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   157381篇
  免费   37812篇
  国内免费   14273篇
化学   131024篇
晶体学   1466篇
力学   9732篇
综合类   891篇
数学   16428篇
物理学   49925篇
  2024年   689篇
  2023年   5564篇
  2022年   5491篇
  2021年   6558篇
  2020年   8849篇
  2019年   6706篇
  2018年   6053篇
  2017年   4484篇
  2016年   10756篇
  2015年   10721篇
  2014年   11504篇
  2013年   13679篇
  2012年   13788篇
  2011年   12086篇
  2010年   10799篇
  2009年   10669篇
  2008年   9124篇
  2007年   7783篇
  2006年   6699篇
  2005年   5398篇
  2004年   4146篇
  2003年   3316篇
  2002年   3170篇
  2001年   2680篇
  2000年   2297篇
  1999年   2399篇
  1998年   1979篇
  1997年   1993篇
  1996年   1940篇
  1995年   1714篇
  1994年   1482篇
  1993年   1398篇
  1992年   1110篇
  1991年   970篇
  1990年   814篇
  1989年   652篇
  1988年   561篇
  1987年   454篇
  1986年   464篇
  1985年   397篇
  1977年   320篇
  1976年   366篇
  1975年   461篇
  1974年   477篇
  1973年   289篇
  1972年   373篇
  1971年   356篇
  1970年   542篇
  1969年   416篇
  1968年   459篇
排序方式: 共有10000条查询结果,搜索用时 15 毫秒
91.
Incorporation of a non-hexagonal ring into a nanographene framework can lead to new electronic properties. During the attempted synthesis of naphthalene-bridged double [6]helicene and heptagon-containing nanographene by the Scholl reaction, an unexpected azulene-embedded nanographene and its triflyloxylated product were obtained, as confirmed by X-ray crystallographic analysis and 2D NMR spectroscopy. A 5/7/7/5 ring-fused substructure containing two formal azulene units is formed, but only one of them shows an azulene-like electronic structure. The formation of this unique structure is explained by arenium ion mediated 1,2-phenyl migration and a naphthalene to azulene rearrangement reaction according to an in-silico study. This report represents the first experimental example of the thermodynamically unfavorable naphthalene to azulene rearrangement and may lead to new azulene-based molecular materials.  相似文献   
92.
Hierarchically porous metal–organic frameworks (HP-MOFs) are promising in various applications. Most reported HP-MOFs are prepared based on the generation of mesopores in microporous frameworks, and the formed mesopores are connected by microporous channels, limiting the accessibility of mesopores for bulky molecules. A hierarchical structure is formed by constructing microporous MOFs in uninterrupted mesoporous tunnels. Using the confined space in as-prepared mesoporous silica, highly dispersed metal precursors for MOFs are coated on the internal surface of mesoporous tunnels. Ligand vapor-induced crystallization is employed to enable quantitative formation of MOFs in situ, in which sublimated ligands diffuse into mesoporous tunnels and react with metal precursors. The obtained hierarchically porous composites exhibit record-high adsorption capacity for the bulky molecule trypsin. The thermal and storage stability of trypsin is improved upon immobilization on the composites.  相似文献   
93.
Su  X. F.  Zhang  Y. L.  Maximov  A. L.  Zhang  K.  Xin  Q.  Feng  C. Q.  Bai  X. F.  Wu  W. 《Russian Journal of Applied Chemistry》2020,93(1):127-136
Russian Journal of Applied Chemistry - Nanoscale ZSM-5 (AlZ5-D) and Ga-substituted ZSM-5 zeolites ((Al,Ga)Z5-D and GaZ5-D) were synthesized by a green dry-gel conversion strategy. For comparison,...  相似文献   
94.
95.
96.
In this communication, we report the synthesis of small‐sized (<10 nm), water‐soluble, magnetic nanoparticles (MNPs) coated with polyhedral oligomeric silsesquioxanes (POSS), which contain either polyethylene glycol (PEG) or octa(tetramethylammonium) (OctaTMA) as functional groups. The POSS‐coated MNPs exhibit superparamagnetic behavior with saturation magnetic moments (51–53 emu g?1) comparable to silica‐coated MNPs. They also provide good colloidal stability at different pH and salt concentrations, and low cytotoxicity to MCF‐7 human breast epithelial cells. The relaxivity data and magnetic resonance (MR) phantom images demonstrate the potential application of these MNPs in bioimaging.  相似文献   
97.
We conducted measurements of black carbon(BC) aerosol in Jiaxing,China during autumn from September 26 to November 30,2013.We investigated temporal and diurnal variations of BC,and its correlations with meteorological parameters and other major pollutants.Results showed that hourly mass concentrations of BC ranged from 0.2 to 22.0 μg/m3,with an average of 5.1 μg/m3.The diurnai variation of BC exhibited a bimodal distribution,with peaks at 07:00 and 18:00.The morning peak was larger than the evening peak.The mass percentages of BC in PM2.5 and PM10 were 7.1%and 4.8%,respectively.The absorption coefficient of BC was calculated to be 44.4 Mm-1,which accounted for 11.1%of the total aerosol extinction.BC was mainly emitted from local sources in southwestern Jiaxing where BC concentrations were generally greater than 11 μg/m3 during the measurement period.Correlation analysis indicated that the main sources of BC were motor vehicle exhaust,and domestic and industrial combustion.  相似文献   
98.
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   
99.
JPC – Journal of Planar Chromatography – Modern TLC - A new high-performance thin-layer chromatographic (HPTLC) method has been developed for the simultaneous estimation of...  相似文献   
100.
Herein, we report an addition to the toolbox for the monitoring and quantification of the hydrolytic decay of pentose-1-phosphates, which are known to be elusive and difficult to quantify. This communication describes how apparent equilibrium shifts of a nucleoside phosphorolysis reaction can be employed to calculate hydrolytic loss of pentose-1-phosphates based on the measurement of post-hydrolysis equilibrium concentrations of a nucleoside and a nucleobase. To demonstrate this approach, we assessed the stability of the relatively stable ribose-1-phosphate at 98 °C and found half-lives of 1.8–11.7 h depending on the medium pH. This approach can be extended to other sugar phosphates and related reaction systems to quantify the stability of UV-inactive and hard-to-detect reaction products and intermediates.  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