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   1662篇
  免费   212篇
  国内免费   43篇
化学   1654篇
晶体学   4篇
力学   29篇
综合类   3篇
数学   33篇
物理学   194篇
  2024年   6篇
  2023年   63篇
  2022年   38篇
  2021年   42篇
  2020年   70篇
  2019年   53篇
  2018年   36篇
  2017年   48篇
  2016年   95篇
  2015年   90篇
  2014年   128篇
  2013年   97篇
  2012年   106篇
  2011年   106篇
  2010年   75篇
  2009年   123篇
  2008年   95篇
  2007年   93篇
  2006年   65篇
  2005年   50篇
  2004年   46篇
  2003年   31篇
  2002年   31篇
  2001年   13篇
  2000年   20篇
  1999年   24篇
  1998年   47篇
  1997年   15篇
  1996年   13篇
  1995年   15篇
  1994年   9篇
  1993年   11篇
  1992年   13篇
  1991年   12篇
  1990年   7篇
  1989年   9篇
  1988年   9篇
  1987年   8篇
  1986年   8篇
  1985年   6篇
  1984年   14篇
  1982年   5篇
  1981年   5篇
  1979年   6篇
  1978年   7篇
  1977年   6篇
  1976年   5篇
  1975年   7篇
  1974年   8篇
  1967年   8篇
排序方式: 共有1917条查询结果,搜索用时 15 毫秒
1.
In the view of substrate availability, atomic efficiency and cost, directly using arenols as coupling partners in cross‐coupling, would be one of the most attractive goals. Up to date, many efforts have been made to activate the C—O bond of phenols with different strategies, for example, through in‐situ formed intermediates, through a catalytic reductive dearomatization‐condensation‐rearomatization sequence or catalytic deoxygenation. In this review, we summarized recent advances in cross‐couplings of arenols as the electrophiles via C—O activation.  相似文献   
2.
Summary A novel approach to solid phase extraction, based on the use of a highly selective molecularly imprinted polymer, is presented. The versatility of this type of sorbent for solid phase extraction was demonstrated in a model batch-wise pre-concentration of sameridine prior to gas chromatography. Problems associated with leakage of remaining imprint molecules during the desorption phase could be eliminated by the use of a close structural analogue of sameridine as the imprint species. It was found that a major benefit of the imprinted polymer was its specificity, which lead to distinctly cleaner chromatographic traces and ability to improve sensitivity by extracting sameridine from larger sample volumes.  相似文献   
3.
Alkenylidenes R2C?C: (= alkylidene carbenes) undergo regio- and stereoselective intramolecular C? H insertion reactions that are excellently suited for the synthesis of cyclopentenes. The 1, 2-shifts occurring with R?H and R?Ar are useful for the preparation of alkynes. Alkenylidenes are efficiently generated from carbonyl compounds by diazomethylation, from vinyl halides by α-elimination, from alkynyliodonium salts by addition of nucleophiles, and from alkynes by retro-1, 2-shifts. Specific applications of the various methods, particularly in the synthesis of natural products, are discussed.  相似文献   
4.
用裂解气相色谱-质谱联用方法研究了橡胶产品中使用的增塑剂邻苯二甲酸二甲酯(DMP)在不同温度条件下的热裂解行为.对不同温度条件下裂解产物的分析表明,在初始阶段DMP的裂解产物主要为二氧化碳、苯、甲苯和苯甲酸甲酯.随着温度的升高苯甲酸甲酯进一步裂解成为分子质量更小的自由基,并发生稠环化反应形成更稳定的菲、蒽、间-联三苯、三亚苯等芳香族多环化合物.根据分析实验提供的裂解产物信息和有机物热裂解化学反应的原理对DMP的热裂解反应机理作了探讨,表明在废旧合成橡胶热裂解回收过程中,增塑剂DMP的高温裂解会产生多环芳烃污染物.应选择合适裂解工艺和裂解温度,以减少对环境的污染.  相似文献   
5.
6.
This paper proposes a method for estimation of a class of partially linear single-index models with randomly censored samples. The method provides a flexible way for modelling the association between a response and a set of predictor variables when the response variable is randomly censored. It presents a technique for “dimension reduction” in semiparametric censored regression models and generalizes the existing accelerated failure-time models for survival analysis. The estimation procedure involves three stages: first, transform the censored data into synthetic data or pseudo-responses unbiasedly; second, obtain quasi-likelihood estimates of the regression coefficients in both linear and single-index components by an iteratively algorithm; finally, estimate the unknown nonparametric regression function using techniques for univariate censored nonparametric regression. The estimators for the regression coefficients are shown to be jointly root-n consistent and asymptotically normal. In addition, the estimator for the unknown regression function is a local linear kernel regression estimator and can be estimated with the same efficiency as all the parameters are known. Monte Carlo simulations are conducted to illustrate the proposed methodology.  相似文献   
7.
Enantioselective biocatalysis in nonaqueous media is becoming increasingly important in preparative synthetic chemistry. This article discusses (1) the general catalytic properties of enzymes in nonaqueous environments, (2) the basic principles that govern lipase-catalyzed enantioselective esterification and transesterification reactions in organic media for the preparation of optically active acids and alcohols, (3) the determination of kinetic and thermodynamic parameters, and (4) the quantitative analysis of published data.  相似文献   
8.
对用索氏提取法和乙醇浸取法提取红景天红色素进行了比较,并探讨浸取的浓度,浸取温度等因素,指出了最佳生产工艺条件,从红景天中提取的天红色素是一种安全无毒的食用色素,本文还研究了几种食品添加剂对红景天红色素稳定性的影响,并对色素的耐氧化性进行了探讨,旨在为红景天红色素的开发利用提供有实用价值的信息。  相似文献   
9.
The light of the sun can be used directly for changing chemical structures photochemically. Any industrial application must conform to the limitations imposed by the spectral distribution of the photons from the sun, the interruptions to the radiation due to the day/night rhythm, and the weather. In this review, we describe the photochemical potential of the sun, give a fundamental treatment of the concept of photoreactors driven by sunlight (abbreviated to solar photoreactors), and give an account of the realization of this concept in the first pilot plant on the “Plataforma Solar de Almeria” in southern Spain and in other activities in this field. Based on experimental data from photochemical investigations on the pilot plant scale, possibilities, limitations, and the potential growth of solar photochemistry are described. Solar photochemistry, in our opinion, is a technique which could make a contribution to the chemistry of the future because of its photochemical synthesis potential, the avoidance of waste products, and the direct utilization of the sun, not only as a primary energy source, but also as a reaction partner.  相似文献   
10.
The syntenic distance between two species is the minimum number of fusions, fissions, and translocations required to transform one genome into the other. The linear syntenic distance, a restricted form of this model, has been shown to be close to the syntenic distance. Both models are computationally difficult to compute and have resisted efficient approximation algorithms with non-trivial performance guarantees. In this paper, we prove that many useful properties of syntenic distance carry over to linear syntenic distance. We also give a reduction from the general linear synteny problem to the question of whether a given instance can be solved using the maximum possible number of translocations. Our main contribution is an algorithm exactly computing linear syntenic distance in nested instances of the problem. This is the first polynomial time algorithm exactly solving linear synteny for a non-trivial class of instances. It is based on a novel connection between the syntenic distance and a scheduling problem that has been studied in the operations research literature.  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