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   4590篇
  免费   94篇
  国内免费   50篇
化学   391篇
晶体学   5篇
力学   34篇
综合类   5篇
数学   4034篇
物理学   265篇
  2023年   13篇
  2022年   12篇
  2021年   29篇
  2020年   23篇
  2019年   132篇
  2018年   142篇
  2017年   65篇
  2016年   64篇
  2015年   43篇
  2014年   146篇
  2013年   318篇
  2012年   130篇
  2011年   245篇
  2010年   227篇
  2009年   339篇
  2008年   353篇
  2007年   358篇
  2006年   270篇
  2005年   199篇
  2004年   172篇
  2003年   138篇
  2002年   112篇
  2001年   83篇
  2000年   76篇
  1999年   76篇
  1998年   89篇
  1997年   56篇
  1996年   101篇
  1995年   87篇
  1994年   90篇
  1993年   78篇
  1992年   66篇
  1991年   36篇
  1990年   40篇
  1989年   26篇
  1988年   19篇
  1987年   27篇
  1986年   23篇
  1985年   28篇
  1984年   34篇
  1983年   16篇
  1982年   28篇
  1981年   30篇
  1980年   24篇
  1979年   13篇
  1978年   16篇
  1977年   16篇
  1976年   19篇
  1974年   4篇
  1973年   1篇
排序方式: 共有4734条查询结果,搜索用时 65 毫秒
91.
A parallel-plate flow chamber consisting of two transparent electro-conductive glass plates was constructed. The two glass plates were set parallel to each other and connected to a potentiostat apparatus to regulate the strength of the electric field between the plates. A microbial cell suspension was flowed through the chamber. This system enabled the application of an electrostatic force to suspend charged particles, e.g. microbial cells, existing between the two plates. The time course of the cell attachment of Pseudomonas syringae pv. atropurpurea NIAES 1309 suspended in 10 mM phosphate buffer solution (pH 7.0) to the glass plate was investigated at various electric field strengths ranging from −4.2 to +4.1 V cm−1. The attachment rate and the maximum number of attached cells increased linearly with the increase in the strength of the positive electric field. In contrast, the rate and the number of cells decreased linearly with the decrease in the strength of the negative electric field. These linear relations gave a specific value for the strength of the electric field (−5.9 ± 0.7 V cm−1) where the electrostatic repulsion and the microbial attachment force were thought to be equal, resulting in no cell attachment. From this value, the electrostatic repulsion, i.e. the microbial attachment force, was calculated to be 5.0 × 10−11 N cell−1 for cells of average size.  相似文献   
92.
The polysaccharides associated with free (planktonic) and surface-attached (biofilm) cells from cultures of Pseudomonas fluorescens strain B52 were compared. Variations in the attached matrix due to surface material (glass or stainless steel) were also analyzed. Two digestion methods were used to optimize the recoveries of sugars, uronic acids and acidic substituents. The yield of analyzable material after digestion reached 90% for the material associated to the biofilms, though only 20–30% for that bound to planktonic cells. The polysaccharide(s) in the biofilm had glucuronic and guluronic acids as main components, besides rhamnose, glucose and glucosamine. The proportion of glucuronic to guluronic acid was higher in the polysaccharide(s) found in biofilms formed on stainless steel than in those on glass.  相似文献   
93.
Takamoto M  Himeno S 《Talanta》2003,59(3):637-642
On the basis of the formation and pre-concentration of an α-Keggin-type [PMo12O40]3− complex, a novel voltammetric method was developed for the determination of trace levels of P(V). The α-[PMo12O40]3− complex was formed by heating a 5×10−4 M Mo(VI)-0.2 M HCl-40% (v/v) CH3CN system containing a trace amount of P(V) at 70 °C for 30 min. During the electrochemical polymerization of pyrrole in the α-[PMo12O40]3− solution, the α-[PMo12O40]3− complex was accumulated into the polypyrrole film on a glassy carbon electrode. The differential pulse voltammetric peak current due to the α-[PMo12O40]3− complex incorporated in the polypyrrole film was linearly dependent on the P(V) concentration in the range of 5×10−9-5×10−7 M; a detection limit of 2×10−9 M was achieved.  相似文献   
94.
Summary The surface properties of silicas modified with – diols having between 4 and 16 carbon atoms were investigated by inverse gas chromatography. It is shown, that the value of the dispersive component of the surface energy does not change monotonously: a minimum value is recorded when the surface is covered by a monolayer of methylene groups. Further, when measuring the adsorption enthalpies of polar probes, an alternation of their H values is observed: grafts having an odd number of carbon atoms systematically show higher H values than the others. A trans-trans configuration of the grafted chains which allows optimum interactions is proposed, suggesting a preferential diesterification reaction of both terminal hydroxyl groups of odd diols.  相似文献   
95.
TiSiW12O40/TiO2催化合成己酸异戊酯   总被引:6,自引:0,他引:6  
报道了以固载杂多酸盐TiSiW12O40/TiO4为多相催化剂,通过己酸和异戊醇反应合成了己酸异戊酯,探讨了TiSiW12O40/TiO4对酯化反应的催化活性,较系统地研究了醇酸摩尔比,催化剂用量,反应时间诸因素对收率的影响,实验表明:TiSiW12O40/TiO4是合成己酸异戊酯的良好催化剂,在n(醇):n(酸)=1.6:1,催化剂用量为反应物总质量的1.5%,反应时间45min,使用环己烷为带水剂的适宜条件下,己酸异戊酯的收率可达91.9%。  相似文献   
96.
12-钼磷酸—聚乙烯醇的光电子转移反应   总被引:4,自引:0,他引:4  
12-钼磷酸—聚乙烯醇体系具有不可逆光致变色的特性。根据X射线光电子能谱、电子自旋共振谱、紫外及可见光谱的测试结果,笔者认为:在PMo_(12)-PVA的光电子转移反应中,PMo_(12)既是氧化剂也是光敏剂。PMo_(12)分子中氧可分成O_p、O_b和O_t三种情况.其中O_t可成为光化学的活性位置,它和PVA羟基上的氧均较易被紫外光激活。激活的0_t边使周围的一个电荷向金属原子(Mo~(Ⅵ))转移,边与PVA羟基上被激活的氧作用,电子就由此羟基上的氧向O_t转移,致使体系中部分PMo_(12)与PVA发生二电子或四电子氧化还原反应,形成Mo(Ⅵ、Ⅴ)配合物而变色,同时,PVA分子的部分羟基及该羟基位的碳上脱氢形成羰基而具有酮结构。此外,从Mo(V)的ESR特征信号随时间变化而减弱,但其吸收光谱的吸光度未变,于是推断该光化学反应过程中尚有Mo(Ⅳ)生成,已由XPS谱证实。  相似文献   
97.
The attractive utilization route for one-step catalytic oxidation of dimethyl ether to dimethoxymethane was successfully carried out over the H3PW12O40(40%)/SiO2 catalyst, modified by Cs, K, Ni, and V. The Cs modification of H3PW12O40(40%)/SiO2 gave the most promising result of 20% dimethyl ether conversion and 34.8% dimethoxymethane selectivity. Dimethoxymethane could be synthe- sized via methoxy groups decomposed from dimethyl ether through the synergistic effect between the acid sites and the redox sites of Cs modified H3PW12O40(40%)/SiO2.  相似文献   
98.
TiSiW_(12)O_(40)/TiO_2催化合成磷酸三甲苯酯的研究   总被引:8,自引:1,他引:8  
杨锦飞 《有机化学》2003,23(11):1317-1319
应用TiSiW_(12)O_(40)/TiO_2催化剂合成磷酸三甲苯酯研究结果表明,该催化 剂具有较高的催化活性。考察了催化剂用量、反应温度和反应时间对酯产率的影响 。在典型反应条件(催化剂用量为原料总量的1.0%,反应温度为100-120 ℃,反应 时间为8h)下所得磷酸三甲苯酯的产率为85.5%。该催化剂易于回收且可重复使用 ,具有良好的活性稳定性。  相似文献   
99.
Summary. The fact that cyclic arrangements of double bonds have a dramatic effect on the behavior of conjugated organic molecules is known since the 19th century. The fact that in monocyclic conjugated systems the size of the cycle and the number of -electrons involved is decisive for their stability (aromaticity) or lack of stability (antiaromaticity) is known since the 1930s. In polycyclic -electron systems several cyclic effects are present simultaneously and their separation became possible only recently. A molecular orbital method has been elaborated, by means of which the energy effects of individual cycles in polycyclic -electron systems can be estimated. This method is briefly outlined and illustrated by pertinent examples. An exhaustive bibliography of the topic considered is given.  相似文献   
100.
Three pyochelin analogues and their methyl esters all containing a thiazole ring have been synthesised from the same Weinreb amide key intermediate. One of these analogues called HPTT-COOH, a molecule released in the course of pyochelin and yersiniabactin biosynthesis, was efficiently synthesised using a new base induced conversion of the key compound 2′-(2-hydroxyphenyl)-2′-thiazoline-4′-(N-methoxy,N-methyl) carboxamide into 2′-(2-hydroxyphenyl)-2′-thiazole-4′-(N-methoxy,N-methyl) carboxamide.  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