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   2065篇
  免费   292篇
  国内免费   205篇
化学   1503篇
晶体学   27篇
力学   127篇
综合类   16篇
数学   209篇
物理学   680篇
  2024年   6篇
  2023年   51篇
  2022年   60篇
  2021年   70篇
  2020年   119篇
  2019年   102篇
  2018年   73篇
  2017年   67篇
  2016年   118篇
  2015年   97篇
  2014年   107篇
  2013年   170篇
  2012年   175篇
  2011年   202篇
  2010年   114篇
  2009年   103篇
  2008年   139篇
  2007年   119篇
  2006年   75篇
  2005年   71篇
  2004年   59篇
  2003年   60篇
  2002年   62篇
  2001年   68篇
  2000年   48篇
  1999年   48篇
  1998年   23篇
  1997年   26篇
  1996年   18篇
  1995年   11篇
  1994年   17篇
  1993年   13篇
  1992年   13篇
  1991年   7篇
  1990年   11篇
  1988年   7篇
  1987年   4篇
  1986年   3篇
  1985年   4篇
  1984年   4篇
  1983年   3篇
  1982年   4篇
  1981年   2篇
  1980年   1篇
  1979年   1篇
  1978年   1篇
  1977年   1篇
  1975年   1篇
  1973年   1篇
  1957年   2篇
排序方式: 共有2562条查询结果,搜索用时 15 毫秒
41.
Pt–Ni/-Al2O3 catalysts have been prepared and studied in n-hexane dehydrocyclization. The selectivity for benzene and toluene, a chain lengthening product formation was improved by Ni and correlated with its content.
Pt–Ni/-Al2O3 -. Ni . Ni , .
  相似文献   
42.
The conversion of n-hexane was studied on a Pt-Sn/Al2O3 catalyst, a PtSn alloy and on the corresponding Pt catalysts. The results indicate the same catalytic effect of tin in supported and unsupported catalysts. It is concluded that the role of tin is connected with alloy formation.
- Pt-Sn/Al2O3, PtSn Pt-. . , .
  相似文献   
43.
44.
A highly-efficient preparative procedure for ( R, S )- and ( S, S)-pyrroHdine-2-carboxyHc acid 3,5-dioxa-4-boracyclohepta[2, 1-α ; 3,4-α′] dlnaphthalen-4-yl esters [ namely ( R, S )-BNBAP and (S, S )-BNBAP] is described and the crystal structure of (R, S )-BNBAP was obtained. The data indicate that ( R, S )-BNBAP is a spirocyclic inner borate salt with almost normal te-trahedral configuration. This structural form may be the basic reason for their high chemical, optical and thermodynamic sta-bility.  相似文献   
45.
The ever-increasing travel demand has brought great challenges to the organization, operation, and management of the subway system. An accurate estimation of passenger flow distribution can help subway operators design corresponding operation plans and strategies scientifically. Although some literature has studied the problem of passenger flow distribution by analyzing the passengers’ path choice behaviors based on AFC (automated fare collection) data, few studies focus on the passenger flow distribution while considering the passenger–train matching probability, which is the key problem of passenger flow distribution. Specifically, the existing methods have not been applied to practical large-scale subway networks due to the computational complexity. To fill this research gap, this paper analyzes the relationship between passenger travel behavior and train operation in the space and time dimension and formulates the passenger–train matching probability by using multi-source data including AFC, train timetables, and network topology. Then, a reverse derivation method, which can reduce the scale of possible train combinations for passengers, is proposed to improve the computational efficiency. Simultaneously, an estimation method of passenger flow distribution is presented based on the passenger–train matching probability. Finally, two sets of experiments, including an accuracy verification experiment based on synthetic data and a comparison experiment based on real data from the Beijing subway, are conducted to verify the effectiveness of the proposed method. The calculation results show that the proposed method has a good accuracy and computational efficiency for a large-scale subway network.  相似文献   
46.
彭芳  朱德荣  司士辉  肖辉 《化学进展》2008,20(4):586-593
光电化学型半导体生物传感器是一种利用半导体的光电特性来检测与光生电流或光生电压相关的待测物质浓度及生化过程参数的分析新技术。随着新兴半导体功能材料及相关加工技术的不断涌现,光电化学型半导体生物传感器已在微型化、集成化、多点及多参数测量方面显现出优势、有望在复杂体系中实现在线高灵敏、快速测定,在生物、医药、环境监测、食品等领域显示出广阔的应用前景。本文主要介绍了光电化学型半导体传感器的基本原理、特点及近几年的研究进展,并对其发展前景做了展望。  相似文献   
47.
质子化双氧/硫杂卟啉内氢原子迁移反应的理论研究   总被引:1,自引:0,他引:1  
在确定各反应体系反应物、产物稳定构象的基础上, 采用B3LYP/6-31G**方法在Gaussian 03程序下, 对质子化的双氧/硫杂卟啉的内氢迁移(IHAT)反应进行研究, 寻找并优化相应的过渡态, 比较其迁移反应速率的差异. 计算结果表明, 质子化双氧/硫杂卟啉的构象稳定性仍然是由芳香性、空间位阻、静电作用共同决定的. 质子化后的双取代体系的内氢迁移反应速率大小差异显著, 内环取代对IHAT反应速率的影响主要来源于电子效应, 而非构象变化; 且双取代对体系IHAT反应速率的影响要远大于单取代.  相似文献   
48.
As an important microbial resource, Actinomycetes, especially Streptomyces, have important application values in medicine and biotechnology. Streptomyces fungicidicus SYH3 was isolated from soil samples in tomato-growing areas and showed good inhibitory effects on Alternaria solani in tomato. To obtain pure active compounds, SYH3 fermentation broth was subjected to XAD-16 macroporous resin and silica gel column chromatography. Combined with the repeated preparation and separation of preparative high-performance liquid chromatography (HPLC), a total of four monomer compounds were obtained after activity tracking. Compound 4 was identified as a new six-membered lactone ring compound named 6-(5-hydroxy-6-methylheptyl)-5,6-dihydro-2H-pyran-2-one by 1D and 2D nuclear magnetic resonance (NMR) data and mass spectrometry (MS). The other three active compounds belong to the cyclodipeptide, and their half maximal inhibitory concentration (IC50) values against A. solani were 43.4, 42.9, and 30.6 μg/mL, respectively. Compound 4 significantly inhibited the spore germination and induced swollen and deformed local hyphae of A. solani with an IC50 value of 24.9 μg/mL. Compound 4 also had broad-spectrum antifungal activity and had a good antifungal effect on the tested plant-pathogenic fungi. The modes of action of new compound (4) still require further investigation, representing a novel and effective anti-fungal agent for future application.  相似文献   
49.
Organic charge-transfer complexes (CTCs) can function as versatile second near-infrared (NIR-II) theranostic platforms to tackle complicated solid tumors, while the structure–property relationship is still an unanswered problem. To uncover the effect of molecular stacking modes on photophysical and biochemical properties, herein, five ferrocene derivatives were synthesized as electron donors and co-assembled with electron-deficient F4TCNQ to form the corresponding CTCs. The crystalline and photophysical results showed that only herringbone-aligned CTCs (named anion-radical salts, ARS NPs) possess good NIR-II absorption ability and a photothermal effect for short π–π distances (<3.24 Å) and strong π-electron delocalization in the 1D F4TCNQ anion chain. More importantly, the ARS NPs simultaneously possess ·OH generation and thiol (Cys, GSH) depletion abilities to perturb cellular redox homeostasis for ROS/LPO accumulation and enhanced ferroptosis. In vitro experiments, FcNEt-F4 NPs, and typical ARS NPs, show outstanding antitumor efficiency for the synergistic effect of NIR-II photothermal therapy and ferroptosis, which provides a new paradigm to develop versatile CTCs for anti-tumor application.

Based on crystal engineering of charge transfer complexes (CTCs), ferrocene-based CTCs, with Fenton-catalyzing, biothiol-responsive and NIR-II photothermal abilities, were controllably developed and the structure–property relationship was revealed.  相似文献   
50.
The imbalance of intestinal microbiota can cause the accumulation of endotoxin in the main circulation system of the human body, which has a great impact on human health. Increased work and life pressure have led to a rise in the number of people falling into depression, which has also reduced their quality of life. The gut–brain axis (GBA) is closely related to the pathological basis of depression, and intestinal microbiota can improve depressive symptoms through GBA. Previous studies have proven that prebiotics can modulate intestinal microbiota and thus participate in human health regulation. We reviewed the regulatory mechanism of intestinal microbiota on depression through GBA, and discussed the effects of prebiotics, including plant polysaccharides and polyphenols on the regulation of intestinal microbiota, providing new clues for the prevention and treatment of depression.  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