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   22957篇
  免费   3357篇
  国内免费   2481篇
化学   16135篇
晶体学   276篇
力学   1358篇
综合类   187篇
数学   2297篇
物理学   8542篇
  2024年   69篇
  2023年   428篇
  2022年   740篇
  2021年   842篇
  2020年   850篇
  2019年   835篇
  2018年   716篇
  2017年   738篇
  2016年   1017篇
  2015年   1037篇
  2014年   1171篇
  2013年   1615篇
  2012年   1881篇
  2011年   2002篇
  2010年   1302篇
  2009年   1279篇
  2008年   1475篇
  2007年   1353篇
  2006年   1222篇
  2005年   972篇
  2004年   776篇
  2003年   662篇
  2002年   632篇
  2001年   461篇
  2000年   454篇
  1999年   483篇
  1998年   422篇
  1997年   423篇
  1996年   463篇
  1995年   365篇
  1994年   381篇
  1993年   272篇
  1992年   254篇
  1991年   233篇
  1990年   165篇
  1989年   129篇
  1988年   117篇
  1987年   97篇
  1986年   95篇
  1985年   85篇
  1984年   58篇
  1983年   49篇
  1982年   38篇
  1981年   28篇
  1980年   31篇
  1979年   18篇
  1978年   10篇
  1977年   8篇
  1975年   7篇
  1973年   6篇
排序方式: 共有10000条查询结果,搜索用时 0 毫秒
161.
Ge-132对小鼠H22肝癌移植瘤的实验研究证明:1.Ge-132对H22肝癌移植瘤有一定的抑制作用,300mg/kg体重剂量抑瘤率达到36.19%;2.增强机体的抗氧化作用,抑制脂质的过氧化物水平;3.促进免疫功能,当Ge-132和环磷酰胺联合使用时,可抵抗环磷酰胺的免疫抑制作用,而且并不减弱其抑制瘤作用。  相似文献   
162.
Highly ordered rod-like large-pore periodic mesoporous organosilica (PMO) was successfully synthesized at low acid concentration with the assistance of inorganic salt using triblock copolymer P123 as a template. The roles of inorganic salt and acidity in the production of highly ordered mesostructure and the morphology control of PMOs were investigated. It was found that the inorganic salt can significantly widen the range of the synthesis parameters to produce highly ordered 2D hexagonal pore structure of p6mm symmetry. However, the uniform rod-like PMOs can only be synthesized in a narrow range of acid and salt concentrations, which were sensitive to induction time. The adsorption of lysozyme on PMO was studied at different pH values in comparison with adsorption on pure silica material under controlled morphology and pore structure. It was found that the adsorption capacity of lysozyme on the PMO was lower than that on pure SBA-15 silica material and the adsorption amounts are larger at pH 9.6 than at 7.0 for both materials. The results show that the electrostatic interaction between lysozyme and PMO/SBA-15 surface is more dominant than the hydrophobic forces and the interaction of neighboring lysozyme molecules also plays an important role.  相似文献   
163.
Baker's yeast mediated reduction of acenaphthenequinone within 4-10 h afforded mono-hydroxyacenaphthenone mainly with low enantioselectivity, the substrate and mono-hydroxyacenaphthenone product almost converted to dihydroxyacenaphthene after 48 h. By control of the reaction time and in the presence of DMF as co-solvent, the reduction of 6-substituted acenaphthenequinones under vigorous agitation afforded the corresponding 2-hydroxyacenaphthenones in 24-84% yields with 10-93% ee.  相似文献   
164.
Ren X  Meng Q  Song Y  Lu C  Hu C  Chen X 《Inorganic chemistry》2002,41(22):5686-5692
Three ion-pair complexes, [RbzPy](+)[Ni(mnt)(2)](-) (mnt(2)(-) = maleonitriledithiolate; [RbzPy](+) = 4-R-benzylpyridinium; R = Br (1), Cl (2), and NO(2) (3)), with unusual magnetic properties have been synthesized and characterized. The crystal structures of 1 and 2 have been solved. The two complexes belong to the P2(1)/c space group with Z = 4 and C(20)H(11)BrN(5)NiS(4), a = 12.0744(17) A, b = 26.369(4) A, c = 7.440(3) A, and beta = 102.63(3) degrees for 1 and C(20)H(11)ClN(5)NiS(4), a = 12.105(2) A, b = 26.218(4) A, c = 7.374(2) A, and beta = 102.55(2) degrees for 2, respectively. The [Ni(mnt)(2)](-) anions in 1-3 form uniformly spaced one-dimensional (1-D) magnetic chains of s = 1/2 at room temperature. The temperature dependences of the susceptibility for 1-3 show that they undergo phase transitions. All three complexes are paramagnetic in their high-temperature (abbreviation HT) phase and diamagnetic in the low-temperature (abbreviation LT) phase because of strong dimerization along the stacking direction. The results of thermal analysis (DSC) further confirm that the phase transition for 1 and 2 is first-order but maybe second-order for 3. The phenomena observed in this study are similar to those of the 1-D radical systems.  相似文献   
165.
卢水明  毛丽娟 《合成化学》1998,6(4):335-338
利用N,N-二(2-氯乙基)氨基磷酰二异氰酸酯和胺的加成反应,合成了2,4,6三氧-1,3,5,2三氮磷杂环己烷衍生物,它们的结构经^1HNMR,IR和元素分析所证实。初步生物活性测试结果表明,部分化合物具有一定的抗肿瘤活性。  相似文献   
166.
取代苯酚中共振增强的分子内氢键   总被引:2,自引:0,他引:2  
根据晶体结构资料,计算了59个邻位取代苯酚中分子内氢键的几何.在STO-3G水平上计算了一些分子中原子部分电荷.结果表明,酚基氧与苯环上碳之间的键长,酚基上氢原子的部分电荷,酚基所在位置处的苯环环内角与取代苯酚的酸常数pKa均有近似线性关系,当邻位上存在硝基或羰基时,内氢键由于共振而得到显著的增强,据此可说明这一类酚的显著酸性  相似文献   
167.
Studiesonkineticsofradicalreactions[1]andonCHbonddissociationenergies(BDE)[2]haveshownthatcarbonradicalsarestabilizedbyeitheranelectrondonatinggroup(EDG)oranelectronwithdrawinggroup(EWG),andthatifacarbonradicalissubstitutedwithbothanEDGandanEWGatthesamecen…  相似文献   
168.
A Taylor dispersion tube has been used to measure mutual diffusion in aqueous solutions of glycine hydrochloride at 25°C and concentrations from 0.0005 to 0.5 M. Analysis of the dispersion profiles shows that the diffusion of glycine hydrochloride (GlyHCl) produces a subtantial additional flow of hydrochloric acid that is liberated by the dissociation: GlyH+ + Cl- Gly + H+ + Cl-. Diffusion in this system is, therefore, a ternary process described by the equations J 1(GlyHCl) = – D 11C 1D 12C 2 and J 2(HCl) = –D 21C 1D 22C 2 for the coupled fluxes of total glycine hydrochloride (1) and hydrochloric acid (2) components. The ratio D 21/D 11 of measured diffusion coefficients indicates that up to two moles of HCl are cotransported per mole of GlyHCl. Although protonated glycine diffuses with relatively mobile Cl counterions, the main diffusion coefficient of glycine hydrochloride, D 11, is lower than or nearly identical to the diffusion coefficient of aqueous glycine. A model for the diffusion of protonated solutes is developed to interpret this result and the large coupled flows of HCl. Diffusion coefficients are also reported for the aqueous hydrochlorides of 3- and 4-aminobenzoic acids.  相似文献   
169.
A plasma induced degradation process has been studied to treat 4-nitrotoluene (4-NT) present as an aqueous pollutant. The plasma was locally generated from a glow discharge around a tip of a platinum anode in an electrolytic solution. The influence of initial pH and Fe2+ on the degradation was examined. Major intermediates resulting from the degradation process were identified. Amongst the aromatic intermediates, p-hydroxybenzoic acid was the predominant degradation product. The formation of oxalic acid, malic acid was also observed. The final products of degradation were NH 4 + , NO 3 and CO2. Based on the analysis of intermediates and the kinetic considerations, the degradation was shown to follow a pseudo-first order reaction hence, a possible reaction pathway was proposed.  相似文献   
170.
测定了Pt-Sn型催化剂浸渍状态下的Sn-119、Pt-195的多核核磁共振。当SnCl2/DCl溶液体系中加入H2PtCl6以后,出现了Sn(Ⅳ)和另外一种Sn(Ⅱ)的构型,Sn-119峰向高场位移,说明部分Sn(Ⅱ)被氧化成Sn(Ⅳ),H2PtCl6的量对这种氧化性影响较小。而H2PtCl6/D2O溶液体系中加入SnCl2以后部分Pt(Ⅳ)被还原成Pt(Ⅱ),随着SnCl2量的增加,Pt(Ⅱ)  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