全文获取类型
收费全文 | 24580篇 |
免费 | 906篇 |
国内免费 | 129篇 |
专业分类
化学 | 16469篇 |
晶体学 | 252篇 |
力学 | 725篇 |
数学 | 2272篇 |
物理学 | 5897篇 |
出版年
2023年 | 163篇 |
2022年 | 426篇 |
2021年 | 582篇 |
2020年 | 458篇 |
2019年 | 464篇 |
2018年 | 404篇 |
2017年 | 385篇 |
2016年 | 719篇 |
2015年 | 627篇 |
2014年 | 863篇 |
2013年 | 1487篇 |
2012年 | 1793篇 |
2011年 | 2010篇 |
2010年 | 1270篇 |
2009年 | 1096篇 |
2008年 | 1672篇 |
2007年 | 1453篇 |
2006年 | 1479篇 |
2005年 | 1259篇 |
2004年 | 1112篇 |
2003年 | 940篇 |
2002年 | 882篇 |
2001年 | 544篇 |
2000年 | 484篇 |
1999年 | 335篇 |
1998年 | 214篇 |
1997年 | 211篇 |
1996年 | 273篇 |
1995年 | 187篇 |
1994年 | 202篇 |
1993年 | 209篇 |
1992年 | 153篇 |
1991年 | 123篇 |
1990年 | 130篇 |
1989年 | 101篇 |
1988年 | 74篇 |
1987年 | 74篇 |
1986年 | 52篇 |
1985年 | 75篇 |
1984年 | 52篇 |
1983年 | 42篇 |
1982年 | 64篇 |
1981年 | 64篇 |
1979年 | 48篇 |
1978年 | 45篇 |
1977年 | 36篇 |
1976年 | 41篇 |
1975年 | 37篇 |
1974年 | 36篇 |
1973年 | 34篇 |
排序方式: 共有10000条查询结果,搜索用时 15 毫秒
831.
832.
833.
834.
835.
836.
A polyacrylonitrile (PAN) fiber was adopted for the backbone of a chelate polymer and poly(acrylo‐amidino ethylene amine) (PAEA) was prepared through a one‐step reaction between the PAN fiber and ethylenediamine (EDA). The maximum removal capacity and degree of substitution were 7.8 meq per gram of dried PAEA and 98%, respectively. The PAEA was tested as an adsorbent in single and two‐component metal aqueous solutions under changing pH. The Cu2+ ion accomplished maximum adsorption amount at pH 3 and the order of maximum adsorbed amounts on PAEA is Cu2+ > Ag+ > Zn2+ > Ni2+ > Pb2+ in molar basis. FT‐IR spectroscopy was employed to characterize the chemical bonding in metal aqueous solutions and surface morphology was examined using atomic force microscopy (AFM) and scanning electron microscopy (SEM). Copyright © 2004 John Wiley & Sons, Ltd. 相似文献
837.
A novel zirconia-based hybrid organic-inorganic sol-gel coating was developed for capillary microextraction (CME) (in-tube SPME). High degree of chemical inertness inherent in zirconia makes it very difficult to covalently bind a suitable organic ligand to its surface. In the present work, this problem was addressed from a sol-gel chemistry point of view. Principles of sol-gel chemistry were employed to chemically bind a hydroxy-terminated silicone polymer (polydimethyldiphenylsiloxane, PDMDPS) to a sol-gel zirconia network in the course of its evolution from a highly reactive alkoxide precursor undergoing controlled hydrolytic polycondensation reactions. A fused silica capillary was filled with a properly designed sol solution to allow for the sol-gel reactions to take place within the capillary for a predetermined period of time (typically 15-30 min). In the course of this process, a layer of the evolving hybrid organic-inorganic sol-gel polymer got chemically anchored to the silanol groups on the capillary inner walls via condensation reaction. At the end of this in-capillary residence time, the unbonded part of the sol solution was expelled from the capillary under helium pressure, leaving behind a chemically bonded sol-gel zirconia-PDMDPS coating on the inner walls. Polycyclic aromatic hydrocarbons, ketones, and aldehydes were efficiently extracted and preconcentrated from dilute aqueous samples using sol-gel zirconia-PDMDPS coated capillaries followed by thermal desorption and GC analysis of the extracted solutes. The newly developed sol-gel hybrid zirconia coatings demonstrated excellent pH stability, and retained the extraction characteristics intact even after continuous rinsing with a 0.1 M NaOH solution for 24 h. To our knowledge, this is the first report on the use of a sol-gel zirconia-based hybrid organic-inorganic coating as an extraction medium in solid phase microextraction (SPME). 相似文献
838.
Kim SY Augustine S Eo YJ Bae BS Woo SI Kang JK 《The journal of physical chemistry. B》2005,109(19):9397-9403
We use a first-principles calculation and small-angle neutron scattering (SANS) to investigate the mechanism and the nanosize products of the sol-gel reaction with diphenylsilanediol (DPD) and 3-methacryloxypropyltrimethoxysilane (MEMO) precursors in synthesizing a hybrid waveguide material. It is predicted that switching between a DPD hydroxyl and a MEMO methoxy with a reaction rate of 6.8 x 10(-6) s(-1) at 300 K is the fastest process for the first reaction step, thus generating diphenylmethoxysilanol (DPM) and 3-methacryloxypropyldimethoxysilanol (MEDO) as products. However, we determine that this reaction pathway could be modified by the presence of the H2O released from a catalyst such as Ba(OH)2.H2O. Next, switching between the DPM hydroxyl and the MEDO methoxy is followed to generate diphenyldimethoxysilane (DPDM) and 3-methacryloxypropylmethoxysilanediol (MEMDO). However, condensation between a MEMDO hydroxyl and a DPDM methoxy is found to be most favorable for the third reaction step, which generates the DPDM-MEMDO dimer and CH3OH molecule as products. In a similar fashion, a DPDM methoxy of the DPDM-MEMDO dimer can condense with a MEMDO hydroxyl of the second DPDM-MEMDO dimer to increase the chain, but its reaction rate of 2.8 x 10(-11) s(-1) is predicted to be about 5 times smaller than that between a DPDM methoxy and a MEMDO hydroxyl. This implies that the reaction rate for the larger nanostructures becomes smaller. Additionally, our SANS measurements determine that the final products from our sol-gel reaction are on the nanometer scale, at sizes from 1.76 to 2.36 nm. 相似文献
839.
Mildred M. Maguire Huang Do Son Kim Nguyen Chau Vo Douglas Smith Grant Koher Gregg Doutt Martyn C.R. Symons 《Journal of organometallic chemistry》1984,269(2):183-189
Exposure of (C5H5)2MO(CH3)2 and (C5H5)2W(CH3)2, prepared from the corresponding dichlorides, to 20Co γ-rays at 77 K gave H2C.CML3 carbene species characterised by their ESR spectra, together with a central feature possibly due to the parent cations. Dilute solutions in CD3OD gave features assigned to the parent anions which were converted on bleaching with visible light into methyl radicals, and H2C.ML3 radicals. From the magnitude of the 1H and 183W hyperfine coupling constants, it is deduced that the SOMO for H2C.WL3 radicals is strongly localised on carbon.Dilute solutions in aqueous sulphuric acid also gave species with A(2H) = 20 G, identified as the carbene derivatives, H2C.Ml3. These were formed on annealing, as signals assigned to HSO4 · radicals were lost. 相似文献
840.
Fujishima H Takeshita H Toyota M Kim HS Wataya Y Tanaka M Sasaki T Ihara M 《Chemical & pharmaceutical bulletin》2001,49(5):572-575
Biological evaluations of bicyclo[6.4.0]dodecenone derivatives on antimalarial activity in vitro against Plasmodium falciparum and cytotoxicity against human KB cells were made. (+/-)-(1R*,4S*,7R*,8S*)-4-tert-Butyl-dimethylsiloxy-5,5-dimethyl-1-methyl-9-methylene-7-phenylsulfonylbicyclo[6.4.0]dodec-2,11-dien-10-one (15) exhibited potent antimalarial activity, whereas (+/-)-(1R*,7R*,8S*)-1-methyl-9-methylene-7-phenylsulfonylbicyclo[6.4.0]dodec-2,11-dien-10-one (14) showed significant cytotoxic activity in human KB cells. Both 14 and 15 possess, as a structural character, the exo-methylene moiety in their 6-membered ring of the 8-6 fused ring system. 相似文献