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   14870篇
  免费   2162篇
  国内免费   1334篇
化学   10725篇
晶体学   179篇
力学   830篇
综合类   67篇
数学   1766篇
物理学   4799篇
  2024年   50篇
  2023年   323篇
  2022年   561篇
  2021年   593篇
  2020年   673篇
  2019年   579篇
  2018年   506篇
  2017年   440篇
  2016年   699篇
  2015年   729篇
  2014年   752篇
  2013年   1102篇
  2012年   1257篇
  2011年   1256篇
  2010年   826篇
  2009年   831篇
  2008年   972篇
  2007年   830篇
  2006年   741篇
  2005年   704篇
  2004年   513篇
  2003年   421篇
  2002年   409篇
  2001年   323篇
  2000年   291篇
  1999年   294篇
  1998年   196篇
  1997年   155篇
  1996年   197篇
  1995年   165篇
  1994年   138篇
  1993年   123篇
  1992年   102篇
  1991年   86篇
  1990年   91篇
  1989年   68篇
  1988年   63篇
  1987年   49篇
  1986年   40篇
  1985年   42篇
  1984年   37篇
  1983年   17篇
  1982年   16篇
  1981年   20篇
  1980年   11篇
  1979年   8篇
  1976年   10篇
  1975年   11篇
  1971年   7篇
  1969年   5篇
排序方式: 共有10000条查询结果,搜索用时 15 毫秒
961.
Lithium (Li) metal has attracted significant attention in areas that range from basic research to various commercial applications due to its high theoretical specific capacity (3860 mA h g−1) and low electrochemical potential (−3.04 vs. standard hydrogen electrode). However, dendrites often form on the surfaces of Li metal anodes during cycling and thus lead to battery failure and, in some cases, raise safety concerns. To overcome this problem, a variety of approaches that vary the electrolyte, membrane, and/or anode have been proposed. Among these efforts, the use of three-dimensional frameworks as Li hosts, which can homogenize and minimize the current density at the anode surface, is an effective approach to suppress the formation of Li dendrites. Herein, we describe the development of using carbon-based materials as Li hosts. While these materials can be fabricated into a variety of porous structures, they have a number of intrinsic advantages including low costs, high specific surface areas, high electrical conductivities, and wide electrochemical stabilities. After briefly summarizing the formation mechanisms of Li dendrites, various methods for controlling structural and surface chemistry will be described for different types of carbon-based materials from the viewpoint of improving their performance as Li hosts. Finally, we provide perspective on the future development of Li host materials needed to meet the requirements for their use in flexible and wearable devices and other contemporary energy storage techniques.  相似文献   
962.
The first useful enantioselective Pd-catalyzed asymmetric allylic alkylation of α-fluoro-β-ketoesters has been achieved using the Trost family of chiral ligands yielding products in up to 92 % ee. This work provides new insights regarding the typically modest selectivities associated with acyclic α-fluoroenolates and shows experimental evidence that the typically poor levels of enantiocontrol associated with these systems are not necessarily due to the presence of E/Z enolate mixtures. Finally, this methodology allows the easy preparation of useful 3-fluoropiperidine intermediates, and it is demonstrated that these systems are applicable to a range of functionalization reactions leading to new building blocks for the discovery of bioactive products.  相似文献   
963.
Hydrogen energy is an abundant, clean, sustainable and environmentally friendly renewable energy source. Therefore, the production of hydrogen by photocatalytically splitting water on semiconductors has been considered in recent years as a promising and sustainable strategy for converting solar energy into chemical energy to replace conventional energy sources and to solve the growing problem of environmental pollution and the global energy crisis. However, highly efficient solar-driven photocatalytic hydrogen production remains a huge challenge due to the poor visible light response of available photocatalytic materials and the low efficiency of separation and transfer of photogenerated electron-hole pairs. In the present work, organic heterojunction structures based on bacteriochlorophyll (BChl) and chlorophyll (Chl) molecules were introduced and used for solar-driven photocatalytic hydrogen production from water under visible light. Also, noble metal-free photocatalyst was successfully constructed on Ti3C2Tx nanosheets by simple successive deposition of Chl and BChl, which was used for the photocatalytic splitting water to hydrogen evolution reaction (HER). The results show that the optimal BChl@Chl@Ti3C2Tx composite has a high HER performance with 114 μmol/h/gcat, which is much higher than the BChl@Ti3C2Tx and Chl@Ti3C2Tx composites.  相似文献   
964.
Tetraiodotetraazapentacene I4TAP , the last missing derivative in the series of halogenated silylated tetraazapentacenes, was synthesized via condensation chemistry from a TIPS-ethynylated diaminobenzothiadiazol in three steps. Single and double reduction furnished its air-stable monoanion and relatively air-stable dianion, both of which were characterized by crystallography. All three species are structurally and spectroscopically compared to non-halogenated TAP and Br4TAP . I4TAP is an n-channel material in thin-film transistors with average electron mobilities exceeding 1 cm2 (Vs)−1.  相似文献   
965.
Lu  Deli  Xu  Yumeng  Chen  Zhe  Han  Sheng 《Research on Chemical Intermediates》2022,48(1):321-337
Research on Chemical Intermediates - Several attempts have been made to obtain aliphatic dicarboxylic diesters from esterification reaction to develop the biomass-derived platform molecules and...  相似文献   
966.
The gold-catalyzed ring-opening rearrangement of cyclopropenes affords an efficient route to either polysubstituted naphthols or aryl-substituted furans. Owing to the unique dichotomy of gold−carbenes, this protocol provides a switchable reaction selectivity between naphthols and furans enabled by the use of TFP−Au(MeCN)SbF6 (tri(2-furyl) phosphine) or PNP(AuNTf2)2 (bis(diphenylphosphino)(isopropyl) amine) as catalysts respectively. It is proposed that the gold−carbene intermediate might be involved in the cyclopropene→naphthol rearrangement while the gold-carbocation is more likely to be involved in the cyclopropene→furan rearrangement.  相似文献   
967.
We present a new full-dimensional diabatic potential energy matrix (DPEM) for electronically nonadiabatic collisions of OH(A 2Σ+) with H2, and we calculate the probabilities of electronically adiabatic inelastic collisions, nonreactive quenching, and reactive quenching to form H2O+H. The DPEM was fitted using a many-body expansion with permutationally invariant polynomials in bond-order functions to represent the many-body part. The dynamics calculations were carried out with the fewest-switches with time uncertainty and stochastic decoherence (FSTU/SD) semiclassical trajectory method. We present results both for head-on collisions (impact parameter b equal to zero) and for a full range of impact parameters. The results are compared to experiment and to earlier FSTU/SD and quantum dynamics calculations with a previously published DPEM. The various theoretical results all agree that nonreactive quenching dominates reactive quenching, but there are quantitative differences between the two DPEMs and between the b=0 results and the all-b results, especially for the probability of reactive quenching.  相似文献   
968.
Ephedrae Herba is one of the most commonly used herbal medicines, and it has been shown that most of the clinical efficacy for cold and asthma is exerted by its alkaloidal components. A simple and sensitive high-performance liquid chromatography method was developed using a perfluorooctyl column for the simultaneous determination of five alkaloids (norephedrine, norpseudoephedrine, ephedrine, pseudoephedrine, and methylephedrine) in Ephedrae Herba. The mobile phase comprising acetonitrile and 15 mM ammonium trifluoroacetate was used to elute the targets in isocratic elution mode. The method was validated for linearity (R2 > 0.999), repeatability, intraday and interday precision, recoveries with trueness (93.87–110.99%), limits of detection (5.35–5.76 µg/mL), and limits of quantification (20 µg/mL). The quantitative results revealed that the developed method was precise and accurate. Then it was successfully applied to determine the difference in the contents of three batches of Ephedrae Herba from three pharmaceutical companies.  相似文献   
969.
Mycotoxin contamination is a globally concerned problem for food and agricultural products since it may directly or indirectly induce severe threats to human health. Sensitive and selective screening is an efficient strategy to prevent or reduce human and animal exposure to mycotoxins. However, enormous challenges exist in the determination of mycotoxins, arising from complex sample matrices, trace-level analytes, and the co-occurrence of diverse mycotoxins. Appropriate sample preparation is essential to isolate, purify, and enrich mycotoxins from complicated matrices, thus decreasing sample matrix effects and lowering detection limits. With the cross-disciplinary development, new solid-phase extraction strategies have been exploited and integrated with nanotechnology to meet the challenges of mycotoxin analysis. This review summarizes the advance and progress of solid-phase extraction techniques as the methodological solutions for mycotoxin analysis. Emphases are paid on nanomaterials fabricated as trapping media of solid-phase extraction techniques, including carbonaceous nanoparticles, metal/metal oxide-based nanoparticles, and nanoporous materials. Advantages and limitations are discussed, along with the potential prospects.  相似文献   
970.
Cell membrane chromatography is an effective method for screening bioactive components acting on specific receptors in complex systems, which maintains the biological activity of the membrane receptors and improves screening efficiency. However, traditional cell membrane chromatography suffers from poor stability, resulting in a limited life span and low reproducibility, greatly limiting the application of this method. To address this problem, cyanuric chloride-decorated silica gel was used for the covalent immobilization of the cell membranes. Cyanuric chloride reacts with amino groups on the cell membranes and membrane receptors to form covalent bonds. In this way, the cell membranes are not easy to fall off. The column life of the cyanuric chloride-decorated epidermal growth factor receptor/cell membrane chromatography column was extended to more than 8 days, whereas the column life of the normal cell membrane chromatography column dropped sharply in the first 3 days. A cyanuric chloride-decorated epidermal growth factor receptor/cell membrane chromatography online HPLC-IT-TOF-MSn system was applied for screening drug leads from Trifolium pratense L. One potential drug lead, formononetin, which acts on the epidermal growth factor receptor, was screened. Our strategy of covalently immobilizing cell membrane receptors also improved the stability of cell membrane chromatography.  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