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   1444篇
  免费   121篇
  国内免费   24篇
化学   1118篇
晶体学   25篇
力学   26篇
数学   228篇
物理学   192篇
  2023年   13篇
  2022年   16篇
  2021年   27篇
  2020年   39篇
  2019年   30篇
  2018年   29篇
  2017年   29篇
  2016年   59篇
  2015年   54篇
  2014年   78篇
  2013年   115篇
  2012年   105篇
  2011年   116篇
  2010年   80篇
  2009年   69篇
  2008年   95篇
  2007年   79篇
  2006年   87篇
  2005年   78篇
  2004年   60篇
  2003年   59篇
  2002年   38篇
  2001年   23篇
  2000年   20篇
  1999年   18篇
  1998年   22篇
  1997年   6篇
  1996年   9篇
  1995年   9篇
  1994年   7篇
  1993年   8篇
  1992年   10篇
  1991年   7篇
  1990年   7篇
  1989年   10篇
  1988年   8篇
  1987年   7篇
  1986年   7篇
  1985年   9篇
  1984年   6篇
  1983年   3篇
  1982年   5篇
  1981年   6篇
  1980年   3篇
  1978年   3篇
  1976年   2篇
  1973年   2篇
  1969年   2篇
  1962年   2篇
  1961年   2篇
排序方式: 共有1589条查询结果,搜索用时 15 毫秒
91.
Allylrhodium species generated from potassium allyltrifluoroborates can undergo isomerization by 1,4‐rhodium(I) migration to give more complex isomers, which then react with cyclic imines to provide products with up to three new stereochemical elements. High enantioselectivities are obtained using chiral diene–rhodium complexes.  相似文献   
92.
Low-energy inverse photoelectron spectroscopy (LEIPS) and ultraviolet photoelectron spectroscopy (UPS) incorporated into the multitechnique XPS system were used to probe the ionization potential and the electron affinity of organic materials, respectively. By utilizing gas cluster ion beam (GCIB), in situ analyses and depth profiling of LEIPS and UPS were also demonstrated. The band structures of the 10-nm-thick buckminsterfullerene (C60) thin film on Au (100 nm)/indium tin oxide (100 nm)/glass substrate were successfully evaluated in depth direction.  相似文献   
93.
Reliable methods for enantioselective cis‐dihydroxylation of trisubstituted alkenes are scarce. The iron(II) complex cis‐α‐[FeII(2‐Me2‐BQPN)(OTf)2], which bears a tetradentate N4 ligand (Me2‐BQPN=(R,R)‐N,N′‐dimethyl‐N,N′‐bis(2‐methylquinolin‐8‐yl)‐1,2‐diphenylethane‐1,2‐diamine), was prepared and characterized. With this complex as the catalyst, a broad range of trisubstituted electron‐deficient alkenes were efficiently oxidized to chiral cis‐diols in yields of up to 98 % and up to 99.9 % ee when using hydrogen peroxide (H2O2) as oxidant under mild conditions. Experimental studies (including 18O‐labeling, ESI‐MS, NMR, EPR, and UV/Vis analyses) and DFT calculations were performed to gain mechanistic insight, which suggested possible involvement of a chiral cis‐FeV(O)2 reaction intermediate as an active oxidant. This cis‐[FeII(chiral N4 ligand)]2+/H2O2 method could be a viable green alternative/complement to the existing OsO4‐based methods for asymmetric alkene dihydroxylation reactions.  相似文献   
94.
The deuteriodifluoromethyl group (CF2D) represents a challenging functional group due to difficult deuterium incorporation and unavailability of precursor reagents. Herein, we report the use of chlorodifluoromethane (ClCF2H) gas in the continuous flow deuteriodifluoromethylation and gem‐difluoroalkenylation of aldehydes. Mechanistic studies revealed that the difluorinated oxaphosphetane (OPA) intermediate can proceed via alkaline hydrolysis in the presence of D2O to provide α‐deuteriodifluoromethylated benzyl alcohols or undergo a retro [2+2] cycloaddition under thermal conditions to provide the gem‐difluoroalkenylated product.  相似文献   
95.
The preparation and the influence of low ohmic multilayer thin film contacts of lead-salt homo- and heterolasers on the degradation of lasing parameters during recycling processes between low working temperatures and room temperatures storage are described and discussed in detail.  相似文献   
96.
97.
Dysfunction of the blood–brain barrier (BBB) is involved in the pathogenesis of many cerebral diseases. Oxidative stress and inflammation are contributing factors for BBB injury. Piceatannol, a natural ingredient found in various plants, such as grapes, white tea, and passion fruit, plays an important role in antioxidant and anti-inflammatory responses. In this study, we examined the protective effects of piceatannol on lipopolysaccharide (LPS) insult in mouse brain endothelial cell line (bEnd.3) cells and the underlying mechanisms. The results showed that piceatannol mitigated the upregulated expression of adhesion molecules (ICAM-1 and VCAM-1) and iNOS in LPS-treated bEnd.3 cells. Moreover, piceatannol prevented the generation of reactive oxygen species in bEnd.3 cells stimulated with LPS. Mechanism investigations suggested that piceatannol inhibited NF-κB and MAPK activation. Taken together, these observations suggest that piceatannol reduces inflammation and oxidative stress through inactivating the NF-κB and MAPK signaling pathways on cerebral endothelial cells in vitro.  相似文献   
98.
Results on applied infrared photoluminescence investigations of lead salt chalcogenides are presented. Interpretations of spectra and wafer maps are given. The results obtained may be applied to the investigation of material properties important for laser and detector fabrication.  相似文献   
99.
The clustered regularly interspaced short palindromic repeat (CRISPR)/Cas system is best known for its role in genomic editing. It has also demonstrated great potential in nucleic acid biosensing. However, the specificity limitation in CRISPR/Cas has created a hurdle for its advancement. More recently, nucleic acid aptamers known for their high affinity and specificity properties for their targets have been integrated into CRISPR/Cas systems. This review article gives a brief overview of the aptamer and CRISPR/Cas technology and provides an updated summary and discussion on how the two distinctive nucleic acid technologies are being integrated into modern diagnostic and therapeutic applications  相似文献   
100.
Materials exhibiting excitation wavelength‐dependent photoluminescence (Ex‐De PL) in the visible region have potential applications in bioimaging, optoelectronics and anti‐counterfeiting. Two multifunctional, chiral [Au(NHC)2][Au(CN)2] (NHC=(4R,5R)/(4S,5S)‐1,3‐dimethyl‐4,5‐diphenyl‐4,5‐dihydro‐imidazolin‐2‐ylidene) complex double salts display Ex‐De circularly polarized luminescence (CPL) in doped polymer films and in ground powder. Emission maxima can be dynamically tuned from 440 to 530 nm by changing the excitation wavelength. The continuously tunable photoluminescence is proposed to originate from multiple emissive excited states as a result of the existence of varied AuI???AuI distances in ground state. The steric properties of the NHC ligand are crucial to the tuning of AuI???AuI distances. An anti‐counterfeiting application using these two salts is demonstrated.  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