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   38933篇
  免费   492篇
  国内免费   312篇
化学   18055篇
晶体学   364篇
力学   1550篇
综合类   13篇
数学   10373篇
物理学   9382篇
  2023年   103篇
  2022年   434篇
  2021年   495篇
  2020年   302篇
  2019年   304篇
  2018年   1443篇
  2017年   1687篇
  2016年   1131篇
  2015年   864篇
  2014年   883篇
  2013年   1364篇
  2012年   3771篇
  2011年   3008篇
  2010年   2279篇
  2009年   1899篇
  2008年   1122篇
  2007年   1135篇
  2006年   1047篇
  2005年   4757篇
  2004年   4188篇
  2003年   2527篇
  2002年   699篇
  2001年   438篇
  2000年   191篇
  1999年   249篇
  1998年   200篇
  1997年   133篇
  1996年   121篇
  1995年   106篇
  1994年   108篇
  1993年   81篇
  1992年   232篇
  1991年   205篇
  1990年   187篇
  1989年   171篇
  1988年   148篇
  1987年   97篇
  1986年   86篇
  1985年   114篇
  1984年   82篇
  1983年   70篇
  1982年   73篇
  1981年   58篇
  1980年   56篇
  1979年   68篇
  1978年   60篇
  1976年   122篇
  1975年   56篇
  1974年   73篇
  1973年   72篇
排序方式: 共有10000条查询结果,搜索用时 15 毫秒
1.
Reactivity studies of the GeII→B complex L(Cl)Ge⋅BH3 ( 1 ; L=2-Et2NCH2-4,6-tBu2-C6H2) were performed to determine the effect on the GeII→B donation. N-coordinated compounds L(OtBu)Ge⋅BH3 ( 2 ) and [LGe⋅BH3]2 ( 3 ) were prepared. The possible tuning of the GeII→B interaction was proved experimentally, yielding compounds 1-PPh2-8-(LGe)-C10H6 ( 4 ) and L(Cl)Ge⋅GaCl3 ( 5 ) without a GeII→B interaction. In 5 , an unprecedented GeII→Ga coordination was revealed. The experimental results were complemented by a theoretical study focusing on the bonding in 1 − 5 . The different strength of the GeII→E (E=B, Ga) donation was evaluated by using energy decomposition analysis. The basicity of different L(X)Ge groups through proton affinity is also assessed.  相似文献   
2.
The design of new solid-state proton-conducting materials is a great challenge for chemistry and materials science. Herein, a new anionic porphyrinylphosphonate-based MOF ( IPCE-1Ni ), which involves dimethylammonium (DMA) cations for charge compensation, is reported. As a result of its unique structure, IPCE-1Ni exhibits one of the highest value of the proton conductivity among reported proton-conducting MOF materials based on porphyrins (1.55×10−3 S cm−1 at 75 °C and 80 % relative humidity).  相似文献   
3.
4.
5.
A tertiary hydroxy group α to a carboxyl moiety comprises a key structural motif in many bioactive substances. With the herein presented metal‐free rearrangement of imides triggered by hypervalent λ3‐iodane, an easy and selective way to gain access to such a compound class, namely α,α‐disubstituted‐α‐hydroxy carboxylamides, was established. Their additional methylene bromide side chain constitutes a useful handle for rapid diversification, as demonstrated by a series of further functionalizations. Moreover, the in situ formation of an iodine(III) species under the reaction conditions was proven. Our findings clearly corroborate that hypervalent λ3‐benziodoxolones are involved in these organocatalytic reactions.  相似文献   
6.
Raman chemical imaging provides chemical and spatial information about pharmaceutical drug product. By using resolution methods on acquired spectra, the objective is to calculate pure spectra and distribution maps of image compounds. With multivariate curve resolution-alternating least squares, constraints are used to improve the performance of the resolution and to decrease the ambiguity linked to the final solution. Non negativity and spatial local rank constraints have been identified as the most powerful constraints to be used.  相似文献   
7.
Electrospun nonwovens of poly(L-lactide) (PLLA) modified with multiwall carbon nanotubes (MWCNT) and linear ladder-like poly(silsesquioxane) with methoxycarbonyl side groups (LPSQ-COOMe) were obtained. MWCNT and LPSQ-COOMe were added to the polymer solution before the electrospinning. In addition, nonwovens of PLLA grafted to modified MWCNT were electrospun. All modified nonwovens exhibited higher tensile strength than the neat PLA nonwoven. The addition of 10 wt.% of LPSQ-COOMe and 0.1 wt.% of MWCNT to PLLA increased the tensile strength of the nonwovens 2.4 times, improving also the elongation at the maximum stress.  相似文献   
8.
In this study, the functional interaction of HPLW peptide with VEGFR2 (Vascular Endothelial Growth Factor Receptor 2) was determined by using fast 15N‐edited NMR spectroscopic experiments. To this aim, 15N uniformly labelled HPLW has been added to Porcine Aortic Endothelial Cells. The acquisition of isotope‐edited NMR spectroscopic experiments, including 15N relaxation measurements, allowed a precise characterization of the in‐cell HPLW epitope recognized by VEGFR2.  相似文献   
9.
Numerous biological processes are connected with the efficient electron transfer reactions in proteins and peptides. In this review, we discuss briefly the relevance and current challenges associated with the voltammetric analysis of peptides and proteins with and without a metal redox center. Special attention is paid to the integration of electrochemical methods with new nanomaterials which offers amplification of multiplexing capabilities for simultaneous and very sensitive examination of various proteins. After critically discussing the most interesting approaches in the proteins/peptides voltammetric analysis reported so far, for the single or multiplexed examination of such biomolecules with demonstrated applicability in the real-sample analysis, existing challenges still need to be addressed and future directions in this field will be pointed out.  相似文献   
10.
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