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   48523篇
  免费   8927篇
  国内免费   7806篇
化学   36259篇
晶体学   810篇
力学   3188篇
综合类   562篇
数学   5793篇
物理学   18644篇
  2024年   107篇
  2023年   914篇
  2022年   1278篇
  2021年   1739篇
  2020年   2035篇
  2019年   2068篇
  2018年   1697篇
  2017年   1808篇
  2016年   2425篇
  2015年   2542篇
  2014年   3113篇
  2013年   3933篇
  2012年   4633篇
  2011年   4696篇
  2010年   3531篇
  2009年   3481篇
  2008年   3773篇
  2007年   3168篇
  2006年   2944篇
  2005年   2397篇
  2004年   1874篇
  2003年   1550篇
  2002年   1663篇
  2001年   1372篇
  2000年   1089篇
  1999年   930篇
  1998年   662篇
  1997年   594篇
  1996年   553篇
  1995年   439篇
  1994年   445篇
  1993年   326篇
  1992年   251篇
  1991年   231篇
  1990年   188篇
  1989年   117篇
  1988年   115篇
  1987年   84篇
  1986年   100篇
  1985年   72篇
  1984年   35篇
  1983年   45篇
  1982年   24篇
  1981年   25篇
  1980年   13篇
  1979年   21篇
  1977年   14篇
  1974年   10篇
  1957年   11篇
  1925年   10篇
排序方式: 共有10000条查询结果,搜索用时 15 毫秒
981.
A series of 2-alkylbenzimidazole derivatives 9a-n have been designed and synthesized as a novel class of non-peptide angiotensin Ⅱ AT1 receptor antagonists. The synthesized compounds were evaluated for their antagonism of angiotensin Ⅱ, induced contraction in the rabbit thoracic aortic ring and the results showed that compounds 9a, 9g and 9j exhibited potent antagonistic activity of AT1 receptor.  相似文献   
982.
This paper compares the kinetics of exchanges of phenylethanethiolate ligands (PhC2S-) of the monolayer-protected clusters (MPCs) Au(38)(SC2Ph)(24) and Au(140)(SC2Ph)(53) with p-substituted arylthiols (p-X-PhSH), where X = NO(2), Br, CH(3), OCH(3), and OH. First-order rate constants at 293 K for exchange of the first ca. 25% of the ligands on the molecule-like Au(38)(SC2Ph)(24) MPC, measured using (1)H NMR, vary linearly with the in-coming arythiol concentration; ligand exchange is an overall second-order reaction. Remarkably, the second-order rate constants for ligand exchange on Au(38)(SC2Ph)(24) are very close to those of corresponding exchange reactions on the larger nanoparticle Au(140)(SC2Ph)(53) MPCs. These are the first results that quantitatively show that the chemical reactivity of different sized nanocrystals is almost independent of size; presumably, this is because the locus of the initial ligand exchanges is a common kind of site, thought to be the nanocrystal vertexes. The rates of later stages of exchange (beyond ca. 25%) differ for Au(38) and Au(140) cores, the latter being much slower presumably due to its larger terrace-like surface atom content. The reverse exchange reaction was studied for Au(38)(p-X-arylthiolate)(24) MPCs (X = NO(2), Br, and CH(3)), where the in-coming ligand is now phenylethanethiol. Remarkably, the rate constants of both forward and reverse exchanges display identical substituent effects, which implies a concurrent bonding of both in-coming and leaving ligands to the Au core in the rate-determining step, as in an associative mechanism. X = NO(2) gives the fastest rates, and the ratio of forward and reverse rate constants gives an equilibrium constant of K(EQ,PE) = 4.0 that is independent of X.  相似文献   
983.
煤的孔结构特征对水煤浆性质的影响   总被引:7,自引:3,他引:7  
本文选用17种不同变质程度的中国煤,详细研究了煤孔结构特征对煤浆性质的影响。发现煤孔体积通过影响煤在分散体系中的吸水性,从而影响煤之成浆性。但由于不同变质程度煤表面亲水性的显著差异,煤孔体积在影响煤成浆性的能力方面差别很大,这使得煤吸水性和浆体最高煤浓度与煤孔体积并不存在直接的相关性,而是取决于煤孔体积V和以煤-水接触角(θ)的余弦值表示的煤表面亲水性因子的乘积,即煤之有效孔体积:V×cos(θ/  相似文献   
984.
白卡奴鸽动脉粥样硬化模型微量元素谱的计算机多元分析   总被引:1,自引:0,他引:1  
用ICP-AES测定了白卡奴鸽动脉粥样硬化模型和对照组的器官和组织中19种元素含量,通过因子分析,取得一系列因子得分图,结果表明,动脉粥样硬化和对照组样品点分布在不同区域,且可分辨。  相似文献   
985.
用HNO3-HCl溶解试样,在几个相同量的试液中,分别加入质量浓度依次递增的5种元素的标准溶液,用火焰原子吸收法连续测定了Fe、Pb、Sb、Zn和Ni的含量,建立了优化的仪器测定条件,并对可能存在的元素进行了干扰试验。结果表明,Fe、Pb、Sb等5种元素的回收率为98.0%~102.3%,相对标准偏差为1.4%~2.5%。  相似文献   
986.
By using 13C MAS NMR spectroscopy (MAS = magic angle spinning), the conversion of selectively 13C-labeled n-butane on zeolite H-ZSM-5 at 430-470 K has been demonstrated to proceed through two pathways: 1) scrambling of the selective 13C-label in the n-butane molecule, and 2) oligomerization-cracking and conjunct polymerization. The latter processes (2) produce isobutane and propane simultaneously with alkyl-substituted cyclopentenyl cations and condensed aromatic compounds. In situ 13C MAS NMR and complementary ex situ GC-MS data provided evidence for a monomolecular mechanism of the 13C-label scrambling, whereas both isobutane and propane are formed through intermolecular pathways. According to 13C MAS NMR kinetic measurements, both pathways proceed with nearly the same activation energies (E(a) = 75 kJ mol(-1) for the scrambling and 71 kJ mol(-1) for isobutane and propane formation). This can be rationalized by considering the intermolecular hydride transfer between a primarily initiated carbenium ion and n-butane as being the rate-determining stage of the n-butane conversion on zeolite H-ZSM-5.  相似文献   
987.
LB films of three amphiphilic tris(phthalocyaninato) rare earth triple-decker complexes with crown-ethers as hydrophilic heads and long alkyl chains as hydrophobic tails have been prepared and found to display very well ordered layer structures, as proved by pi-A isotherms, UV-vis and polarized absorption spectra, X-ray diffraction experiments, and microscopic morphology characterization. These LB films have been fabricated into field-effect transistor (FET) devices, which show carrier mobilities as high as 0.24-0.60 cm2 V-1 s-1, among the highest mobilities achieved thus far for all LB film-based OFETs.  相似文献   
988.
Neutron diffraction data have been collected on a powdered sample of Sr2IrD5 over a range of temperatures. The compound, which is cubic at room temperature, has been found to exhibit a gradual transformation to a tetragonal phase in the temperature range 200-140 K. As a result of the transition, deuterium atoms which randomly occupy sixfold positions in the cubic phase, become tetragonally ordered. A small fraction of the cubic phase remained untransformed at 4.2 K. Both the cubic and tetragonal structures are consistent with square pyramidal IrD5 units with average Ir---D distances of 1.714 and 1.718 Å, respectively. Agreement factors, R1, for the two structural analyses are 3.44 and 4.94%.  相似文献   
989.
The micro construction of poly(epsilon-caprolactone) (PCL) and poly(L-lactic acid) (PLLA) blend films fabricated by solution casting under microwave irradiation was investigated by selective enzymatic degradation and scanning electron microscopy (SEM). The results were totally different from the blends obtained by conventional methods. The blend was more homogeneous and the PCL continuous phase more compact as no spherulites and tiny zone separation were observed from the film surface and no PCL network was observed inside the film, and the degradation of a PCL plank by Pseudomonas lipase was significantly retarded. The distributed PLLA micro spheres were enlarged and amorphous. The thermal behavior of the blend by microwave heating revealed that PCL and PLLA underwent a melting process, which induced the variations of the PCL phase and PLLA spheres. The weight loss caused by degradation of the PCL/PLLA blend obtained by conventional methods (B50c) is greater than that of the blend obtained by microwave methods (B50m), which reflects the change in morphology from a loose PCL network (B50c) to a dense PCL plank (B50m).  相似文献   
990.
Among the reactions in which C-C bonds are formed, the Baylis-Hillman coupling of aldehydes with α, β-unsaturated carbonylic compounds is currently attracting much interest due to the atom economy, the mild conditions and the generation of functional groups1,2. Furthermore, compared to the Heck, Suzuki and other palladium catalyzed C-C bond forming reaction3, the Baylis-Hillman reaction can be promoted by using organic bases in the complete absence of any metal4. However, almost all the …  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