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   10927篇
  免费   2052篇
  国内免费   1567篇
化学   8905篇
晶体学   38篇
力学   889篇
综合类   52篇
数学   510篇
物理学   4152篇
  2024年   43篇
  2023年   446篇
  2022年   268篇
  2021年   303篇
  2020年   381篇
  2019年   425篇
  2018年   446篇
  2017年   403篇
  2016年   465篇
  2015年   553篇
  2014年   755篇
  2013年   982篇
  2012年   722篇
  2011年   816篇
  2010年   636篇
  2009年   765篇
  2008年   713篇
  2007年   666篇
  2006年   655篇
  2005年   601篇
  2004年   549篇
  2003年   481篇
  2002年   324篇
  2001年   230篇
  2000年   241篇
  1999年   209篇
  1998年   195篇
  1997年   177篇
  1996年   145篇
  1995年   159篇
  1994年   116篇
  1993年   98篇
  1992年   78篇
  1991年   39篇
  1990年   58篇
  1989年   45篇
  1988年   43篇
  1987年   37篇
  1986年   27篇
  1985年   32篇
  1984年   31篇
  1983年   9篇
  1982年   26篇
  1981年   24篇
  1980年   15篇
  1979年   15篇
  1977年   16篇
  1976年   17篇
  1974年   9篇
  1973年   13篇
排序方式: 共有10000条查询结果,搜索用时 15 毫秒
21.
锥形光纤间耦合特性的分析与检测   总被引:2,自引:0,他引:2  
将通信光纤的末端拉制成锥形,利用光信号在光纤锥形区特有的传输和耦合特性,实现了光纤的耦合、连接和分束。用耦合模理论分析了锥形光纤间的传输和耦合性质,给出了光信号两锥形光纤间的耦合与两锥形光纤的距离和锥形区重叠长度等实验结果。  相似文献   
22.
A convenient and higher yielding synthetic route to N‐alkyl‐bis(thiophene)phenothiazine derivatives is reported and their aggregation, electrochemical properties and polymerization are characterized. The key step in the synthesis of this group of compounds has been the Stille type coupling reaction between the N‐alkyldibromophenothiazine and tin derivatives of thiophene as the best way for preparation of conjugated N‐alkylphenothiazine derivatives. For this group of compounds we also present an electrochemical polymerization effect and widely adopted approach to prepare structurally ordered thin, electroconducting films by Langmuir–Blodgett technique.  相似文献   
23.
Aminonaphthols are easily transformed into a variety of 1- and 2-naphthyl piperazines using a sequence of diazotization, iodide substitution and Pd(0) catalyzed coupling reactions.  相似文献   
24.
Grindstone Chemistry--a greatly evolved version of Toda’s method of grinding solids together for solvent-free chemical reactions--has been described and its usefulness illustrated by the successful application of this technique to a simplified process for conducting the multi-component Biginelli reaction for the synthesis of physiologically active tetrahydropyrimidinones.  相似文献   
25.
A new type I palladium-catalyzed pseudo-domino process is developed, in which a single Pd-based catalytic system promotes two mechanistically unrelated, sequential catalytic cycles in chronologically distinct order. Suitable precursors undergo an allylic alkylation and a Heck coupling in sequence, affording polycondensed pyrrolidone derivatives. Depending on the starting precursors, intra/inter or doubly intramolecular processes can be obtained. The allylic alkylation process takes place always very smoothly. On the other hand, the Heck coupling turns out to be rather difficult either when the process is intermolecular, or when an intramolecular process generates polycondensed structures featuring three fused bonds connected to a common carbon atom. In such difficult cases, use of the Herrmann-Beller phosphapalladacycle allowed to catalyze the coupling. This study demonstrates also that allylic alkylations can be catalyzed by the Herrmann-Beller phosphapalladacycle.  相似文献   
26.
27.
Dehydropeptides containing dehydroamino acid (ΔAA) are frequently found in natural resources with important biological activity. Herein, we report the selective synthesis of Z- and E-ΔAbu from l- and l-allo-threonine as starting materials through selenation and oxidative elimination. The detailed reaction mechanism of phosphine-assisted selenoether formation is also discussed.  相似文献   
28.
Coupling constants of nuclear spin systems can be determined from phase modulation of multiplet resonances. Strongly coupled systems such as citrate in prostatic tissue exhibit a more complex modulation than AX connectivities, because of substantial mixing of quantum states. An extreme limit is the coupling of n isochronous spins (An system). It is observable only for directly connected spins like the methylene protons of creatine and phosphocreatine which experience residual dipolar coupling in intact muscle tissue in vivo. We will demonstrate that phase modulation of this “pseudo-strong” system is quite simple compared to those of AB systems. Theory predicts that the spin-echo experiment yields conditions as in the case of weak interactions, in particular, the phase modulation depends linearly on the line splitting and the echo time.  相似文献   
29.
A nucleophilic substitution reaction between 4-tert-butylbenzyl bromide and a series of iodide salts has been performed in oil-in-water microemulsions based on either a fatty alcohol ethoxylate or a sugar surfactant. The reaction kinetics was compared with the kinetics of the same reaction performed in a microhomogeneous reaction medium, d-MeOH. Previous results showing a particularly high reactivity in the microemulsion based on the fatty alcohol ethoxylate was confirmed. It was shown that in both microemulsions the reaction rate was almost independent of the choice of counterion to iodide. This indicates that complexation of the cation with the surfactant headgroup, which, in particular, could have taken place with surfactants containing oligooxyethylene chains (a “crown ether effect”), seems not to be of importance.

127I NMR studies, as well as quadrupole splitting experiments performed by 2H NMR, indicate that there is a certain accumulation of iodide at the oil–water interface of the microemulsions. It is difficult to draw any quantitative conclusions in this respect, however.

The results obtained in this study, combined with results from previous investigations of the same reaction, indicate that the unexpectedly high reactivity obtained in the microemulsion based on a surfactant containing an oligooxyethylene headgroup is most probably due to the nucleophile being poorly solvated when present in the headgroup layer of such a microemulsion. Poorly solvated anions are known to be highly reactive nucleophiles.  相似文献   

30.
A Glaser coupling reaction of terminal alkynes in the presence of nickel chloride withoutany organics and bases in hot water has been developed, which produces the correspondinghomo-coupling products in good yields.  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