全文获取类型
收费全文 | 94959篇 |
免费 | 3514篇 |
国内免费 | 2827篇 |
专业分类
化学 | 36658篇 |
晶体学 | 979篇 |
力学 | 7913篇 |
综合类 | 167篇 |
数学 | 33729篇 |
物理学 | 21854篇 |
出版年
2023年 | 376篇 |
2022年 | 655篇 |
2021年 | 611篇 |
2020年 | 773篇 |
2019年 | 671篇 |
2018年 | 10875篇 |
2017年 | 10661篇 |
2016年 | 6790篇 |
2015年 | 1635篇 |
2014年 | 1284篇 |
2013年 | 1516篇 |
2012年 | 5369篇 |
2011年 | 12063篇 |
2010年 | 6672篇 |
2009年 | 7031篇 |
2008年 | 7717篇 |
2007年 | 9728篇 |
2006年 | 1280篇 |
2005年 | 2164篇 |
2004年 | 2198篇 |
2003年 | 2520篇 |
2002年 | 1566篇 |
2001年 | 713篇 |
2000年 | 681篇 |
1999年 | 606篇 |
1998年 | 510篇 |
1997年 | 438篇 |
1996年 | 534篇 |
1995年 | 403篇 |
1994年 | 346篇 |
1993年 | 296篇 |
1992年 | 243篇 |
1991年 | 222篇 |
1990年 | 183篇 |
1989年 | 170篇 |
1988年 | 166篇 |
1987年 | 124篇 |
1986年 | 117篇 |
1985年 | 89篇 |
1984年 | 73篇 |
1983年 | 63篇 |
1982年 | 56篇 |
1981年 | 56篇 |
1980年 | 53篇 |
1979年 | 46篇 |
1914年 | 45篇 |
1913年 | 40篇 |
1912年 | 40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 31 毫秒
991.
Xu-Chun Wang Jian-Feng Li He-Ping Chen Jie-Ying Wu Hong-Ping Zhou Jia-Xiang Yang Bao-Kang Jin Yu-Peng Tian 《Transition Metal Chemistry》2007,32(5):551-557
The novel compound, 3-(E)-ferrocenyl-vinyl-N-hexylcarbazole (FVHC) was first synthesized and fully characterized by elemental analysis, IR, 1H-NMR, single-crystal X-ray diffraction, ultraviolet (UV) absorption, cyclic voltammograms (CV) and optical limiting (OL)
measurements. The result of single crystal X-ray diffraction for the compound reveals that the ferrocenyl and carbazole groups
are approximately coplanar, and bridged by double-bond with E configuration, showing that there is a well-delocalized π-electron
system in the molecule. The electrochemical investigation indicated that the electron in the FVHC may partially be delocalized
over the π-conjugated system and CT process in functionalized carbazole systems. Besides, the compound exhibited strong UV
absorption and large optical limiting effect, indicating promising potential applications as useful OL materials. 相似文献
992.
Zhang Z Blom DA Gai Z Thompson JR Shen J Dai S 《Journal of the American Chemical Society》2003,125(25):7528-7529
One-dimensional (1D) magnetic nanomaterials have attracted much attention recently because of their applications in magnetic recording and spintronics. Nevertheless, it remains a challenge to prepare free-standing magnetic nanowires in high yield. This Communication reports the successful high-yield synthesis of an interesting 1D ferromagnetic CoPt alloy by direct decomposition of platinum acetylacetonate and cobalt carbonyl compound in ethylenediamine solvent through a solvothermal reaction. The CoPt alloy nanowires obtained have a tunable diameter of 10-50 nm and a length along the longitudinal axis of up to several microns, depending on crystallization temperature and reaction time. A unique formation mechanism involving coarsening and ripening under solvothermal conditions was discovered. This research opens new opportunities in synthesizing nanomaterials through low-temperature solvothermal processes. 相似文献
993.
Carbon nanotube array-based biosensor 总被引:8,自引:0,他引:8
Aligned multi-wall carbon nanotubes (MWNT) grown on platinum substrate are used for the development of an amperometric biosensor. The opening and functionalization by oxidation of the nanotube array allows for the efficient immobilization of the model enzyme, glucose oxidase. The carboxylated open-ends of nanotubes are used for the immobilization of the enzymes, while the platinum substrate provides the direct transduction platform for signal monitoring. It is also shown that carbon nanotubes can play a dual role, both as immobilization matrices and as mediators, allowing for the development of a third generation of biosensor systems, with good overall analytical characteristics. 相似文献
994.
Pyrolytic process has a promising potential for the environmentally friendly upgrading of lignocellulosic and plastic waste.
Thermogravimetry and pyrolysis-gas chromatography-mass spectrometry (Py-GC/MS) were used to get information about the reactive
decomposition of PCL in binary mixtures with microcrystalline cellulose (MC) or sisal fibres (SF). Preliminary thermogravimetric
investigation showed that biomass is thermally degraded at lower temperatures than PCL and this process has a predominant
influence on the thermal behaviour of the mixtures. Discrepancies between the experimental and predicted TG/DTG profiles were
considered as a measurement of the extent of interactions occurring on co-pyrolysis. It was found that reactivity of PCL was
slightly increased in PCL-SF binary mixtures. Evolution of acidic products from cellulose and hemicelluloses decomposition
may promote PCL degradation in binary mixtures with SF. It seems that the co-pyrolysis process could have potential for the
environmentally friendly transformation of biocomposites. 相似文献
995.
The hydrothermal reaction of VOSO4, As2O5, piperazine and H2O produces [H2N(CH2)4NH2]4[β‐As8V14O42(SO4)]·2HSO4 ( 1 ), which is the first arsenic‐vanadium cluster containing a spherical β‐As8V14O42 shell. The structure of this compound was characterized by single crystal X‐ray diffraction, elemental analysis, TG, and IR spectrum. Crystal data for 1 : Orthorhombic, Cmcm, a = 15.369(1) Å, b = 16.404(1) Å, c = 25.772(1) Å, V = 6497.4(9) Å3, Z = 4. 相似文献
996.
The refolding of the reduced-denatured insulin from bovine pancreas was investigated with the size exclusion chromatography (SEC). It was shown that the reduced-denatured insulin originally denatured with 7.0 mol L?1 guanidine hydrochloride (GuHCI) or 8.0 mol L?1 urea could not be refolded with a non-oxidized mobile phase. Although the oxidized and reduced glutathione (GSSG and GSH) were employed in the oxidized mobile phase, the reduced-denatured insulin still could not be renatured. However, in the presence of 2.0 mol Lt-1 urea in the oxidized mobile phase employed, the reduced-denatured insulin can be refolded with SEC, and the aggregation of denatured insulin can be diminished by urea. In addition, the disulfide exchange of reduced-denatured insulin also can be accelerated with GSSG/GSH in the oxidized mobile phase. The three disulfide bridges of insulin were formed correctly and the reduced-unfolded insulin can be renatured completely. The results were further tested with reversed-phase liquid chromatography (RPLC) and hydrophobic interaction chromatography (HIC). 相似文献
997.
Xiu‐Li Dong Zheng‐Yu Zhou Lai‐Jin Tian Gang Zhao 《International journal of quantum chemistry》2005,102(4):461-469
The hydrogen bonding complexes HO(H2O)n (n = 1–3) were completely investigated in the present study using DFT and MP2 methods at varied basis set levels from 6‐31++G(d,p) to 6‐311++G(2d,2p). For n = 1 two, for n = 2 two, and for n = 3 five reasonable geometries are considered. The optimized geometric parameters and interaction energies for various complexes at different levels are estimated. The infrared spectrum frequencies and IR intensities of the most stable structures are reported. Finally, thermochemistry studies are also carried out. The results indicate that the formation and the number of hydrogen bonding have played an important role in the structures and relative stabilities of different complexes. © 2004 Wiley Periodicals, Inc. Int J Quantum Chem, 2005 相似文献
998.
This study aims to clarify the effects of carbon activation type and physical form on the extent of adsorption capacity and
desorption capacity of a bi-solute mixture of phenol and 2-chlorophenol (2-CP). For this purpose, two different PACs; thermally
activated Norit SA4 and chemically activated Norit CA1, and their granular countertypes with similar physical characteristics,
thermally activated Norit PKDA and chemically activated Norit CAgran, were used. The thermally activated carbons were better
adsorbers for phenol and 2-CP compared with chemically activated carbons, but adsorption was more reversible in the latter
case. 2-CP was adsorbed preferentially by each type of activated carbon, but adsorption of phenol was strongly suppressed
in the presence of 2-CP. The simplified ideal adsorbed solution (SIAS) model underestimated the 2-CP loadings and overestimated
the phenol loadings. However, the improved and modified forms of the SIAS model could better predict the competitive adsorption.
The type of carbon activation was decisive in the application of these models. For each activated carbon type, phenol was
desorbed more readily in the bi-solute case, but desorption of 2-CP was less compared with single-solute. This was attributed
to higher energies of 2-CP adsorption. 相似文献
999.
原子簇化合物的合成方法,由于条件限制,只有B、C、St等非金属元素与过渡金属袈基化合物等较为成熟.贵金属原子簇的合成则较困难.然而,应用激光等离子体反应,可使周期表内几乎所有元素都生成原子簇,为原子簇的生成与研究提供了一条新途径.该方法生成的原子簇在飞行时间质谱仪上可记录到一系列信号,某些信号呈现区域极大(或被称为‘匈数’吵].郑兰芬等用纯化的红磷粉分别与金粉、银粉混合,在激光等离子作源飞行时间质谱仪上得到一系列谱图【2]:ig与P作用只得到单核xg与P形成的lgy:iE离子簇.谱图较简单,*沪X最大可达叱叱… 相似文献
1000.
Solution redox chemistry of carbon nanotubes 总被引:1,自引:0,他引:1
UV/vis/NIR absorbance spectra were used to monitor electron transfer between small-molecule redox reagents and carbon nanotubes (CNTs). The oxidation of (6, 5)-enriched nanotubes in water with K(2)Ir(Cl)(6) reveals a valence electron density of 0.2-0.4 e(-)/100 carbon atoms and a reduction potential of approximately 800 mV versus NHE. The reduction potential of CNTs is found to increase with increasing band gap and to decrease with the introduction of an anionic dispersant. In light of this newly revealed redox chemistry of CNTs, we propose that the previously observed bleaching of the CNT absorbance spectrum at low pH is most likely a consequence of the oxidation of the nanotubes by oxygen. These results demonstrate facile oxidation and reduction of CNTs, provide a way to quantify the population of valence electrons, and point to possible applications of CNT in the catalysis of redox reactions. 相似文献