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   40484篇
  免费   3997篇
  国内免费   10063篇
化学   44994篇
晶体学   643篇
力学   891篇
综合类   309篇
数学   2415篇
物理学   5292篇
  2024年   70篇
  2023年   526篇
  2022年   824篇
  2021年   1249篇
  2020年   1759篇
  2019年   1484篇
  2018年   1539篇
  2017年   1516篇
  2016年   1699篇
  2015年   1535篇
  2014年   2270篇
  2013年   3755篇
  2012年   3149篇
  2011年   2580篇
  2010年   2040篇
  2009年   2415篇
  2008年   2701篇
  2007年   2873篇
  2006年   2679篇
  2005年   2518篇
  2004年   2431篇
  2003年   1894篇
  2002年   1354篇
  2001年   1085篇
  2000年   1118篇
  1999年   989篇
  1998年   862篇
  1997年   788篇
  1996年   707篇
  1995年   683篇
  1994年   582篇
  1993年   432篇
  1992年   491篇
  1991年   371篇
  1990年   288篇
  1989年   231篇
  1988年   183篇
  1987年   120篇
  1986年   123篇
  1985年   99篇
  1984年   89篇
  1983年   49篇
  1982年   54篇
  1981年   50篇
  1980年   37篇
  1979年   31篇
  1978年   36篇
  1977年   34篇
  1976年   37篇
  1974年   39篇
排序方式: 共有10000条查询结果,搜索用时 234 毫秒
1.
Parabolic subgroups are the building blocks of Artin groups. This paper extends previous results of Cumplido, Gebhardt, Gonzales-Meneses and Wiest, known only for parabolic subgroups of finite type Artin groups, to parabolic subgroups of FC-type Artin groups. We show that the class of finite type parabolic subgroups is closed under intersection. We also study an analog of the curve complex for mapping class group constructed by Cumplido et al. using parabolic subgroups. We extend the construction of this complex, called the complex of parabolic subgroups, to FC-type Artin groups. We show that this simplicial complex is, in most cases, infinite diameter and conjecture that it is δ-hyperbolic.  相似文献   
2.
The artificially accurate design of nonmetal electrocatalysts’ active site has been a huge challenge because no pure active species with the specific structure could be strictly controlled by traditional synthetic methods. Species with a multiconfiguration in the catalyst hinder identification of the active site and the subsequent comprehension of the reaction mechanism. We have developed a novel electro-assisted molecular assembly strategy to obtain a pure pentagon ring on perfect graphene avoiding other reconstructed structures. More importantly, the active atom was confirmed by the subtle passivation process as the topmost carbon atom. Recognition of the carbon-defect electrocatalysis reaction mechanism was first downsized to the single-atom scale from the experimental perspective. It is expected that this innovative electro-assisted molecular assembly strategy could be extensively applied in the active structure-controlled synthesis of nonmetal electrocatalysts and verification of the exact active atom.  相似文献   
3.
《Mendeleev Communications》2022,32(6):777-779
The reactions of aryllithium reagents o-LiC6H4CH2NR2 with (MeO)2CO afford two new tris(aryl)carbinols bearing pendant-NR2 donor groups in the side chain [o-R NCH C H ] COH [R = Me, R + R = (CH) ]. These alcohols feature helical chirality due to differently inclined aromatic fragments and are presented in a crystalline cell as two M and P enantiomers. Carbinol (R = Me) readily reacts with (Me3SiCH2)3Sc(THF)2 to give a scandium bis(alkyl) complex [(o-C6H4CH2NMe2)3CO]Sc(CH2SiMe3)2 featuring rigid binding of the alkoxy anion through a κ1-O, κ2-N chelating coordination mode  相似文献   
4.
Enhancement of axial magnetic anisotropy is the central objective to push forward the performance of Single-Molecule Magnet (SMM) complexes. In the case of mononuclear lanthanide complexes, the chemical environment around the paramagnetic ion must be tuned to place strongly interacting ligands along either the axial positions or the equatorial plane, depending on the oblate or prolate preference of the selected lanthanide. One classical strategy to achieve a precise chemical environment for a metal centre is using highly structured, chelating ligands. A natural approach for axial-equatorial control is the employment of macrocycles acting in a belt conformation, providing the equatorial coordination environment, and leaving room for axial ligands. In this review, we present a survey of SMMs based on the macrocycle belt motif. Literature systems are divided in three families (crown ether, Schiff-base and metallacrown) and their general properties in terms of structural stability and SMM performance are briefly discussed.  相似文献   
5.
6.
The requirement of green and sustainable materials to prepare heterogeneous catalysts has intensified for practical reasons over the past few decades. Carbohydrates are possibly the most plentiful and renewable organic materials in nature with inimitable physiochemical properties, plausible low-cost and large-scale production, and sustainability features could be exploited in the generation of nanostructured heterogeneous catalysts. This review article outlines the organic transformations catalyzed by diverse carbohydrate-based nanostructured catalysts in greener and environmentally friendly processes. Selected examples are highlighted for a variety of organic reactions exploiting the proposed catalysts’ reactivity and reusability, and interactions with the intrinsic nature of the applied carbohydrate supports; advantages and speculated challenges of the introduced catalysts are deliberated as well.  相似文献   
7.
Human societies are characterized by three constituent features, besides others. (A) Options, as for jobs and societal positions, differ with respect to their associated monetary and non-monetary payoffs. (B) Competition leads to reduced payoffs when individuals compete for the same option as others. (C) People care about how they are doing relatively to others. The latter trait—the propensity to compare one’s own success with that of others—expresses itself as envy. It is shown that the combination of (A)–(C) leads to spontaneous class stratification. Societies of agents split endogenously into two social classes, an upper and a lower class, when envy becomes relevant. A comprehensive analysis of the Nash equilibria characterizing a basic reference game is presented. Class separation is due to the condensation of the strategies of lower-class agents, which play an identical mixed strategy. Upper-class agents do not condense, following individualist pure strategies. The model and results are size-consistent, holding for arbitrary large numbers of agents and options. Analytic results are confirmed by extensive numerical simulations. An analogy to interacting confined classical particles is discussed.  相似文献   
8.
In this study, we investigated an alternative method for the chemical CO2 reduction reaction in which power ultrasound (488 kHz ultrasonic plate transducer) was applied to CO2-saturated (up to 3%) pure water, NaCl and synthetic seawater solutions. Under ultrasonic conditions, the converted CO2 products were found to be mainly CH4, C2H4 and C2H6 including large amount of CO which was subsequently converted into CH4. We have found that introducing molecular H2 plays a crucial role in the CO2 conversion process and that increasing hydrogen concentration increased the yields of hydrocarbons. However, it was observed that at higher hydrogen concentrations, the overall conversion decreased since hydrogen, a diatomic gas, is known to decrease cavitational activity in liquids. It was also found that 1.0 M NaCl solutions saturated with 2% CO2 + 98% H2 led to maximum hydrocarbon yields (close to 5%) and increasing the salt concentrations further decreased the yield of hydrocarbons due to the combined physical and chemical effects of ultrasound. It was shown that CO2 present in a synthetic industrial flue gas (86.74% N2, 13% CO2, 0.2% O2 and 600 ppm of CO) could be converted into hydrocarbons through this method by diluting the flue gas with hydrogen. Moreover, it was observed that in addition to pure water, synthetic seawater can also be used as an ultrasonicating media for the sonochemical process where the presence of NaCl improves the yields of hydrocarbons by ca. 40%. We have also shown that by using low frequency high-power ultrasound in the absence of catalysts, it is possible to carry out the conversion process at ambient conditions i.e., at room temperature and pressure. We are postulating that each cavitation bubble formed during ultrasonication act as a “micro-reactor” where the so-called Sabatier reaction -CO2+4H2UltrasonicationCH4+2H2O - takes place upon collapse of the bubble. We are naming this novel approach as the “Islam-Pollet-Hihn process”.  相似文献   
9.
硒是动植物及人体生长必需的十五种微量元素之一,具有清除体内自由基、抗氧化、增强免疫力等功能,但其安全剂量的范围却很窄。利用扫描电子显微镜(SEM)和X射线衍射仪(XRD)对湿法球磨制备的硫铁矿形貌进行了表征。SEM观测发现加乙醇助磨后的硫铁矿为粒径大小较均匀的球形颗粒团聚体,粒径范围在17~200 nm之间,平均粒径138 nm。XRD衍射图谱中的特征峰与FeS2衍射图谱中各峰位置基本一致,因此判定硫铁矿中主要化学组分为FeS2,且图谱中基本没有杂峰,表明制备过程中并未混入杂质,样品纯度较高。实验结果表明,该法制备的硫铁矿具有颗粒粒径小、比表面积大、反应活性高等优点。研究中利用X射线光电子能谱仪(XPS)对硫铁矿去除水体中SeO2-3的机理进行了研究。研究结果表明, (1)在较为广泛的实验pH范围(pH 2.2~11.5),硫铁矿均能有效去除水体中SeO2-3,去除效率(除pH值7.8以外)均达到90%以上;(2)硫铁矿与SeO2-3发生反应后,其主要组成元素的XPS特征峰结合能有所减小,表明硫铁矿表面发生了一定化学变化;(3)酸碱环境下硫铁矿去除SeO2-3的机理不完全相同,酸性环境下,硫铁矿对SeO2-3的去除是单纯的氧化还原过程,即硫铁矿中被酸活化的S2-2将SeO2-3还原为单质Se(0),并且酸性越强,SeO2-3去除效果越好;碱性环境下,SeO2-3的去除过程中氧化还原与络合反应并存,硫铁矿表面有络合态Fe(OH)SeO3和单质Se(0)两种存在形态,且碱性越强,络合态Fe(OH)SeO3含量越高。以上研究结果为硫铁矿去除固定水体和土壤中以SeO2-3为代表的可变价金属阴离子提供重要理论依据和应用基础。  相似文献   
10.
《Mendeleev Communications》2022,32(4):507-509
We report on the synthesis of new Ru(bpy)2(phen) catalyst for the oscillatory Belousov–Zhabotinsky chemical reaction and on the preparation of novel Ru(bpy)2(phen)-based self-oscillating gels. The synthesized gels exhibit high-amplitude autonomous mechanical oscillations when the Belousov–Zhabotinsky reaction proceeds inside these gels  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