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   1895篇
  免费   108篇
  国内免费   107篇
化学   1270篇
晶体学   17篇
力学   92篇
综合类   3篇
数学   112篇
物理学   616篇
  2025年   4篇
  2024年   28篇
  2023年   41篇
  2022年   53篇
  2021年   79篇
  2020年   73篇
  2019年   75篇
  2018年   63篇
  2017年   42篇
  2016年   83篇
  2015年   82篇
  2014年   84篇
  2013年   100篇
  2012年   156篇
  2011年   156篇
  2010年   99篇
  2009年   81篇
  2008年   115篇
  2007年   106篇
  2006年   94篇
  2005年   103篇
  2004年   59篇
  2003年   40篇
  2002年   48篇
  2001年   28篇
  2000年   27篇
  1999年   26篇
  1998年   18篇
  1997年   20篇
  1996年   16篇
  1995年   17篇
  1994年   12篇
  1993年   6篇
  1992年   11篇
  1991年   19篇
  1990年   12篇
  1989年   2篇
  1988年   3篇
  1987年   7篇
  1985年   2篇
  1983年   5篇
  1982年   1篇
  1981年   1篇
  1980年   4篇
  1979年   1篇
  1978年   2篇
  1976年   2篇
  1974年   1篇
  1947年   1篇
  1946年   1篇
排序方式: 共有2110条查询结果,搜索用时 15 毫秒
81.
Preface     
Owing to the fast economic growing and the concern over greenhouse gases and air pollution,the development of nuclear energy is one important option to meet the expanded energy consumption in our future.To achieve that goal,continuing and reliable supplies of uranium are critical to future nuclear power projects.As is well known,global terrestrial reserves of uranium are limited and the deposits in China are relatively small.Given the projected big growth in nuclear power in the future,reliable supply of uranium at a reasonable price is essential for China.  相似文献   
82.
Han J  Zhuo Y  Chai YQ  Mao L  Yuan YL  Yuan R 《Talanta》2011,85(1):130-135
A new label-free amperometric immunosensor was developed for detection of carcinoembryonic antigen (CEA) based on chitosan-ferrocene (CS-Fc) and nano-TiO2 (CS-Fc + TiO2) complex film and gold nanoparticles-graphene (Au-Gra) nanohybrid. CS-Fc + TiO2 composite membrane was first modified on a bare glass carbon electrode. Then Au-Gra nanohybrid was formed on the CS-Fc + TiO2 membrane by self-assembly strategy. Next, further immobilization of anti-CEA was constructed according to the strong interaction between Au-Gra and the amido groups of anti-CEA. Since Au-Gra nanohybrid films provided a congenial microenvironment for the immobilization of biomolecules, the surface coverage of antibody protein could be enhanced and the sensitivity of the immunosensor has been improved. The good electronic conductive characteristic might be attributed to the synergistic effect of graphene nanosheets and Au NPs. The modified process was characterized by scanning electron microscope (SEM) and cyclic voltammetry (CV). Under optimized conditions, the resulting biosensor displayed good amperometric response to CEA with linear range from 0.01 to 80 ng/mL and a detection limit of 3.4 pg/mL (signal/noise = 3). The results demonstrated that the immunosensor has advantages of high conduction, sensitivity, and long life time. This assay approach showed a great potential in clinical applications and detection of low level proteins.  相似文献   
83.
A highly sensitive amperometric immunosensor has been developed for the detection of carcinoembryonic antigen (CEA). It is based on (a) Prussian Blue nanoparticles coated with poly(diallyldimethylammonium chloride) (P-PB) and (b) double-layer gold nanocrystals. The sensor was obtained by first electrodepositing porous gold nanocrystals on the glassy carbon electrode (GCE), and then by modifying the electrode with the coated P-PB. Subsequently, colloidal gold nanoparticles (nano-Au) were adsorbed onto the GCE by electrostatic interactions between the negatively charged nano-Au and the positively charged P-PB to immobilize CEA antibodies. Finally, bovine serum albumin was employed to block possible remaining active sites and to prevent the non-specific adsorption on the nano-Au. This immunosensor was characterized by cyclic voltammetry and scanning electron microscopy. The working range was adjusted to two concentration ranges, viz. from 0.5 to 10 ng.mL?1, and from 10 to 120 ng.mL?1 of CEA, with a detection limit of 0.2 ng.mL?1 at three times the background noise.  相似文献   
84.
Wenjuan Li  Yaqin Chai 《Talanta》2010,82(1):367-111
A new glucose biosensor had been developed by immobilizing positively charged gold nanoparticles (PGNs) on organosilica nanosphere functionalized prussian blue (OSiFPB)-modified gold electrode. The OSiFPB compound could not only effectively prevent the leakage of the PB mediator during measurements, but also easily form stable film on the electrode surface with efficient redox-activity and excellent conductivity. Furthermore, with the negatively charged surface of OSiFPB, this film could be used as an interface to adsorb the PGNs, which provided a congenial microenvironment for adsorbing biomolecules and decreased the electron-transfer impedance. So, with glucose oxidase as a model biomolecular, the proposed sensor showed rapid and highly sensitive amperometric response to glucose and this immobilization approach effectively improved the stability of the electron-transfer mediator. This work would be promising for construction of biosensor and bioelectronic devices.  相似文献   
85.
A chemical investigation on a South China Sea gorgonian, Menella sp. resulted in the isolation and elucidation of menellin A (1), a highly oxygenated racemate with C(8) skeleton, and a polyhydroxylated steroid, menellsteroid C (2), along with eight known compounds (3-10). The structures of the new compounds were elucidated by means of MS, 1D and 2D NMR spectra, and the relative stereochemistry of 1 was determined by X-ray single-crystal diffraction analysis. In addition, compound 7 was isolated as a new natural product. Compounds 1-3 and 7 were selected to test the anti-inflammatory inhibition against lipopolysaccharide (LPS)-induced nitric oxide (NO) production in RAW264.7 macrophages. 1 and 3 exhibited modest inhibitory effects with IC(50) of 71.3, 33.9 μM, respectively, compared to the positive control aminoguanidine (IC(50) 25.0 μM).  相似文献   
86.
In this work, an enzyme biosensor based on the immobilization of horseradish peroxidase (HRP) on SiO2/BSA/Au/thionine/nafion-modified gold electrode was fabricated successfully. Firstly, nafion was dropped on the surface of the gold electrode to form a nafion film followed by chemisorption of thionine (Thi) as an electron mediator via the ion-exchange interaction between the Thi and nafion. Subsequently, the SiO2/BSA/Au composite nanoparticles were assembled onto Thi film through the covalent bounding with the amino groups of Thi. Finally, HRP was immobilized on the SiO2/BSA/Au composite nanoparticles due to the covalent conjugation to construct an enzyme biosensor. The surface topographies of the SiO2/BSA/Au composite nanoparticles were investigated by using scanning electronic microscopy. The stepwise self-assemble procedure of the biosensor was further characterized by means of cyclic voltammetry and chronoamperometry. The enzyme biosensor showed high sensitivity, good stability and selectivity, a wide linear response to hydrogen peroxide (H2O2) in the range of 8.0 × 10-6 ∼ 3.72 × 10-3 mol/L, with a detection limit of 2.0 × 10-6 mol/L. The Michaelies-Menten constant KMapp K_M^{app} value was estimated to be 2.3 mM.  相似文献   
87.
An efficient highly regio- and stereoselective iron-catalyzed conjugate addition of 2,3-allenoates with primary or secondary alkyl, phenyl, or vinyl Grignard reagents to synthesize multi-substituted beta,gamma-unsaturated enoates has been reported. The in situ formed magnesium dienolate may readily react with different electrophilic reagents to construct an allylic quaternary carbon at the alpha-position of the ester group.  相似文献   
88.
The purpose of this paper was to study the chiral recognition mechanism of enantioseparation of adrenaline and its analogues using capillary electrophoresis. The enantiomeric separation of adrenaline and its analogues has been developed using beta-cyclodextrins as the chiral selectors. All the tested compounds were separated under the same experimental conditions to study the chiral recognition mechanisms, using a low-pH buffer (50 mM Tris buffer at pH 2.5). By means of molecular docking the inclusion course between beta-cyclodextrins and enantiomers was investigated and thus the interaction energy was obtained by molecular mechanics calculations. The results suggest that the difference in interaction energy for the side chain part is most likely responsible for enantiomeric separation.  相似文献   
89.
A new electrochemical biosensor for determination of hydrogen peroxide (H2O2) has been developed by immobilizing horseradish peroxidase (HRP) on silver colloids (nanosilver) and use of a DNA-functionalized interface. In the presence of the DNA and the nanosilver the immobilized HRP gives a pair of well-defined redox peaks with an electron-transfer rate constant of 3.27 ± 0.91 s−1 in pH 7.0 PBS. The presence of DNA also provides a biocompatible microenvironment for enzyme molecules, greatly amplifies the amount of HRP molecules immobilized on the electrode surface, and improves the sensitivity of the biosensor. Under optimum conditions the biosensor has electrocatalytic activity in the reduction of hydrogen peroxide with linear dependence on H2O2 concentration in the range 1.5 × 10−6 to 2.0 × 10−3 mol L−1; the detection limit is 5.0 × 10−7 mol L−1 at a signal-to-noise ratio of 3. The value of HRP in the composite membrane was found to be 1.62 mmol L−1. These results suggest that the properties of the complex film, with its bioelectrochemical catalytic activity, could make it useful for development of bioelectronic devices and for investigation of protein electrochemistry at functional interfaces.  相似文献   
90.
Chemical speciation of platinum metals and some other siderophile elements in Precambrian/Cambrian black shale, south China, were studied using stepwise dissolution, fire assay preconcentration, inductively coupled plasma mass spectrometry and instrumental neutron activation analysis. The results indicate that platinum metals in Precambrian/Cambrian black shale, south China, are enriched through a syngenetical mineralizing process.  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