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   934篇
  免费   42篇
  国内免费   7篇
化学   610篇
晶体学   12篇
力学   36篇
综合类   1篇
数学   89篇
物理学   235篇
  2023年   7篇
  2022年   25篇
  2021年   27篇
  2020年   23篇
  2019年   25篇
  2018年   23篇
  2017年   14篇
  2016年   37篇
  2015年   27篇
  2014年   51篇
  2013年   80篇
  2012年   76篇
  2011年   81篇
  2010年   39篇
  2009年   39篇
  2008年   47篇
  2007年   45篇
  2006年   59篇
  2005年   40篇
  2004年   31篇
  2003年   26篇
  2002年   30篇
  2001年   30篇
  2000年   18篇
  1999年   8篇
  1998年   4篇
  1997年   3篇
  1996年   4篇
  1995年   3篇
  1994年   4篇
  1992年   4篇
  1991年   3篇
  1990年   2篇
  1988年   3篇
  1987年   7篇
  1986年   3篇
  1985年   6篇
  1984年   7篇
  1982年   4篇
  1981年   3篇
  1980年   2篇
  1977年   1篇
  1976年   1篇
  1975年   1篇
  1974年   2篇
  1972年   1篇
  1967年   1篇
  1965年   1篇
  1917年   1篇
  1911年   2篇
排序方式: 共有983条查询结果,搜索用时 328 毫秒
161.
The metabolism and excretion of 2-methylaminoethoxycarbonyl-4,4'-dimethoxy-5,6,5',6'-dimethylenedioxybiphenyl-2'-carboxylic acid (DDB-S) were investigated in both rats and humans using liquid chromatography/electrospray ion trap mass spectrometry (LC/ESI-MS/MS). In rats, DDB-S was rapidly eliminated from the body after a single 50 mg/kg intravenous injection, with urine being a major excretion route. DDB-S was metabolically stable; approximately 96% of the administered dose was recovered in the form of the parent compound. Nevertheless, 12 metabolites were detected in the urine and feces collected from DDB-S-treated rats. The structural characterizations of the metabolites were elucidated from the MS(n) spectral analysis. Because DDB-S has a pseudo-symmetrical methylenedioxy biphenyl structure, regioselective deuterium-substituted DDB-S (d(5)-DDB-S) was used to assign the metabolic modification. The major metabolic pathways of DDB-S were identified as demethylenation of the methylenedioxy moiety, O-demethylation of the methoxy moiety and glucuronidation. In addition, N-demethylation of the methylaminoethyl group was also detected as a minor reaction.  相似文献   
162.
Shape-coded silica nanotubes (SNTs) were fabricated on the basis of template synthesis as a new dispersible microarray system. The template synthesis of shape-coded SNTs begins with the fabrication of a porous alumina film that has well-defined cylindrical pores with two or more different diameter segments by multistep anodization of an aluminum substrate. Then, SNTs were fabricated with a surface sol-gel method that can control the wall thickness of SNTs on the single-nanometer level. Attractively, the difference in optical reflectance between the segmented parts of individual silica nanotube makes it very convenient to identify each nanotube and enables these shape-coded SNTs to work as coding materials for biosensing.  相似文献   
163.
Hybrid wires composed of metal and conducting polymer (polypyrrole, Ppy) were electrochemically synthesized using a template synthesis method. We showed that the dimensions of the hybrid wires can be tailored by controlling the time of electrolysis. The electrical properties of Ppy having different lengths were measured using a scanning probe microscope (SPM) tip as an electrode without aligning the hybrid wires on a substrate. Especially, temperature-dependent characteristics of the I-V curve were determined. As we expected, the shorter the Ppy wire is, the better the current response produced. The activation energy of each Ppy wire is determined. It is confirmed that the electrical properties of a single wire of Ppy can be measured by SPM.  相似文献   
164.
Cubic-phase InSe nanowires were synthesized. Obtaining an appropriate high reaction temperature for formation of nanocrystals using poor solubility of Se powder in oleylamine induced the generation of unusual cubic phase of InSe to form nanowires. In comparison, hexagonal-phase nanoplates were formed by dissolving Se powder in oleylamine before increase of reaction temperature. The diameter of highly monodisperse wires was controlled by varying the amount of Se.  相似文献   
165.
Multifunctionality of nanotubes (NTs) is essential in biomedical and biotechnological applications, such as drug/gene delivery, bioseparation, and single-molecule detection. Each functionality should be located at optimal positions, depending on their roles such as targeting, tracking, and transporting. This enables avoidance of possible malfunctions or interference caused by having randomly distributed multiple groups (e.g., hydrophobic and hydrophilic) in the same space. In the aspect of multifunctionality, however, a general selective partial functionalization method of NT inner surfaces still remains a challenge. For this reason, we investigated a selective partial functionalization method of NTs using controlled gold nanoparticle (Au NP) diffusion in nanotubes and the preparation method of Au-capped silica nanotubes. Silica nanotubes (SNTs) were prepared using template sol-gel synthesis, and the inside of SNT was selectively modified with (3-trimethoxysilylpropyl) diethylenetriamine (DETA-silane). Au NPs of 2-nm size were then incubated with SNTs with DETA layer inside. Spontaneous diffusion of negatively charged Au NPs from bulk into the positively charged nanochannels of SNTs led trapped Au NPs onto the inner surface of SNTs. The degree of functionalization was controlled by the channel diameter, Au NP concentration, and solvent type. These SNTs partially modified with Au NPs were then used for localized selective chemical functionalization of SNTs. This was accomplished by the reaction between thionylated Au NPs trapped on the inside of SNTs and Alexa555-maleimide. Au-capped SNTs were prepared from SNTs with Au NPs inside by seed-mediated gold growth.  相似文献   
166.
The mechanism of the catalytic, enantioselective addition of trichlorosilyl enolates to aldehydes has been investigated. Kinetic studies using ReactIR and rapid injection NMR (RINMR) spectroscopy have confirmed the simultaneous operation of dual mechanistic pathways involving either one or two phosphoramides bound to a siliconium ion organizational center. This mechanistic dichotomy was initially postulated on the basis of catalyst loading studies and nonlinear effects studies. This duality explains the difference in reactivity and stereoselectivity of various classes of phosphoramides. Determination of Arrhenius activation parameters revealed that aldol addition occurs through the reversible albeit unfavorable formation of an activated complex, and natural-abundance 13C NMR kinetic isotope effect (KIE) studies have determined that the turnover limiting step is the aldol addition. A thorough examination of a range of phosphoramides has established empirical structure-activity selectivity relationships. In addition, the effects of catalyst loading, rate of addition, solvents, and additives have been studied and together allow the formulation of a unified mechanistic picture for the aldol addition.  相似文献   
167.
From the aerial parts of Scoparia dulcis L. (Scrophulariaceae) grown in Vietnam, four scopadulane-type diterpenoids (4-7), of which 7 is new and was given the trivial name scopadulcic acid C, together with nine known compounds were isolated. Their structures were elucidated by spectroscopic analyses. The absolute configurations of 4-7 were ascertained by applying the modified Mosher's method to iso-dulcinol (6). The isolation of the lignans nirtetralin and niranthin for the first time from S. dulcis is also of chemotaxonomic interest. The cytotoxic activity in KB cells, inhibitory effect on LPS/IFNgamma-induced NO production, inhibition of multidrug resistance (MDR), and antibacterial and antifungal activities of the scopadulane-type diterpenoids 4-7 were examined in this study.  相似文献   
168.
The charge structure and interaction mechanism on In-doped sulphur spinel FeInxCr2−xS4 are studied. The temperature dependence of magnetization μB, measured from 60 K to room temperature, suggests that FeInxCr2−xS4 (x=0.1x=0.1, 0.3) are ferrimagnetic. The Néel temperature is decreased with increasing non-magnetic In substitution as consequence of reduction of superexchange interaction for increased lattice parameter. FeInxCr2−xS4 is investigated by Mössbauer spectra from 4.2 K to room temperature. The asymmetric line broadening is observed for the sample FeInxCr2−xS4 and considered to be dynamic Jahn–Teller relaxation. The charge state of Fe ions is ferrous in character.  相似文献   
169.
The condensation pressure drop characteristics for pure refrigerants R22, R134a, and a binary refrigerant mixture R410A without lubricating oil in a single circular microtube were investigated experimentally. The test section consists of 1,220?mm length with horizontal copper tube of 3.38?mm outer diameter and 1.77?mm inner diameter. The experiments were conducted at refrigerant mass flux of 450–1,050?kg/m2s, and saturation temperature of 40°C. The main experimental results showed that the condensation pressure drop of R134a is higher than that of R22 and R410A for the same mass flux. The experimental data were compared against 14 two-phase pressure drop correlations. A new pressure drop model that is based on a superposition model for refrigerants condensing in the single circular tube is presented.  相似文献   
170.
Metallic glasses find wide applications in nanotechnology and micro electro-mechanical systems because of their unique physical properties due to their amorphous structures. The material removal mechanism in nanometric cutting of Cu50Zr50, a typical metallic glass, is studied using molecular dynamics method. The chip formation, workpiece deformation and scratching forces under various scratching depths, scratching velocities and temperatures are investigated. The effect of void defect on the cutting behaviors of metallic glass is also explored. The results show that the material removal in nanometric cutting process is based on extrusion instead of shearing, achieving a good understanding of material removal at the nanoscale.  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