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   5659篇
  免费   433篇
  国内免费   662篇
化学   4990篇
晶体学   57篇
力学   74篇
综合类   40篇
数学   282篇
物理学   1311篇
  2025年   3篇
  2024年   51篇
  2023年   76篇
  2022年   150篇
  2021年   165篇
  2020年   243篇
  2019年   203篇
  2018年   165篇
  2017年   162篇
  2016年   193篇
  2015年   205篇
  2014年   243篇
  2013年   494篇
  2012年   352篇
  2011年   342篇
  2010年   261篇
  2009年   317篇
  2008年   292篇
  2007年   292篇
  2006年   295篇
  2005年   280篇
  2004年   258篇
  2003年   242篇
  2002年   218篇
  2001年   143篇
  2000年   137篇
  1999年   133篇
  1998年   133篇
  1997年   91篇
  1996年   88篇
  1995年   85篇
  1994年   77篇
  1993年   58篇
  1992年   65篇
  1991年   39篇
  1990年   32篇
  1989年   32篇
  1988年   29篇
  1987年   19篇
  1986年   19篇
  1985年   11篇
  1984年   15篇
  1983年   6篇
  1982年   9篇
  1981年   5篇
  1979年   5篇
  1978年   6篇
  1977年   5篇
  1976年   3篇
  1975年   2篇
排序方式: 共有6754条查询结果,搜索用时 0 毫秒
21.
The analytic properties of scattering amplitudes provide a meeting point for experimental and theoretical investigations of baryon resonances. Pole positions and residues allow for a parameterization of resonances in a well-defined way which relates different reactions. The recent progress made within the Jiilich model is summarized.  相似文献   
22.
Abstract

The water exchange reaction of [Pd(dien)H2O]2+ (dien = diethylenetriamine) was studied as function of temperature (268-308 K) and pressure 0.1-197 MPa) using 17O NMR techniques. The rate and activation parameters are: kcx = 5100 s?1 at 298 K; ΔH# =38 kJ mol?1; ΔS# = -47 JK?1 mol?1; ΔV# = -2.8 cm3 mol?1 at 296 K. The results are discussed in reference to solvent exchange data for other Pt(II) and Pd(II) complexes, and are interpreted in terms of an associatively activated substitution process.  相似文献   
23.
Es wurde ein Trennverfahren ausgeabeitet, das es gestattet, die Aktivitätsausbeuten für Mono-, Di- und Triphenylarsenverbindungen, für Tetraphenylarsoniumverbindungen und für Pentaphenylarsen sowie für nicht organisch gebundenes Arsen in neutronenbestrahlten Tetraphenylarsoniumver erbindungen und in Pentaphenylarsen zu bestimmen. Als Trennmethoden werden Extraktion, Ionenaustauwsch und Al2O3-Chromatographic benutzt. Zur Reinigung und Ausbeutebestimmung von Di- und Triphenylarsenprodukten sowie von Tetraphenylarsonimverbindungen finden Kristallisations- bzw. Fällungsreaktionen Anwendung unter Ausnutzung des Prinzips der Isotopenverdünnungsanalyse.  相似文献   
24.
离子交换树脂催化对羟基苯甲酸酯化反应的研究*   总被引:16,自引:0,他引:16  
本文研究了一种固体酸催化剂一阳离子交换树脂催化剂,用于对羟基苯甲酸的酯化反应。通过对不同树脂进行筛选,发现JK008的催化活性比较高。本文还进一步考察了JK008催化剂的使用寿命,研究了合成对羟基苯甲酸乙酯的最佳反应条件。  相似文献   
25.
It has been proven qualitatively by a number of authors using variable temperature NMR experiments that most metal carbonyl complexes are nonrigid. A quantitative determination of the ligand exchange frequency ve is often achieved by a line shape analysis or by measurement of the transverse relaxation time T2 using the Carr-Purcell method. In the case of a “very fast” exchange, however, both methods prove unsuccessful. It is shown in this study that a simultaneous fit of IR or Raman spectra on the one hand and NMR spectra on the other can make possible the determination of ve for the “very fast” exchange and can also facilitate the determination of ve in “slow” and “medium” exchange cases considerably. The ligand exchange frequency thus found for Fe(CO)5, 1.1 × 1010s?1, is unexpectedly high; comparison with variable temperature measurements on solid Fe(CO)5, yields similar energy barriers. A mechanism of exchange closely related to the “Berry mechanism” is proposed. Finally the consequences of this surprisingly large ligand exchange rate are discussed with respect to IR band assignments for molecular “fragments” M(CO)x (where x=coordination number, and M is a transition metal, typically lanthanoid or actinoid).  相似文献   
26.
A new μ3-O triiron(Ⅲ) complex [Fe_3O(OBz)_6(CH_3OH)_3](NO_3)(CH_3OH)_2 (HOBZ = benzoic acid) has been synthesized, its structure has been determined and variable temperature magnetic susceptility has also been measured. In the molecule, three iron atoms formed an equilateral triangle with u_3-O in center. The fitting to the magnetic susceptibility showed that an intramolecular antiferromagnetic exchange interaction occurred between iron atoms with J=-25.51 cm~(-1), and a weaker intermolecular antiferromagnetic exchange interaction occurred with zJ' = -2.30cm~(-1).  相似文献   
27.
A new μ3-O triiron(III) complex [Fe3O(OBz)6(CH3OH)3](NO3)(CH3OH)2 (HOBZ = benzoic acid) has been synthesized, its structure has been determined and variable temperature magnetic susceptility has also been measured. In the molecule, three iron atoms formed an equilateral triangle with μ3-O in center. The fitting to the magnetic susceptibility showed that an intramolecular antiferromagnetic exchange interaction occurred between iron atoms with J=-25.51 cm?1, and a weaker intermolecular autiferromagnetic exchange interaction occurred with zJ' = ?2.30 cm?1.  相似文献   
28.
A cation adsorption model is presented and its recent applications are discussed. The model combines electrostatic equations with specific binding, and considers neutral and positively charged complexes between the negative surface sites and organic cations in a closed system. Extensions in the model account for dye aggregation in solution, and for the formation of solution complexes of inorganic cations, such as [M++ Cl]+. The amounts of 45Ca2+ adsorbed to vesicles extracted from the plasma membranes of melon root cells could be adequately simulated and predicted. The binding coefficients determined for Ca2+, Na+, and Mg2+ are in the range of values previously deduced for binding to phospholipid components. Model calculations were applied to the test of hypotheses on the effect of salt stress on the growth of roots. The adsorption of monovalent organic cations to montmorillonite is characterized by binding coefficients that are at least six orders of magnitude larger than those of Na+, Mg2+, Ca2+, and Cd2+, or those of CdCl+ or CaCl+. Monovalent organic cations were found to adsorb 140–200% of the cation exchange capacity of the clay and to cause charge reversal. Deductions from adsorption results of acriflavin are consistent with those drawn from the application of other experimental methods. Preliminary results on the adsorption of divalent organic cations are presented. Agro-environmental applications of organo-clays are discussed.  相似文献   
29.
The synthesis, metal, ammonium and alkyl ammonium cation coordination chemistry and electrochemical recognition studies of new diester-and diamide-calix[4]arenediquinone receptors are described. In addition the synthesis and coordination properties of a novel diamide benzo-15-crown-5-calix[4]arene molecule is reported.This paper is dedicated to the commemorative issue on the 50th anniversary of calixarenes.  相似文献   
30.
    
Cationic framework materials, especially pure inorganic cationic frameworks that can efficiently and selectively capture harmful heavy metal oxyanions from aqueous solution are highly desired yet scarcely reported. Herein, we report the discovery of a 2D cationic aluminum oxyhydroxide, JU-111, which sets a new benchmark for heavy metal oxyanion sorbents, especially for CrVI. Its structure was solved based on 3D electron diffraction tomography data. JU-111 shows fast sorption kinetics (ca. 20 min), high capture capacity (105.4 mg g−1), and broad working pH range (3–10) toward CrVI oxyanions. Unlike layered double hydroxides (LDHs), which are poorly selective in the presence of CO32−, JU-111 retains excellent selectivity for CrVI even under a large excess of CO32−. These superior features coupled with the ultra-low cost and environmentally benign nature make JU-111 a promising candidate for toxic metal oxyanion remediation as well as other potential applications.  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