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   11812篇
  免费   1952篇
  国内免费   1975篇
化学   9570篇
晶体学   165篇
力学   595篇
综合类   155篇
数学   1384篇
物理学   3870篇
  2023年   126篇
  2022年   227篇
  2021年   274篇
  2020年   373篇
  2019年   411篇
  2018年   334篇
  2017年   285篇
  2016年   565篇
  2015年   560篇
  2014年   683篇
  2013年   833篇
  2012年   938篇
  2011年   1048篇
  2010年   797篇
  2009年   812篇
  2008年   986篇
  2007年   871篇
  2006年   788篇
  2005年   650篇
  2004年   603篇
  2003年   477篇
  2002年   633篇
  2001年   487篇
  2000年   387篇
  1999年   235篇
  1998年   167篇
  1997年   123篇
  1996年   144篇
  1995年   120篇
  1994年   106篇
  1993年   97篇
  1992年   61篇
  1991年   58篇
  1990年   40篇
  1989年   36篇
  1988年   33篇
  1987年   28篇
  1986年   25篇
  1985年   30篇
  1984年   26篇
  1983年   22篇
  1982年   20篇
  1981年   21篇
  1980年   18篇
  1979年   23篇
  1978年   26篇
  1977年   18篇
  1976年   19篇
  1975年   15篇
  1974年   13篇
排序方式: 共有10000条查询结果,搜索用时 15 毫秒
151.
Wang CH  Chen SM  Wang CM 《The Analyst》2002,127(11):1507-1511
The anodic polymerization of 3-aminophthalhydrazide (luminol) and iron(II) tris 5-aminophenanthroline (Fe(phen-NH2)3(2+)) has been reported in this paper. A bilayer electrode was developed based on these polymers and the ITO conductive glass (denoted ITO[Fe(phen-NH2)3(2+)]luminol electrode). This electrode emitted light (lambdaem: 430 nm) as it was brought into contact with H2O2. At pH 10, the resulting electrochemiluminescence (ECL) showed a linear relationship with the concentration of H2O2 in the range of 10 microM(-1) mM. This bilayer electrode also showed an application potential for the detection of glucose after being further modified with glucose oxidase (denoted ITO[Fe(phen-NH2)3(2+)]luminol]GOx electrode). Although the resulting ECL decayed more rapidly in concentrated glucose solutions (e.g., I M) because of the consumption of luminol during use, the decay became less severe in diluted glucose solutions (e.g., 10 mM). According to the flow injection analysis, a linear relationship existed between the ECL and the concentration of glucose from 10(-5)-10(-3) M at pH 9. The detection limit could reach a level of 5 x 10(-5) M at this pH.  相似文献   
152.
153.
The secondary reduction in the direct and oxazaborolidine‐catalyzed asymmetric borane reduction of ketones was investigated by the use of GC/MS tracing titration and control experiments. The results indicate that the secondary reduction affects the enantioselectivity only in noncoordinated solvents at low temperature and not under the usual catalytic reduction conditions because the intermediate alkoxyborane is unstable and quickly converts to borane and dialkoxyborane. The function of an alcohol additive in the asymmetric borane reduction of ketones is to consume excess borane in the reduction system thus inhibiting noncatalytic reduction, which leads to increased enantioselectivity in the catalytic reduction.  相似文献   
154.
A novel process is proposed for synthesis of spinel LiMn2O4 with spherical particles from the inexpensive materials MnSO4, NH4HCO3, and NH3H2O. The successful preparation started with carefully controlled crystallization of MnCO3, leading to particles of spherical shape and high tap density. Thermal decomposition of MnCO3 was investigated by both DTA and TG analysis and XRD analysis of products. A precursor of product, spherical Mn2O3, was then obtained by heating MnCO3. A mixture of Mn2O3 and Li2CO3 was then sintered to produce LiMn2O4 with retention of spherical particle shape. It was found that if lithium was in stoichiometric excess of 5% in the calcination of spinel LiMn2O4, the product had the largest initial specific capacity. In this way spherical particles of spinel LiMn2O4 were of excellent fluidity and dispersivity, and had a tap density as high as 1.9 g cm–3 and an initial discharge capacity reaching 125 mAh g–1. When surface-doped with cobalt in a 0.01 Co/Mn mole ratio, although the initial discharge capacity decreased to 118 mAh g–1, the 100th cycle capacity retention reached 92.4% at 25°C. Even at 55°C the initial discharge capacity reached 113 mAh g–1 and the 50th cycle capacity retention was in excess of 83.8%.  相似文献   
155.
Phenylsulfonic acid functionalized mesoporous silica was synthesized by condensation of tetraethylorthosilicate with phenyltrimethoxysilane, and then sulfonation using 30% fuming sulfuric acid. The material was characterized using FT‐IR, DSC, XPS, TEM and N2 adsorption/desorption measurements. DSC revealed that sulfonic acid group of the catalyst was decomposed at 354.8°C, indicating that the catalyst exhibited high thermal stability. XPS showed that there existed three kinds of different silicon species on surface of the catalyst. The catalytic performance of the catalyst was evaluated using transetherification of alcohols with dimethoxymethane. It was found that among primary alcohols, the selectivities of the two long‐chain alcohols for n‐dedocanol and n‐tetradecyl alcohol were higher than 97.0% at the conversions of 43.6% and 65.3%, respectively, while the selectivities of the short‐chain alcohols except for n‐hexanol were less than 90.0% at the conversions of over 80.0%. Due to steric barrier, the secondary alcohols such as iso‐butanol and cyclohexanol afforded conversions of 79.4% and 60.5%, and the selectivities of the two alcohols were more than 90.0%. The sequence in conversion of the substituted phenols is as follows: p‐nitrophenol>p‐fluorophenol≥p‐bromophenol>p‐cresol>m‐cresol.  相似文献   
156.
We have characterized, in vitro, interactions between hippocampal neuronal cells and silica microbeads coated with synthetic, fluid, lipid bilayer membranes containing the glycosylphosphatidyl inositol (GPI)-linked extracellular domain of the postsynaptic membrane protein neuroligin-1. These bilayer-neuroligin-1 beads activated neuronal cells to form presynaptic nerve terminals at the point of contact in a manner similar to that observed for live PC12 cells, ectopically expressing the full length neuroligin-1. The synthetic membranes exhibited biological activity at neuroligin-1 densities of approximately 1 to 6 proteins/microm(2). Polyolycarbonate beads with neuroligin-1 covalently attached to the surface failed to activate neurons despite the fact that neuroligin-1 binding activity is preserved. This implies that a lipid membrane environment is likely to be essential for neuroligin-1 activity. This technique allows the study of isolated proteins in an environment that has physical properties resembling those of a cell surface; proteins can diffuse freely within the membrane, retain their in vivo orientations, and are in a nondenatured state. In addition, the synthetic membrane environment affords control over both lipid and protein composition. This technology is easily implemented and can be applied to a wide variety of cellular studies.  相似文献   
157.
Selenium nanoparticles were prepared by a reverse microemulsion system. Sodium selenosulfate was used as selenium source. The results showed that hydrochloric acid concentration and reaction temperature had great influence on the morphology of products. The crystalline selenium nanowires and amorphous selenium nanorods were obtained in given condition.  相似文献   
158.
PU大分子单体水溶液性质   总被引:2,自引:0,他引:2  
双亲聚合物一般由亲水和亲油 2种链段构成 ,有嵌段型[1,2 ] 和接枝型[3 ] 2种 ,其中通过大分子单体法合成双亲接枝聚合物备受关注[4] 。如以亲水性大分子单体和亲油性小分子单体共聚 ,大分子单体构成共聚物主链上支链 ,具有较大活动性 ,亲水效能高。采用对氯甲基苯乙烯[5] 或甲基丙烯酰氯[6] 与聚氧化乙烯大分子的一端相反应 ,可得到亲水性大分子单体 ,但其分子量及结构变化有限。本文采用常规条件 ,合成了嵌段式水溶性聚氨酯大分子单体 ,其分子量较大 ,共聚接枝的支链较长。利用该大分子单体具有非离子高分子表面活性剂的性质 ,采用无皂乳…  相似文献   
159.
The formation of a water meniscus between a sharp tip and a solid surface is one of the prevailing requirements for scanning probe microscope (SPM)-based lithographies, such as dip-pen nanolithography (DPN) and conductive tip induced oxidation. The water meniscus functions as a medium for the oxidation of or mass transfer to the solid surface. Here we report a simple, efficient, and effective approach to enhance the local relative humidity and thus increase the size of the water meniscus by bringing a water-containing capillary tube to the proximity of the tip-surface contact area. The enhancement in local relative humidity is confirmed via an increase in the measured tip-surface adhesion forces and the widths of DPN generated parallel lines. Compared to the global control of relative humidity for the whole lithography system, the short distance between the "water reservoir" and the tip-surface contact area enables rapid increase in the local vapor pressure of water, less perturbation, and minimal erosion to the state-of-the-art electronics. As a result, most scanning probe lithography experiments at high relative humidity can now be performed in a reasonable time frame.  相似文献   
160.
The crystal structure of 1-[(1'-phenyl-5'-methyl-4'-pyrazolcarbonyl)]-3-methyl thio-5-amino-1H-yl-1,2,4-triazole (C14H14N6OS, Mr = 314.37) has been determined by single-crystal X-ray diffraction analysis. The crystal belongs to triclinic, space group P with a = 8.026(3), b = 8.651(4), c = 11.369(5) (A), α = 89.917(7), β= 89.084(7), γ = 68.470(6)°, V = 734.2(5) (A)3, Z = 2, Dc = 1.422 g/cm3, ( = 0.232 mm-1, F(000) = 328, R = 0.0376 and wR = 0.0890 for 2950 unique reflections. The crystal structure shows the presence of a dimmer with intermolecular N(4)-H(4)…N(3A) hydrogen bonds.  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