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   52673篇
  免费   7463篇
  国内免费   5684篇
化学   27802篇
晶体学   530篇
力学   1953篇
综合类   349篇
数学   4545篇
物理学   12839篇
无线电   17802篇
  2024年   153篇
  2023年   1179篇
  2022年   1428篇
  2021年   2018篇
  2020年   1911篇
  2019年   1897篇
  2018年   1558篇
  2017年   1581篇
  2016年   2069篇
  2015年   2366篇
  2014年   2732篇
  2013年   3446篇
  2012年   4190篇
  2011年   4346篇
  2010年   3262篇
  2009年   3392篇
  2008年   3595篇
  2007年   3332篇
  2006年   2988篇
  2005年   2620篇
  2004年   1938篇
  2003年   1613篇
  2002年   1564篇
  2001年   1278篇
  2000年   1108篇
  1999年   991篇
  1998年   861篇
  1997年   775篇
  1996年   760篇
  1995年   629篇
  1994年   580篇
  1993年   534篇
  1992年   489篇
  1991年   403篇
  1990年   348篇
  1989年   262篇
  1988年   224篇
  1987年   161篇
  1986年   184篇
  1985年   192篇
  1984年   127篇
  1983年   78篇
  1982年   84篇
  1981年   61篇
  1980年   60篇
  1979年   64篇
  1978年   50篇
  1976年   48篇
  1974年   49篇
  1973年   47篇
排序方式: 共有10000条查询结果,搜索用时 281 毫秒
871.
Fe-Co-Ni合金纳米线有序阵列的模板合成与磁性   总被引:10,自引:0,他引:10  
以二次阳极氧化的氧化铝膜为模板,用电化学沉积的方法成功地合成了Fe-Co-Ni三组份有序纳米线阵列.扫描电子显微镜(SEM)和透射电子显微镜(TEM)观察表明纳米线表面光滑、有序、高长径比;磁性测量表明,其矫顽力较同组份的膜材料有较大的提高.将样品在惰性气体氛围中不同温度下退火,随着退火温度增加,其纵向矫顽力有一个极值,而对应的横向矫顽力没有类似的变化,关于这一现象的机理,本文进行了初步的讨论. 图5参15  相似文献   
872.
根据CR传输线模型和QR电路之间的关系,建立了拟合其初值的计算方法,借助Z-View软件,可求得各元件精确值.根据电容(Ci)和电阻(Ri)随特征频率(f*)的分布,推导了元件相对增量与恒相位角元件(Q)指数参数n的关系. 结果表明, 当n小于0.5时,Ci比Ri增加得更快,从新的角度说明了n的物理意义及其和界面脱层之间的关系.作为应用实例,拟合了不同特征的电化学阻抗谱,分析了有机涂层/金属腐蚀体系阻抗变化的具体过程,区分了点蚀和脱层因素对阻抗谱的影响,从高阻抗体系同时得到了与不同空隙率有关的涂层电容和电阻值,并根据涂层体系的不均匀特征探讨了模型结构的物理意义.  相似文献   
873.
Yeo WC  Tee SY  Tan HB  Tan GK  Koh LL  Leung PH 《Inorganic chemistry》2004,43(25):8102-8109
An organopalladium complex containing ortho-metalated (S)-(1-(dimethylamino)ethyl)naphthalene as the chiral auxiliary has been used to promote the asymmetric hydrophosphination reactions between diphenylphosphine and (E)- or (Z)-diphenyl-1-propenylphosphine in high regio- and stereoselectivities under mild conditions. Hydrophosphination of (Z)-diphenyl-1-propenylphosphine with diphenylphosphine gave (S)-(-)-prophos as the major product. Using the same chiral metal template, the corresponding hydrophosphination reaction with (E)-diphenyl-1-propenylphosphine gave (R)-(+)-prophos predominantly. The hydrophosphination reactions generated the asymmetric diphosphines as bidentate chelates on the chiral naphthylamine palladium templates. The template products obtained undergo cis-trans isomerization in solution to form an equilibrium mixture of regioisomers. X-ray analysis of the major template products obtained from the hydrophosphination of (Z)-diphenyl-1-propenylphosphine reveals that the two regioisomers are cocrystallized in a 1:1 ratio. The naphthylamine auxiliary could be removed chemoselectively from the template products by treatment with concentrated hydrochloric acid to form the corresponding optically pure neutral complexes [(R)- or (S)-(prophos)PdCl(2)]. Subsequently, the (R)- and (S)-dichloro complexes undergo ligand displacement with aqueous cyanide to generate the corresponding optically pure diphosphine ligands in high yields. Mechanistic pathways explaining the stereoselectivity of the chiral organopalladium template promoted hydrophosphination reactions are also proposed.  相似文献   
874.
玻璃载体表面脱氧核糖核酸的固定及其化学发光检测   总被引:2,自引:0,他引:2  
张国军  周宜开 《分析化学》1998,26(10):1205-1208
用硅烷化偶联剂把DNA直接共价固定在载玻片表面,将辣根过氧化物酶标记的探针与之进行核酸杂交,杂交后用增强的化学发光检测。方法的检出限为75pg。研究了DNA分子固定在玻璃载体表面的各种条件,并建立了在玻璃载体表面进行核酸杂交的体系,为研究光纤DNA生物传感器打下了基础。  相似文献   
875.
Simultaneous interpenetrating polymer networks (SINs) based on diglycidyl ether of bis-phenol A (DGEBA) and poly(ethylene glycol) diacrylate (PEGDA) in weight ratios of 100/0, 50/50, and 0/100 were blended and cured simultaneously by using benzoyl peroxide (BPO) and m-xylenediamine (MXDA) as curing agents. A kinetic study during SIN formation was carried out at 45, 55, 63, and 70°C. Concentration changes for both the epoxide and C?C bond were monitored with FTIR. A rate expression for DGEBA cure kinetics was established with a model reaction of phenyl glycidyl ether (PGE) and benzylamine. Experimental results revealed that lower rate constants and higher activation energy for the SIN were found, compared with those for the constituent DGEBA and PEGDA network formation. A model of network interlock was proposed to account for this phenomenon. During simultaneous cure of DGEBA and PEGDA, the interlock (mutual entanglement) between DGEBA and PEGDA networks provided a sterically hindered environment, which subsequently increased the activation energy and reduced cure rates for both DGEBA and PEGDA. © 1993 John Wiley & Sons, Inc.  相似文献   
876.
The effect of the addition of a second metals such as Zn and Ni on the calcinaton and reduction of alumina, magnesia and silicasupported iron catalysis with total iron loading of 5wt% is investigated by Mössbauer spectroscopy. It is shown that the reducibility of supported α-Fe2O3 is gradually increased by adding the second metal. The values of the magnetic hyperfine field obtained from Mössbauer spectra for the Zn or Ni-added α-Fe2O3 or Fe catalysts decreased with increasing second metal loading.  相似文献   
877.
Dioscoreae (Chinese name Shanyao), the rhizome of various species of genus Dioscorea opposita Thunb.(Dioscoreaceae), has been used as an important invigorant in traditional Chinese medicine (TCM) for many years1. Starch, the most abundant carbohydrate in …  相似文献   
878.
Lin CE  Lin SL  Cheng HT  Fang IJ  Kuo CM  Liu YC 《Electrophoresis》2005,26(21):4187-4196
Migration behavior and enantioseparation of racemic hydrobenzoin and structurally related compounds, including benzoin and benzoin methyl ether, in CZE with a dual CD system consisting of heptakis-(2,3-dihydroxy-6-O-sulfo)-beta-CD (SI-S-beta-CD) and beta-CD as chiral selectors in the presence and absence of borate complexation at pH 9.0 were investigated. The results indicate that enantioseparation of hydrobenzoin is mainly governed by CD complexation of hydrobenzoin-borate complexes with SI-S-beta-CD when SI-S-beta-CD concentration is relatively high. Whereas CD complexation of hydrobenzoin-borate complexes with beta-CD plays a significant role in enantioseparation when SI-S-beta-CD concentration is comparatively low. The (S,S)-enantiomer of the hydrobenzoin-borate complex was found to interact more strongly than the corresponding (R,R)-enantiomer with both SI-S-beta-CD and beta-CD. These two types of CD show the same chiral recognition pattern, but they exhibit opposite effects on the mobility of the enantiomers of hydrobenzoin-borate complexes. Enantiomer migration reversal of hydrobenzoin occurred in the presence of borate complexation when varying the concentration of beta-CD, while keeping SI-S-beta-CD at a relatively low concentration. Binding constants of the enantiomers of benzoin-related compounds to beta-CD and those of hydrobenzoin-borate complexes to SI-beta-CD were evaluated; the mobility contributions of all complex species to the effective mobility of the enantiomers of hydrobenzoin as a function of beta-CD concentration in a borate buffer were analyzed. In addition, comparative studies on the enantioseparation of benzoin-related compounds with SI-S-beta-CD and with randomly sulfate-substituted beta-CD were made.  相似文献   
879.
Hua J  Lin W 《Organic letters》2004,6(6):861-864
[structure: see text] A family of chiral metallacyclophanes has been readily assembled based on robust Pt-acetylide linkage and characterized by a variety of spectroscopic techniques and X-ray crystallography. The steric congestion around the chiral dihydroxy groups in rigid metallacyclophane 4 prevents their reactions with Ti(O(i)()Pr)(4) to form active catalysts for enantioselective diethylzinc additions to aromatic aldehydes. In contrast, chiral dihydroxy groups in more flexible unclosed metallacyclophane 5 are effective ligands for enantioselective catalytic diethylzinc additions to aromatic aldehydes.  相似文献   
880.
合成了3种离子对配合物 [1-benzyl-3-bromopyridium]+[Ni(mnt)2]- (1),[1-(4′-flurobenzyl)-3-bromopyridiunm]+[Ni(mnt)2]- (2),[1-(4′-cholorobenzyl)-3-bromopyridium]+[Ni(mnt)2]- (3),(mnt=马来二腈基二硫烯,maleonitrile dithiolate)获得了单晶并解析了它们的单晶结构。  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