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   17267篇
  免费   3146篇
  国内免费   2379篇
化学   12387篇
晶体学   201篇
力学   1253篇
综合类   164篇
数学   1838篇
物理学   6949篇
  2024年   7篇
  2023年   361篇
  2022年   388篇
  2021年   519篇
  2020年   740篇
  2019年   644篇
  2018年   567篇
  2017年   500篇
  2016年   808篇
  2015年   785篇
  2014年   981篇
  2013年   1193篇
  2012年   1599篇
  2011年   1659篇
  2010年   1109篇
  2009年   1035篇
  2008年   1187篇
  2007年   1038篇
  2006年   1059篇
  2005年   874篇
  2004年   687篇
  2003年   573篇
  2002年   568篇
  2001年   448篇
  2000年   371篇
  1999年   439篇
  1998年   308篇
  1997年   288篇
  1996年   333篇
  1995年   285篇
  1994年   272篇
  1993年   197篇
  1992年   187篇
  1991年   157篇
  1990年   133篇
  1989年   112篇
  1988年   108篇
  1987年   66篇
  1986年   59篇
  1985年   43篇
  1984年   31篇
  1983年   26篇
  1982年   13篇
  1981年   18篇
  1980年   7篇
  1979年   2篇
  1966年   1篇
  1957年   5篇
  1936年   2篇
排序方式: 共有10000条查询结果,搜索用时 15 毫秒
101.
化学工业生产中,用氢气为还原剂,通过选择性加氢可以制备多种重要化学品。5-羟甲基糠醛是重要的生物质基平台化合物,而5-甲基糠醛是用途广泛的化学品。由5-羟甲基糠醛加氢得到5-甲基糠醛是一条非常理想的路径,但是选择性活化C-OH非常困难。本文设计并制备了Pt@PVP/Nb2O5(PVP: 聚乙烯吡咯烷酮)催化剂,该催化体系巧妙地结合了位阻效应、氢溢流和催化剂界面的电子效应,系统研究了该催化剂对5-羟甲基糠醛选择性加氢制备5-甲基糠醛催化性能,在最优条件下,5-甲基糠醛的选择性可达92%。利用密度泛函理论计算研究了5-羟甲基糠醛选择性加氢制备5-甲基糠醛反应路径。  相似文献   
102.
Lv  Jiao  Wang  Ling  Sun  Zheng  Li  Qingzhong  Li  Xiaoyan 《Structural chemistry》2019,30(6):2409-2417
Structural Chemistry - The influences of small molecule doping on PdC3/PtC3···thiophene interaction have been investigated by atoms in molecules (AIM) theory, electron location...  相似文献   
103.
Recently, silicone rubber (VMQ) was extensively used in household articles and medical devices. To develop a kind of safe and long‐term antimicrobial VMQ was of great significance. In this work, a kind of vinyl‐contained polyhexamethylene guanidine hydrochloride (VPHMG) was synthesized and used as antimicrobial additive for VMQ. With the increasing of VPHMG addition, the mechanical properties and antimicrobial properties of VMQ‐VPHMG were significantly improved. In particular, the antimicrobial rates against Escherichia coli and Staphylococcus aureus were higher than 99.99% as for 4 wt% of VPHMG addition. Moreover, the surface concentration of VPHMG as well as the antimicrobial rates revealed almost unchanged after being extracted by water and methanol. All the results indicated the vinyl‐contained VPHMG vulcanization and therefore provided the permanent antimicrobial performance for VMQ.  相似文献   
104.
Acta Mathematicae Applicatae Sinica, English Series - The generalized estimating equations(GEE) approach is perhaps one of the most widely used methods for longitudinal data analysis. While the GEE...  相似文献   
105.
Development of effective organocatalysts for the living ring‐opening polymerization (ROP) of lactones is highly desired for the preparation of biocompatible and biodegradable polyesters with controlled microstructures and physical properties. Herein, a new class of hydrogen‐bond donating bisurea catalysts is reported for the ROP of lactones under solvent‐free conditions. ROP of lactones mediated by the bisurea/7‐methyl‐1,5,7‐triazabicyclo[4.4.0]dec‐5‐ene (MTBD) catalyst exhibits a living/controlled manner, affording the polymers and copolymers with the well‐defined structure, predictable molecular weight, narrow molecular weight distribution, and high selectivity for monomer at low catalyst loadings at ambient temperature. The possible mechanism of bisurea/MTBD‐catalyzed ROP of lactones is proposed, in which the bisurea activates the carbonyl group of lactones while MTBD facilitates the nucleophilic attack of the initiating/propagating alcohol by hydrogen bonding. Moreover, the poly(ε‐caprolactone‐co‐δ‐valerolactone) [P(CL‐co‐VL)] random copolymers with various compositions were synthesized using the bisurea/MTBD catalyst. The measurements of thermal properties and crystalline structure demonstrate that the CL and VL units are cocrystallized in the crystalline phase of P(CL‐co‐VL) copolymers. © 2018 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2019 , 57, 90–100  相似文献   
106.
107.
Science China Mathematics - In the framework of complete metric spaces, this paper provides several sufficient conditions for the well-posedness with respect to an admissible function, which...  相似文献   
108.
In this study, a more sensitive and reliable quantitative method based on ultra‐high performance liquid chromatography coupled with Q‐Exactive‐Orbitrap‐MS in full‐mass scan was developed and validated for the determination of PF‐04620110 in dog plasma. After protein precipitation with acetonitrile, the sample separations were carried out on an Acquity BEH C18 column with 1 mm ammonium acetate in water and acetonitrile containing 0.1% acetic acid as mobile phase, at a flow rate of 0.4 mL/min. The assay showed excellent linearity over the concentration range of 1–2000 ng/mL with correlation coefficient >0.9980 (r > 0.9980). The LLOQ was 1 ng/mL. The inter‐ and intra‐day precision (RSD, %) was within 9.69% while the accuracy (RE, %) was in the range of ?8.59–11.24%. The extraction recovery was >85.37% and the assay was free of matrix effects. PF‐04620110 was demonstrated to be stable under various processing and handing conditions. The validated method was successfully applied to the pharmacokinetic study of PF‐04620110 in dogs and the results revealed that PF‐04620110 was slowly eliminated from plasma with a clearance of 60.81 ± 7.11 mL/h/kg for intravenous administration and 81.44 ± 25.79 mL/h/kg for oral administration. The oral bioavailability was determined to be 77.89% in dogs.  相似文献   
109.
110.
In this communication, an unprecedented interception of CnF2n+1(O)SO. radical with a copper-based carbene has been established. Distinguished by wide substrate scopes and mild reaction conditions, this novel radical–carbene coupling reaction (RCC reaction) provides a fundamentally different and mechanistically interesting strategy for the synthesis of perfluoroalkanesulfinate esters.  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