首页 | 本学科首页   官方微博 | 高级检索  
文章检索
  按 检索   检索词:      
出版年份:   被引次数:   他引次数: 提示:输入*表示无穷大
  收费全文   1521篇
  免费   152篇
  国内免费   177篇
化学   1133篇
晶体学   12篇
力学   88篇
综合类   13篇
数学   229篇
物理学   375篇
  2024年   3篇
  2023年   27篇
  2022年   36篇
  2021年   41篇
  2020年   42篇
  2019年   54篇
  2018年   36篇
  2017年   37篇
  2016年   73篇
  2015年   69篇
  2014年   72篇
  2013年   97篇
  2012年   124篇
  2011年   145篇
  2010年   89篇
  2009年   117篇
  2008年   112篇
  2007年   92篇
  2006年   96篇
  2005年   61篇
  2004年   52篇
  2003年   50篇
  2002年   27篇
  2001年   23篇
  2000年   42篇
  1999年   41篇
  1998年   25篇
  1997年   30篇
  1996年   18篇
  1995年   14篇
  1994年   20篇
  1993年   18篇
  1992年   13篇
  1991年   12篇
  1990年   9篇
  1989年   8篇
  1988年   4篇
  1987年   1篇
  1986年   1篇
  1985年   5篇
  1984年   1篇
  1983年   1篇
  1982年   3篇
  1980年   1篇
  1979年   1篇
  1978年   1篇
  1977年   1篇
  1976年   1篇
  1975年   1篇
  1973年   3篇
排序方式: 共有1850条查询结果,搜索用时 250 毫秒
61.
A simple approach to fabricate hybrid monolithic column within the confines of fused-silica capillaries (75 μm i.d.) was introduced. A polyhedral oligomeric silsesquioxanes (POSS) reagent containing a methacrylate group was selected as functional monomer, and copolymerized with bisphenol A dimethacrylate (BPADMA) or ethylene dimethacrylate (EDMA) in the presence of porogenic solvents via thermally initiated free radical polymerization. After optimization of the preparation conditions, two POSS-containing hybrid monoliths were successfully prepared and exhibited good permeability and stability. By comparison of the separation efficiencies of the resulting poly(POSS-co-BPADMA) and poly(POSS-co-EDMA) monoliths in capillary electrochromatography (CEC) and capillary liquid chromatography (cLC), it was indicated the former has better column efficiencies for alkylbenzenes, phenols, anilines and PAHs in CEC and cLC than the latter. Particularly, the hybrid poly(POSS-co-BPADMA) monolith is more suitable for separation of PAHs due to π–π interaction between the analytes and aromatic rings in the surface of monolithic stationary phase.  相似文献   
62.
63.
64.
The reaction of halogenated 9H-carbazoles or carbazole with bromoesters in DMF under microwave irradiation readily affords a series of 9H-carbazoles-9-hydroxylic acids.  相似文献   
65.
Two dinuclear succinato‐bridged nickel(II) complexes [Ni(RR‐L)]2(μ‐SA)(ClO4)2 ( 1 ) and [Ni(SS‐L)]2(μ‐SA)(ClO4)2 ( 2 ) (L = 5, 5, 7, 12, 12, 14‐hexamethyl‐1, 4, 8, 11‐tetraazacyclotetradecane, SA = succinic acid) were synthesized and characterized by EA, Circular dichroism (CD), as well as IR and UV/Vis spectroscopy. Single crystal X‐ray diffraction analyses revealed that the NiII atoms display a distorted octahedral coordination arrangement, and the succinato ligand bridges two central NiII atoms in a bis bidentate fashion to form dimers in 1 and 2 . The monomers of {[Ni(RR‐L)]2(μ‐SA)}2+ and {[Ni(SS‐L)]2(μ‐SA)}2+ are connected by O–H ··· O and N–H ··· O hydrogen bonds into a 1D right‐handed and left‐handed helical chain along the b axis, respectively. The homochiral natures of 1 and 2 are confirmed by the results of CD spectroscopy.  相似文献   
66.
Polydopamine (coded as PDA) is reported to be very adhesive and reactive due to the attached functional groups, such as amine and hydroxyl groups. In this work, taking advantage of the condensation between Si–OH of the hydroxylated alkyltrichlorosilane (ATS) and C–OH on PDA surface, ATS molecules with different chain carbon number of 10, 14 and 18 were grafted onto the 3‐aminopropyl triethoxysilane (APTES)‐PDA dual‐layer film, which was composed of PDA outerlayer and APTES underlayer, on Si substrate. Thus, hydrophobic trilayer films coded as APTES‐PDA‐ATS were prepared successfully. In order to reveal the dependence of the tribological behaviors upon the microstructures of the film, tribological experiments were conducted on an atomic force microscope and a ball‐on‐plate tribometer. Experimental results showed that the (micro‐) friction reducing (characterized by a parameter of relative friction coefficient or friction coefficient, RFC or FC) and macro‐wear resisting (characterized by anti‐wear life) behaviors were related with the chain length of outerlayer and the PDA thickness. Specifically, on one hand, as the chain length increases, RFC/FC decreased and macro anti‐wear life lengthened; on the other hand, as PDA gets thicker, RFC increased and the anti‐wear life enhanced. Copyright © 2013 John Wiley & Sons, Ltd.  相似文献   
67.
A one-pot strategy for the fabrication of the quantum dots loaded cerasome has been successfully developed based on the condensation of dihexadecylamine and 3-isocyanatopropyltriethoxysilane, followed by spontaneous encapsulation and solubilization of hydrophobic quantum dots into the hybrid liposomal cerasomes in combination of self-assembly and sol-gel process. Fourier transform infrared spectroscopy and mass spectra prove the formation of the intermediate organoalkoxysilane with a lipid-like structure, which forms cerasome vesicles. After encapsulation into cerasome, quantum dots become well dispersed in aqueous solution. Such water-soluble QD cerasomes exhibit a better photostability and retain the luminescence property of the original hydrophobic quantum dots.  相似文献   
68.
通过油相热分解法在石墨烯(Gr)的表面修饰单分散的Fe3O4纳米颗粒,然后将二亚乙基三胺五乙酸(DTPA)通过多巴胺(DPA)化学键合到到Gr复合物表面,制备了新型磁性纳米复合材料Gr@Fe3O4-DPA-DTPA,采用X射线衍射、透射电镜、振动样品磁强计、傅里叶红外、拉曼和紫外光谱等技术对该材料进行了表征。结果表明,材料对水中的芳香族化合物和重金属离子具有很强的吸附能力,对水中的萘和Cu2+的吸附容量分别达到207.9和72.2mg/g。  相似文献   
69.
尚秀丽  伍家卫  李薇  胡中爱 《化学通报》2013,(12):1132-1136
通过电化学原位聚合法制备多孔网状结构的聚苯胺(PANI)/醋酸纤维素(CA)复合膜电极,该复合膜的内层(与电极接触的一面)呈墨绿色,外层呈白色。采用原子力显微镜(AFM)、扫描电镜(SEM)、红外光谱(FTIR)对其形貌和化学组成进行表征。通过循环伏安、恒电流充放电和电化学阻抗研究了复合膜电极的超级电容特性。结果表明,多孔网状结构的PANI/CA复合材料具有良好的电容性能,其比电容可达到410F/g,并且该超级电容器具有较小的内阻和较好的循环稳定性,300次循环后,容量仍维持在342F/g,比电容的保持率为83.4%。  相似文献   
70.
Two new organic building units that contain dicarboxylate sites for their self‐assembly with paddlewheel [Cu2(CO2)4] units have been successfully developed to construct two isoreticular porous metal–organic frameworks (MOFs), ZJU‐35 and ZJU‐36, which have the same tbo topologies (Reticular Chemistry Structure Resource (RCSR) symbol) as HKUST‐1. Because the organic linkers in ZJU‐35 and ZJU‐36 are systematically enlarged, the pores in these two new porous MOFs vary from 10.8 Å in HKUST‐1 to 14.4 Å in ZJU‐35 and 16.5 Å in ZJU‐36, thus leading to their higher porosities with Brunauer–Emmett–Teller (BET) surface areas of 2899 and 4014 m2 g?1 for ZJU‐35 and ZJU‐36, respectively. High‐pressure gas‐sorption isotherms indicate that both ZJU‐35 and ZJU‐36 can take up large amounts of CH4 and CO2, and are among the few porous MOFs with the highest volumetric storage of CH4 under 60 bar and CO2 under 30 bar at room temperature. Their potential for high‐pressure swing adsorption (PSA) hydrogen purification was also preliminarily examined and compared with several reported MOFs, thus indicating the potential of ZJU‐35 and ZJU‐36 for this important application. Studies show that most of the highly porous MOFs that can volumetrically take up the greatest amount of CH4 under 60 bar and CO2 under 30 bar at room temperature are those self‐assembled from organic tetra‐ and hexacarboxylates that contain m‐benzenedicarboxylate units with the [Cu2(CO2)4] units, because this series of MOFs can have balanced porosities, suitable pores, and framework densities to optimize their volumetric gas storage. The realization of the two new organic building units for their construction of highly porous MOFs through their self‐assembly with [Cu2(CO2)4] units has provided great promise for the exploration of a large number of new tetra‐ and hexacarboxylate organic linkers based on these new organic building units in which different aromatic backbones can be readily incorporated into the frameworks to tune their porosities, pore structures, and framework densities, thus targeting some even better performing MOFs for very high gas storage and efficient gas separation under high pressure and at room temperature in the near future.  相似文献   
设为首页 | 免责声明 | 关于勤云 | 加入收藏

Copyright©北京勤云科技发展有限公司  京ICP备09084417号