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   1365篇
  免费   25篇
  国内免费   6篇
化学   1057篇
晶体学   8篇
力学   13篇
数学   173篇
物理学   145篇
  2023年   16篇
  2022年   28篇
  2021年   60篇
  2020年   33篇
  2019年   24篇
  2018年   28篇
  2017年   20篇
  2016年   24篇
  2015年   38篇
  2014年   32篇
  2013年   72篇
  2012年   68篇
  2011年   78篇
  2010年   60篇
  2009年   42篇
  2008年   87篇
  2007年   83篇
  2006年   83篇
  2005年   66篇
  2004年   57篇
  2003年   62篇
  2002年   51篇
  2001年   16篇
  2000年   17篇
  1999年   14篇
  1998年   11篇
  1997年   12篇
  1996年   17篇
  1995年   16篇
  1994年   10篇
  1993年   9篇
  1992年   13篇
  1991年   17篇
  1990年   7篇
  1989年   8篇
  1988年   4篇
  1987年   6篇
  1985年   12篇
  1984年   8篇
  1983年   6篇
  1982年   12篇
  1981年   9篇
  1980年   7篇
  1979年   7篇
  1978年   5篇
  1975年   4篇
  1974年   4篇
  1972年   4篇
  1959年   3篇
  1940年   2篇
排序方式: 共有1396条查询结果,搜索用时 31 毫秒
131.
The rigid [6]ferrocenophane, L1, was synthesised by condensation of 1,1′-ferrocene dicarbaldehyde with trans-1,2-diaminocyclohexane in high dilution at r.t. followed by reduction. When other experimental conditions were employed, the [6,6,6]ferrocenephane (L2) was also obtained. Both compounds were characterised by single crystal X-ray crystallography. The protonation of L1 and its metal complexation were evaluated by the effect on the electron-transfer process of the ferrocene (fc) unit of L1 using cyclic voltammetry (CV) and square wave voltammetry (SWV) in anhydrous CH3CN solution and in 0.1 M nBu4NPF6 as the supporting electrolyte. The electrochemical process of L1 between −300 and 900 mV is complicated by amine oxidation. On the other hand, an anodic shift from the fc/fc+ wave of L1 of 249, 225, 81 and 61 mV was observed by formation of Zn2+, Ni2+, Pd2+ and Cu2+ complexes, respectively. Whereas Mg2+ and Ca2+ only have with L1 weak interactions and they promote the acid-base equilibrium of L1. This reveals that L1 is an interesting molecular redox sensor for detection of Zn2+ and Ni2+, although the kinetics of the Zn2+ complex formation is much faster than that of the Ni2+ one. The X-ray crystal structure of [PdL1Cl2] was determined and showed a square–planar environment with Pd(II) and Fe(II) centres separated by 3.781(1) Å. The experimental anodic shifts were elucidated by DFT calculations on the [ML1Cl2] series and they are related to the nature of the HOMO of these complexes and a four-electron, two-orbital interaction.  相似文献   
132.
Novel 2,3-dihydro-4-pyridinones were synthesized via the reaction of curcumin and primary amines or amine acetates under microwave irradiation. Montmorillonite K-10 was used as a catalyst. Reaction times did not exceed 120 s. The structures of the compounds were established by elemental analysis and from their mass, 1H- and 13C-NMR spectra.  相似文献   
133.
The merits and limitations of gas-phase electron diffraction as a technique for determining accurately the structures of small organic molecules are demonstrated by comparing the molecular structures of five benzene derivatives studied in two different laboratories. The existence of many possible representations of the structure of a molecule (r a, r g, r α, r α0, r e, …), implying differences in the physical meaning of geometrical parameters, is discussed in some detail as it may cause difficulties in a comparison. Also illustrated are different ways of estimating and expressing uncertainties in the geometrical parameters from a gas-phase electron diffraction study.  相似文献   
134.
In this paper we study some sequences of weighted means of continuous real valued Gaussian processes. More precisely we consider suitable generalizations of both arithmetic and logarithmic means of a Gaussian process with covariance function which satisfies either an exponential decay condition or a power decay condition. Our aim is to provide limits of variances of functionals of such weighted means which allow the application of some large deviation results in the literature.  相似文献   
135.
Novice students have difficulty with the topic of limits in calculus. We believe this is in part because of the multiple perspectives and shifting metaphors available to solve items correctly. We investigated college calculus instructors' personal concepts of limits. Based upon previous research investigating introductory calculus student metaphorical reasoning, we examined 11 college instructors' metaphorical reasoning on limit concepts. This paper focused on previous research of metaphor clusters observed among students to answer the following: (a) Do college instructors use metaphorical reasoning to conceptualize the meaning of a limit? (b) Can we characterize instructor metaphorical reasoning similar to those observed among students? (c) Will an instructor's self‐identification of metaphor clusters be consistent with our metaphor coding? We found that college instructors' perspectives vary, either graphical or algebraic, in their explanations of limit items. All the instructors used metaphors, and instructor metaphorical reasoning aligned with student metaphor clusters. Instructors tended to change their metaphors with respect to the limit item. Instructors were not aware of their use of metaphors, nor were they aware of their inconsistency in their choice of metaphor. We believe that instructor awareness of their own distinct perspectives and metaphors would assist students' understanding of limit concepts.  相似文献   
136.
Abstract

The title compound 3 has been synthesized from 3,4,6-tri-O-acetyl-2-deoxy-2-nitroso-α-D-glucopyranosyl chloride (1) via compound 2. Azide reduction of 3 is accompanied by ON-acetyl migration to afford N-acetyl-N-(3,4,6-tri-O-acetyl-2-deoxy-2-hydroxyimino-β-D-arabino-hexopyranosyl) amine (4), also characterized as its Z and E peracetates. On the basis of IR, 1H NMR and X-ray structural data from compound 4, its β-NHAc configuration, (Z) 2-hydroxyimino, and °S2 conformation, were established.  相似文献   
137.
We propose a homological approach to two conjectures descended from the Erdös-Ko-Rado Theorem, one due to Chvátal and the other to Frankl and Füredi. We apply the method to reprove, and in one case improve, results of these authors related to their conjectures.  相似文献   
138.
139.
Mycotoxins are important non-anthropogenic food and feed contaminants, which can be present on almost every agricultural commodity. Effective consumer protection therefore essentially depends on food surveillance by reliable quantitative analysis enabled by appropriate quality control. Certified (matrix) reference materials (CRMs) are versatile tools to support quality assurance. However, in the case of ochratoxin A (OTA), a hepato- and nephrotoxic mycotoxin, which is regulated in various foods, there is a lack of suitable CRMs. This lack has now been overcome by the development of two European Reference Materials (ERM?) for the determination of OTA in roasted coffee (ERM?-BD475) and red wine (ERM?-BD476). This article discusses the material preparation process as well as the results of homogeneity and stability testing. Furthermore, the results of the in-house certification studies carried out at BAM Federal Institute for Materials Research and Testing are presented and discussed. Interlaboratory comparison studies involving selected expert laboratories with documented expertise in the field of mycotoxin analysis were conducted to confirm the certified values determined by BAM. The certified ochratoxin A values and their corresponding expanded uncertainties (k?=?2) were assigned in full compliance with the requirements of ISO Guide 35 and are as follows: (6.0?±?0.6)???g?kg?1 for roasted coffee, ERM?-BD475, and (0.52?±?0.11)???g?L?1 for red wine, ERM?-BD476.  相似文献   
140.

1,4-Dichlorobenzene is a frequently used lavatory deodorant although it has strong endocrine disrupting and potential carcinogenic effects. A large amount (approximately 15,000 tonnes annually worldwide) of this compound is released into the environment. This paper deals with the determination of 1,4-dichlorobenzene in a variety of environmental matrices. Various extraction and concentration methods such as charcoal absorbtion tubes and headspace sampling were applied. Sensitive and selective ion monitoring GC-MS measurements were used for determination. Significant concentrations of the compound have been identified in lavatory air, waste water, waste water sludge and human breast milk.

  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