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   17895篇
  免费   3131篇
  国内免费   2391篇
化学   12792篇
晶体学   203篇
力学   1281篇
综合类   159篇
数学   1824篇
物理学   7158篇
  2024年   62篇
  2023年   377篇
  2022年   637篇
  2021年   668篇
  2020年   747篇
  2019年   655篇
  2018年   584篇
  2017年   517篇
  2016年   818篇
  2015年   818篇
  2014年   1005篇
  2013年   1215篇
  2012年   1610篇
  2011年   1645篇
  2010年   1095篇
  2009年   1024篇
  2008年   1185篇
  2007年   1025篇
  2006年   1054篇
  2005年   868篇
  2004年   684篇
  2003年   570篇
  2002年   566篇
  2001年   469篇
  2000年   391篇
  1999年   451篇
  1998年   316篇
  1997年   294篇
  1996年   338篇
  1995年   286篇
  1994年   271篇
  1993年   201篇
  1992年   190篇
  1991年   155篇
  1990年   133篇
  1989年   112篇
  1988年   107篇
  1987年   66篇
  1986年   60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 11 毫秒
61.
A CA19-9 electrochemical immunosensor was constructed using a hybrid self-assembled membrane modified with a gold electrode and applied to detect real samples. Hybrid self-assembled membranes were selected for electrode modification and used to detect antigens. First, the pretreated working electrodes were placed in a 3-mercaptopropionic acid (MPA)/β-mercaptoethanol (ME) mixture for 24 h for self-assembly. The electrodes were then placed in an EDC/NHS mixture for 1 h. Layer modification was performed by stepwise dropwise addition of CA19-9 antibody, BSA, and antigen. Differential pulse voltammetry was used to characterize this immunosensor preparation process. The assembled electrochemical immunosensor enables linear detection in the concentration range of 0.05–500 U/mL of CA19-9, and the detection limit was calculated as 0.01 U/mL. The results of the specificity measurement test showed that the signal change of the interfering substance was much lower than the response value of the detected antigen, indicating that the sensor has good specificity and strong anti-interference ability. The repeatability test results showed that the relative standard deviations were less than 5%, showing good accuracy and precision. The CA19-9 electrochemical immunosensor was used for the actual sample detection, and the experimental results of the standard serum addition method showed that the RSD values of the test concentrations were all less than 10%. The recoveries were 102.4–115.0%, indicating that the assay has high precision, good accuracy, and high potential application value.  相似文献   
62.
Hydrosilylation is one of the most important reactions in synthetic chemistry and ranks as a fundamental method to access organosilicon compounds in industrial and academic processes. However, the enantioselective construction of chiral-at-silicon compounds via catalytic asymmetric hydrosilylation remained limited and difficult. Here we report a highly enantioselective hydrosilylation of ynones, a type of carbonyl-activated alkynes, using a palladium catalyst with a chiral binaphthyl phosphoramidite ligand. The stereospecific hydrosilylation of ynones affords a series of silicon-stereogenic silylenones with up to 94% yield, 20:1 regioselectivity and 98:2 enantioselectivity. The density functional theory(DFT) calculations were conducted to elucidate the reaction mechanism and origin of high degree of stereoselectivity, in which the powerful potential of aromatic interaction in this reaction is highlighted by the multiple C–H-π interaction and aromatic cavity-oriented enantioselectivitydetermining step during desymmetric functionalization of Si–H bond.  相似文献   
63.
64.
ZnO microstructures have been grown from zinc chloride (ZnCl2) and ammonia solution at 100 °C for 1 – 24 hours. X‐ray diffraction, scanning electron microscope and field‐emission scanning microscope were utilized to investigate the structural properties and morphology of the ZnO crystals. Structural investigations show that phase‐pure hexagonal structure ZnO has been successfully synthesized, and the hexagonal structure ZnO can be achieved in solutions with an appropriate range of concentrations. Under our experimental conditions, several different morphologies of ZnO structures were obtained, including flower‐like and bar flower‐like. The relationship between the morphology and experimental conditions are discussed.  相似文献   
65.
Main observation and conclusion Bioorthogonal click chemistry has emerged as a powerful tool for the specific modification of proteins in complex mixtures.Metab...  相似文献   
66.
Vitamin C nanoliposomes were prepared by combining a conventional method (film evaporation) with dynamic high pressure microfluidization. Their physicochemical characterizations (antioxidant activity, particle size, entrapment efficiency, morphology, in vitro drug release, and storage stability) and skin permeation behavior were investigated. The results showed that vitamin C nanoliposomes, having equivalent DPPH (2, 2-diphenyl-1-picrylhydrazyl) free radical scavenging capacity of pure vitamin C solution without loss of their biological activity, exhibited better storage stability at 37°C for 24 hours and at 4°C for 60 days, a more excellent sustained drug release as well as higher skin penetration rate than vitamin C liposomes.  相似文献   
67.
Technetium decontamination factor as a function of the acidity, flow ratio, scrubbing stage number was investigated by counter-current cascade experiments or mixer-settler batch tests. Results showed that the acidity of the scrubbing acid has little influence on the decontamination factor of technetium when the acidity was kept in the range of 4.5–6 M. The most effective method to increase the decontamination factor is to lower the feed-to-acid flow ratio. Keeping other condition same the factor increased to 10.3 from 3.1 when feed-to-acid ratio changed to 4 from 5.6. The loss of uranium and plutonium can be recovered through a re-extraction technology.  相似文献   
68.
69.
The hybridization between the outmost s orbitals of metal (Bi3+,Sn2+,Pb2+,Ag+) and O 2p orbitals has been widely employed to develop innovative semiconductors w...  相似文献   
70.
Qingwei Du  Wei Zhang  Hao Ma  Jia Zheng  Bo Zhou  Yiqun Li 《Tetrahedron》2012,68(18):3577-3584
A palladium-based catalyst (Fe3O4/SiO2/HPG–OPPh2–PNP) supported on chlorodiphenylphosphine-functionalized magnetic nanoparticles was successfully prepared from Fe3O4/SiO2 with sequential attachment of glycerol and chlorodiphenylphosphine, followed by treatment of an ethanolic solution of palladium chloride with hydrazine. The as-prepared catalyst was characterized by ICP-AES, FTIR, XRD, SEM, and TEM. The Fe3O4/SiO2/HPG–OPPh2–PNP was found as a magnetically separable and highly active catalyst for Suzuki coupling reactions of aryl iodides, bromides, and chlorides as well as Heck reactions of aryl iodides and bromides. Under appropriate conditions, all reactions afforded the desired products in moderate to excellent yields. Moreover, this catalyst can be easily recovered by using a magnetic field and directly reused for at least six cycles without significant loss of its activity.  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