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   957篇
  免费   53篇
  国内免费   6篇
化学   621篇
晶体学   7篇
力学   38篇
综合类   1篇
数学   96篇
物理学   253篇
  2022年   6篇
  2021年   11篇
  2020年   13篇
  2019年   23篇
  2018年   10篇
  2017年   6篇
  2016年   25篇
  2015年   34篇
  2014年   31篇
  2013年   47篇
  2012年   76篇
  2011年   73篇
  2010年   44篇
  2009年   57篇
  2008年   44篇
  2007年   47篇
  2006年   46篇
  2005年   39篇
  2004年   31篇
  2003年   19篇
  2002年   26篇
  2001年   17篇
  2000年   19篇
  1999年   23篇
  1998年   8篇
  1997年   17篇
  1996年   14篇
  1995年   11篇
  1994年   10篇
  1993年   7篇
  1992年   6篇
  1991年   15篇
  1990年   9篇
  1989年   5篇
  1988年   13篇
  1987年   8篇
  1986年   6篇
  1985年   21篇
  1984年   13篇
  1983年   5篇
  1982年   5篇
  1981年   13篇
  1980年   4篇
  1979年   7篇
  1978年   6篇
  1977年   8篇
  1974年   7篇
  1973年   4篇
  1970年   4篇
  1969年   3篇
排序方式: 共有1016条查询结果,搜索用时 15 毫秒
981.
Splice site prediction on an RNA virus has two potential difficulties seriously degrading the performance of most conventional splice site predictors. One is a limited number of strains available for a virus species and the other is the diversified sequence patterns around the splice sites caused by the high mutation frequency. To overcome these two difficulties, a new algorithm called Genomic Splice Site Prediction (GSSP) algorithm, was proposed for splice site prediction of RNA viruses. The key idea of the GSSP algorithm was to characterize the interdependency among the nucleotides and base positions based on the eigen-patterns. Identified by a sequence pattern mining technique, each eigen-pattern specified a unique composition of the base positions and the nucleotides occurring at the positions. To remedy the problem of insufficient training data due to the limited number of strains for an RNA virus, a cross-species strategy was employed in this study. The GSSP algorithm was shown to be effective and superior to two conventional methods in predicting the splice sites of five RNA species in the Orthomyxoviruses family. The sensitivity and specificity achieved by the GSSP algorithm was higher than 99 and 94%, respectively, for the donor sites, and was higher than 96 and 92%, respectively, for the acceptor sites. Supplementary data associated with this work are freely available for academic use at http://homepage.ntu.edu.tw/ approximately d91548013/.  相似文献   
982.
Using scanning tunneling microscopy (STM), we demonstrate that oxidation on Pb films is greatly enhanced by atomic Cs catalysts. With only a minute concentration of isolated Cs substitutional atoms in the surface layer (0.004 ML coverage), surface oxidation rates are greatly enhanced. First-principles density functional theory (DFT) calculations reveal that a substitutional Cs atom strongly increases O2 binding on the surface. Then, with additional oxygen exposure this substitutional Cs-initiated oxidation process results in growth of PbO layers in an auto-catalytic manner. Furthermore, we investigate the role of temperature in the oxidation of the Pb films with and without Cs, and we explore the overall morphology of the resultant oxide layers.  相似文献   
983.
Lin ST  Wolfe JC  Dani JA  Shih WC 《Optics letters》2012,37(11):1781-1783
We present optitrode, a miniaturized flexible probe for integrated, localized light delivery and electrical recording. This device features an annular light guide with transparent polymer and fused silica layers surrounding a twisted-wire tetrode. We have developed a novel fabrication process, V-groove guided capillary assembly, to achieve high-precision, coaxial alignment of the various layers of the device. Optitrode with a length-to-diameter ratio ~500 (5 cm long, 100 μm diameter) has been fabricated, and both the electrical and optical functions have been characterized. The prototype can deliver 11% (110 mW) of the total laser power under abrupt bending angle ~25°.  相似文献   
984.
The hydrogen oxidation reaction on Pt-black/Nafion electrode was investigated using a rotating disk electrode and cyclic voltammetry technique. The voltammetric results demonstrated that the electrode can be prepared with good reproducibility and that Pt-black particles without direct contact with Nafion were still electrochemically active in taking part in the H-adsorption/desorption process. For hydrogen oxidation, the limiting current density was reduced by the presence of Nafion coating. The H2 diffusion resistance in Nafion film was avoided when the film thickness was less than 0.2 μm for a Pt-black loading of 20 μg. Moreover, the uncertainties in the kinetic results were discussed.  相似文献   
985.
Water assisted injection molding (WAIM) has gradually become one of the most important polymer processing methods for making hollowed parts. This study examined the morphological development in water assisted injection molded high density polyethylene (HDPE)/polyamide‐6 (PA‐6) blends. Samples for microscopic observation were prepared by an 80‐ton injection‐molding machine equipped with a tube cavity and with a water injection unit. A distinct skin layer, core region, and channel layer were observed across the thickness. The shape and size of the dispersed phase depended on the position both across the part thickness and along the flow direction. Small and large particles coexisted in the skin and channel layers, indicating that both coalescence and disintegration of the dispersed phase occurred in these layers. High water pressures were found to mold parts with smaller polyamide particle distributions. Additionally, the morphology of water assisted injection molded parts was compared to that of gas assisted injection molded products. It was found that water molded parts exhibit a smaller polyamide particle distribution than their gas counterparts. Copyright © 2010 John Wiley & Sons, Ltd.  相似文献   
986.
There are relatively few methods for the catalytic asymmetric synthesis of beta-lactams, and those that have been reported are generally cis selective. This communication describes the first catalytic enantioselective Staudinger reactions that preferentially furnish trans beta-lactams (trans = relationship of Ph to R1). The key to this method is the use of an N-triflyl protecting group for the imine. Along with serving as interesting targets in their own right, N-triflyl beta-lactams readily react with nucleophiles to generate useful families of compounds, such as gamma-amino alcohols and beta-amino acids.  相似文献   
987.
Spectroscopic and electrochemical characterizations of ferrocene- and biferrocene-functionalized terpyridine octanethiolate monolayer-protected clusters were investigated and reported. The electrochemical measurements of Ru2+ coordinated with 4'-ferrocenyl-2,2':6',2' '-terpyridine and 4'-biferrocenyl-2,2':6',2' '-terpyridine complexes were dominated by the Ru2+/Ru3+ redox couple (E(1/2) at approximately 1.3 V), Fe(2+)/Fe(3+) redox couples (E(1/2) from approximately 0.6 to approximately 0.9 V), and terpy/terpy-/terpy2- redox couples (E(1/)(2) at ca. -1.2 and ca. -1.4 V). The substantial appreciable variations detected in the Ru2+/Ru3+ and Fe2+/Fe3+ oxidation potentials indicate that there is an interaction between the Ru2+ and Fe2+ metal centers. The coordination of the Ru2+ metal center with 4'-ferrocenyl-2,2':6',2' '-terpyridine and 4'-biferrocenyl-2,2':6',2' '-terpyridine leads to an intense 1[(d(pi)Fe)6] --> 1[d(pi)Fe)5(pi*terpyRu)1] transition in the visible region. The 1[(d(pi)Fe)6] -->1[d(pi)Fe)5(pi*terpyRu)1] transition observed at approximately 510 nm revealed that there was a qualitative electronic coupling between metal centers. The coordination of the Ru2+ transition metal center lowers the energy of the pi*terpy orbitals, causing this transition.  相似文献   
988.
Fluorescence probe and nuclear magnetic resonance (NMR) methods were employed to investigate the micellation of prepared crown ether surfactants, e.g. decyl 15‐crown‐5 and decyl 18‐crown‐6. Pyrene was employed as the fluorescence probe to evaluate the critical micellar concentration (CMC) of these surfactants in aqueous solutions while spin lattice relaxation times (T1) and chemical shifts of H‐1 NMR were applied in non‐aqueous solutions. Decyl 15‐crown‐5 with lower CMC forms micelles much easier than decyl 18‐crown‐6 with higher CMC in aqueous solutions, whereas decyl 18‐crown‐6 forms micelles easier than decyl 15‐crown‐5 in nonaqueous solutions. Comparison of the CMC of crown ether surfactants and other polyoxyethylene surfactants such as decylhexaethylene glycol was made. Effects of salts and solvents on the micellar formation were also investigated. In general, additions of both alkali metal salts and polar organic solvents into the aqueous surfactant solutions increased in the CMC of these surfactants. The formation of micelles in organic solvents such as methanol and acetonitrile was successfully observed by the NMR method while it was difficult to study these surfactants in organic solutions by the pyrene fluorescence probe method. The NMR study revealed that the formation of micelles resulted in the decrease in all H‐1 spin lattice relaxation times (T1) of hydrophobic groups, e.g. CH3 and CH2, and hydrophilic group OCH2 of these surfactants. However, upon the micellar formation, the H‐1 chemical shifts (δ) of these surfactant hydrophobic groups were found to shift to downfield (increased δ) while the chemical shift of the hydrophilic group OCH2 moved to up‐field. Comparison of the spin lattice relaxation time and H‐1 chemical shift methods was also made and discussed.  相似文献   
989.
Determining eight colorants in milk beverages by capillary electrophoresis   总被引:8,自引:0,他引:8  
Milk beverages are popular because of their high nutritional value, and milk products that are enhanced with various fruit flavors are especially in high demand in Asia. Colorants are usually added to fruit flavored milk in order to increase its attraction and appearance, therefore, the detection and measurement of colorants in this type of beverage are relatively important for health issue reasons. Carminic acid, a natural colorant, along with tartrazine, Fast green FCF, Brilliant blue FCF, Allura Red AC, Indigo carmine, Sunset yellow FCF, and New coccine, which are seven different synthetic food colorants, are commonly used as food additives, therefore, this study would focus on the development of an analytical method for the detection of these common colorants in milk beverages. A high efficiency capillary electrophoresis separation method was finished by a pH 10.0 running buffer containing 7.0 mM beta-cyclodextrin, and the eight colorants were separated with baseline resolution within 9 min. In order to reduce the matrix interference resulting from the constituents of milk, a suitable polyamide column solid-phase extraction (SPE) was also investigated for milk sample pretreatment. The combination of the simple SPE pretreatment and the fast separation method of capillary electrophoresis, was able to determine successfully without matrix interference the content of these colorant additives in commercial milk beverages. The recoveries of the eight food colorants in milk beverages were better than 85% and the detection limits were also lower than 0.5 microg/ml by the developed method.  相似文献   
990.
Mei-Hsiu Shih  Mou-Yung Yeh 《Tetrahedron》2003,59(23):4103-4111
A convenient method for the preparation of sydnonyl-substituted α, β-unsaturated ketones, based on Knoevenagel condensation, is presented. Although well known, this reaction has never been utilized in the condensation involving sydnone derivatives. Thus, 3-aryl-4-formylsydnones (1) are reacted with active methylene compounds such as acetylacetone (2a), ethyl acetoacetate (2b), diethyl malonate (2c), malononitrile (4a), ethyl cyanoacetate (4b) and cyanoacetamide (4c) by modified Knoevenagel condensation to afford multifunctional derivatives. Also, sydnonyl-substituted 1,3-dihydro-indol-2-one derivatives 10 were synthesized successfully by condensing 3-aryl-4-formylsydnones (1) with oxindoles 9.  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