear relationship was obtained
between logF
0/F and C in the range of 0.10 to 13.0 μg/mL (where F
0 is the relative fluorescence intensity of dopamine, F is the relative fluorescence intensity of dopamine in the presence of enoxacin, and C is the concentration of enoxacin). The fluorescence quenching method for the determination of enoxacin was developed. The
linear regression equation of the calibration graph of enoxacin was C = 13.70 (logF
0/F) − 0.5836, with the correlation coefficient 0.9984. The detection limit was 2.0 ng/mL and the relative standard deviation
was 2.52%. The effects of pH, the stability of dopamine in the presence of enoxacin, and foreign ions on the determination
of enoxacin have been examined. The recovery of enoxacin was from 94.9 to 103.0% in a human serum sample and from 94.9 to
108.0% in a urine sample. The method is simple, rapid, and can be used for the determination of enoxacin in human serum and
urine samples with satisfactory results.
The text was submitted by the authors in English. 相似文献
999.
Zhaoyang Cheng Shipei Xing Jun Guo Biao Cheng Lan‐Fang Hu Xing‐Hong Zhang Zhan Lu 《中国化学》2019,37(5):457-461
A regioselective double 1,1‐hydrosilylation of terminal aliphatic alkynes with primary silanes catalyzed by one cobalt catalyst has been developed. gem‐Bis(dihydrosilyl)alkanes containing four silicon‐hydrogen bonds are efficiently constructed in an atom‐economical manner. Tolerated substrates include simplest alkyne‐ethyne, a complicated drug derivative and various functionalized terminal aliphatic alkynes. Asymmetric approach using two catalysts is achieved with excellent enantioselectivities to access corresponding chiral products. The transformations of Si—H bonds into Si—C, Si—O, and Si—F bonds and the synthesis of enantioriched α‐hydroxysilane show synthetic utility. 相似文献
1000.
Peng Yang Xuan Wang Bo Li Yixuan Yang Jinfeng Yue Yanrui Suo Huarong Tong Gang He Xiaojie Lu Gong Chen 《Chemical science》2021,12(16):5804
A highly efficient and versatile method for construction of peptide macrocycles via palladium-catalyzed intramolecular S-arylation of alkyl and aryl thiols with aryl iodides under mild conditions is developed. The method exhibits a broad substrate scope for thiols, aryl iodides and amino acid units. Peptide macrocycles of a wide range of size and composition can be readily assembled in high yield from various easily accessible building blocks. This method has been successfully employed to prepare an 8-million-membered tetrameric cyclic peptide DNA-encoded library (DEL). Preliminary screening of the DEL library against protein p300 identified compounds with single digit micromolar inhibition activity.A highly efficient and versatile method for construction of peptide macrocycles via palladium-catalyzed intramolecular S-arylation of alkyl and aryl thiols with aryl iodides under mild conditions is developed. 相似文献