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   3023篇
  免费   546篇
  国内免费   502篇
化学   2221篇
晶体学   29篇
力学   208篇
综合类   27篇
数学   330篇
物理学   1256篇
  2024年   4篇
  2023年   59篇
  2022年   80篇
  2021年   79篇
  2020年   125篇
  2019年   129篇
  2018年   121篇
  2017年   119篇
  2016年   165篇
  2015年   135篇
  2014年   195篇
  2013年   219篇
  2012年   246篇
  2011年   264篇
  2010年   197篇
  2009年   191篇
  2008年   246篇
  2007年   165篇
  2006年   189篇
  2005年   172篇
  2004年   121篇
  2003年   111篇
  2002年   123篇
  2001年   90篇
  2000年   68篇
  1999年   77篇
  1998年   53篇
  1997年   32篇
  1996年   40篇
  1995年   46篇
  1994年   38篇
  1993年   35篇
  1992年   26篇
  1991年   21篇
  1990年   19篇
  1989年   14篇
  1988年   11篇
  1987年   11篇
  1986年   11篇
  1985年   5篇
  1984年   8篇
  1983年   3篇
  1982年   1篇
  1981年   3篇
  1979年   1篇
  1965年   1篇
  1963年   1篇
  1936年   1篇
排序方式: 共有4071条查询结果,搜索用时 312 毫秒
41.
The well-known Bombieri-A. I. Vinogradov theorem states that (1) $$\sum\limits_{q \leqslant x^{\tfrac{1}{2}} (\log x)^{ - s} } {\mathop {\max }\limits_{(a,q) = 1} \mathop {\max }\limits_{y \leqslant x} } \left| {\psi (y,q;a) - \frac{y}{{\varphi (q)}}} \right| \ll \frac{x}{{(\log x)^A }},$$ whereA is an arbitrary positive constant,B=B(A)>0, and as usual, $$\psi (x,q;a) = \sum\limits_{\mathop {n \leqslant x}\limits_{n = a(q)} } {\Lambda (n),}$$ Λ being the Von Mangoldt's function. The problem of finding a result analogous to (1) for short intervals was investigated by many authors. Using Heath-Brown's identity and the approximate functional equation for DirichletL-functions, A. Perelli, J. Pintz and S. Salerno in 1985 established the following extension of Bombieri's theorem: Theorem 1. (2) $$\sum\limits_{q \leqslant Q} {\mathop {\max }\limits_{(a,q) = 1} \mathop {\max }\limits_{h \leqslant y} \mathop {\max }\limits_{\frac{x}{2}< \approx \leqslant x} } \left| {\psi (z + h,q;a) - \psi (z,q;a) - \frac{h}{{\varphi (q)}}} \right| \ll \frac{y}{{(\log x)^A }}$$ where A>0 is an arbitrary constant,y=x θ $$\frac{7}{{12}}< \theta \leqslant 1, Q = x^{\frac{1}{{40}}} .$$ ,Q=x 1/40. By improving the basic lemma which A. Perelli, J. Pintz and S. Salerno used as the main tool to prove Theorem 1, we obtain Theorem 2.Under the same condition as in Theorem 1,for Q=x 1/38.5, (2)still holds.  相似文献   
42.
烷基季铵盐插层剂的合成及应用   总被引:1,自引:0,他引:1  
Three novel intercalation agents were synthesized for the first time, which arose from oleic acid diethylenetriamine or triethylenetetramine 3 - chloro - 2 - hydroxypropy trimethylammonium choride (CHPTA) and chloroethanol. Organophilic vermicullites were synthesized from sodium type vermiculite by cation exchange with new intercalation agents. The results of X - ray diffraction study showed that the gallery distance of the organophilic vermiculite was enlarged from 1 nm to 5 nm or more. A new idea of making design for intercalation agent was provided.  相似文献   
43.
本文提出了新的硼酸类催化剂体系HB,用该体系对α-蒎烯与无水乙酸相互作用直接合成乙酸正龙脑酯作了较系统的研究。反应得到两种系列产物-酯化产物和异构化产物,酯化产物主要是乙酸正龙脑酯,葑醇酯和松油酯,异构化产物主要是莰烯、烯和松油烯等,总酯化产率为50%以上,其中乙酸正龙脑酯为20%以上,是至今从α-蒎烯直接合成乙酸正龙脑酯的最好结果。通过对产物的 ̄1HNMK图谱分析及动力学考察,确证反应主产物是正龙脑酯而不是异龙脑酯。文章对H_2SO_4、HClO_4、多聚磷酸(PPA)和杂多酸(12-磷钨酸)等催化剂进行了实验考察、对比和评述,表明了自制的HB催化剂体系具有高选择性合成乙酸正龙脑酯的显著优点,并对其反应机理作了初步探讨。  相似文献   
44.
毕克草为一种新型除草剂,通常情况下很难被降解,本文利用物理吸附原理通过自行制备的大孔吸附树脂从农药水中对其进行了回收,回收效果良好,同时也达到了废水处理的目的。优化的最佳实验条件:室温下,pH=1.0以及流速为5BV/h时,对COD为15000mg/L的毕克草废水吸附处理后,其出水可达《污水综合排放标准》(GB89—1996)中的一级排放标准;洗脱再生时,室温下,用95%的乙醇洗脱,流速为2BV/h,(即2倍树脂床体积/h)回收率可达98.4%,纯度达93.7%,总流程一次可处理该废水240mL。  相似文献   
45.
This paper describes a microfluidics-based sensing system that relies on electrochemical detection and electrogenerated chemiluminescent (ECL) reporting. The important result is that the ECL reporting reaction is chemically decoupled from the electrochemical sensing reaction. That is, the electrochemical sensing reaction does not participate directly in the ECL process, but because electrochemical cells require charge balance, the sensing and ECL reactions are electrically coupled. This provides a convenient and sensitive means for direct photonic readout of electrochemical reactions that do not directly participate in an ECL reaction and thus broadens the spectrum of redox compounds that can be detected by ECL. The approach can be implemented in either a two-electrode or bipolar (single-electrode) configuration. By manipulating the placement and dimensions of the conductors, the photonic response can be enhanced. The system is used to electrochemically detect benzyl viologen present in solution and report its presence via Ru(bpy)(3)(2+) (bpy = 2,2'-bipyridine) luminescence.  相似文献   
46.
过渡金属酞等配合物(MPC)用手均相液相氧化中作催化剂已有不少报导,象许多均相催化剂一样,MPC用于均相反应存在着难于从反应体系中分离出来的问题.把均相配合物催化剂固载在无机氧化物如硅股或有机高分子载体上是解决这一问题的一种方法.我们曾尝试把MP。固载在分子筛载体和硅胶载体上,并用ESR研究其对O2的活化作用[1,2].本文报导MPc通过共价键键联固载在SiO2上,并研究其对O2的活化作用.1实验部分1.1试剂HSIC13为日本东京化成株式会社产品,二级试剂·发烟硫酸(SO。质量分数大于20%)为分析纯试剂.PCl5为化学纯试…  相似文献   
47.
Metalation of covalent organic frameworks (COFs) is a critical strategy to functionalize COFs for advanced applications yet largely relies on the pre-installed specific metal docking sites in the network, such as porphyrin, salen, 2,2′-bipyridine, etc. We show in this study that the imine linkage of simple imine-based COFs, one of the most popular COFs, readily chelate transition metal (Ir in this work) via cyclometalation, which has not been explored before. The iridacycle decorated COF exhibited more than 10-fold efficiency enhancement in (photo)catalytic hydrogen evolution from aqueous formate solution than its molecular counterpart under mild conditions. This work will inspire more functional cyclometallated COFs to be explored beyond catalysis considering the large imine COF library and the rich metallacycle chemistry.

This study describes cyclometallation as a new metal binding mode for imine-based COFs. The iridacycle decorated COF could be used for catalytic hydrogen evolution from aqueous formate solution with high stability and high efficacy.  相似文献   
48.
Yang W  Lu C  Zhang Q  Chen S  Zhan X  Liu J 《Inorganic chemistry》2003,42(22):7309-7314
The hydrothermal reaction of NaVO(3).H(2)O, barbituric acid, NH(2)NH(2).2HCl, H(3)PO(4), and H(2)O gave a novel heteropolyoxovanadate Na(6)[(P(V)O(4))V(V)(6)V(IV)(12)O(39)](2).H(3)PO(4).31H(2)O (1) and an unexpected phase Na(2)[C(12)H(6)N(6)O(9)].7H(2)O (2). The basic building blocks in 1 are the six-capped sphere-shaped heteropoly anion [(P(V)O(4))V(V)(6)V(IV)(12)O(39)](3-) with framework similar to that of the reported polyoxovanadates possessing [V(18)O(42)] clusters encapsulating VO(4) or other ions. These heterpoly anionic units are linked via V[bond]O[bond]V bridges into an interesting 3D straight-channel structure. The structure of 2 consists of novel organic anions ([C(12)H(6)N(6)O(9)](2-), 5,5-bis(2',4',6'-trioxopyrimidyl)barbital, representing the first oxidized barbituric acid trimer) linked via sodium ions into 1D hollow tubes with diameter of 4.49 x 6.86 A and further connected into a three-dimensional framework via hydrogen bonds.  相似文献   
49.
Direct optical detection of singlet oxygen from a single cell   总被引:1,自引:0,他引:1  
Singlet oxygen has been detected in single nerve cells by its weak 1270 nm phosphorescence (a1deltag --> X3sigmag-) upon irradiation of a photosensitizer incorporated in the cell. Thus, one can now consider the application of direct optical imaging techniques to mechanistic studies of singlet oxygen at the single-cell level.  相似文献   
50.
Based on carbon nanofibers (CNFs) as a solid phase extraction adsorbent, a microcolumn preconcentration method coupled to inductively coupled plasma mass spectrometry (ICP–MS) was developed for the determination of trace elements (Mn, Co and Ni). The effect of various experimental parameters such as pH, sample flow rate and volume, elution solution and interfering ions on the retention of the studied ions have been investigated systematically. During all the steps of the experimental process, Mn, Co and Ni could be quantitatively sorbed on the microcolumn containing CNFs in the range of pH 6.0–9.0, and then eluted completely with 0.5 mol ml− 1 HNO3. A preconcentration factor of 150-fold was obtained. The detection limits for Mn, Co and Ni were 40, 0.4 and 8.0 pg ml− 1, respectively, with relative standard deviations less than 6.0%. In order to validate the proposed method, two certified reference materials of human hair (GBW 07601) and mussel (GBW 08571), and water sample were analyzed with satisfactory results. The recoveries were between 95.0 and 114%.  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