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   633篇
  免费   13篇
  国内免费   5篇
化学   478篇
晶体学   15篇
力学   9篇
数学   26篇
物理学   123篇
  2022年   5篇
  2021年   5篇
  2020年   7篇
  2019年   11篇
  2018年   4篇
  2016年   9篇
  2015年   11篇
  2014年   16篇
  2013年   29篇
  2012年   26篇
  2011年   38篇
  2010年   19篇
  2009年   18篇
  2008年   27篇
  2007年   38篇
  2006年   41篇
  2005年   37篇
  2004年   34篇
  2003年   36篇
  2002年   31篇
  2001年   4篇
  2000年   10篇
  1999年   11篇
  1998年   6篇
  1997年   9篇
  1996年   6篇
  1995年   6篇
  1994年   4篇
  1993年   5篇
  1992年   3篇
  1991年   8篇
  1990年   4篇
  1989年   4篇
  1988年   5篇
  1987年   4篇
  1986年   6篇
  1985年   8篇
  1984年   14篇
  1983年   7篇
  1982年   11篇
  1981年   10篇
  1980年   8篇
  1979年   10篇
  1978年   10篇
  1977年   8篇
  1976年   5篇
  1975年   3篇
  1974年   5篇
  1973年   10篇
  1959年   1篇
排序方式: 共有651条查询结果,搜索用时 12 毫秒
81.
Migration of Li+ ions via the vacancy mechanism in LiX (X = F, Cl, Br, and I) with the rocksalt and hypothetical zinc blende structures and Li2X (X = O, S, Se, and Te) with the antifluorite structure has been investigated using first-principles projector augmented wave calculations with the generalized gradient approximation. The migration paths and energies, determined by the nudged-elastic-band method, are discussed on the basis of two idealized models: the rigid-sphere and charged-sphere models. The trajectories and energy profiles of the migration in these lithium compounds vary between these two models, depending on the anion species and crystal structure. The migration energies in LiX with both the rocksalt and hypothetical zinc blende structures show a tendency to decrease with increasing periodic number of the anion species in the periodic table. This is consistent with the widely accepted view that anion species with large ionic radii and high polarizabilities are favorable for good ionic conduction. In contrast, Li2O exhibits the lowest migration energy among Li2X compounds, although O is the smallest among the chalcogens, indicating that electrostatic attractive interactions play the dominant role in the inter-ion interactions in Li2O and, therefore, in the ion migration.  相似文献   
82.
Tetraphenylporphine zinc(II) (ZnTPP) was found to be adsorbed from its CH2Cl2 solution into a Nafion (Nf) film. The characteristics of the adsorption of ZnTPP into the Nf film were studied using a visible absorption spectroscopic technique. The initial rate (v0, mol cm(-2) s(-1)) for uptake of ZnTPP was saturated with increasing ZnTPP concentration (c0, M) in the solution. This kinetic profile was analyzed in terms of a Michaelis-Menten model considering preequilibrium of ZnTPP adsorption between the solution and the outer layer of the Nf film, followed by diffusion to an inner bulk region, giving a maximum diffusion reflux of v(max) = (2.2 +/- 0.2) x 10(-13) mol cm(-2) s(-1). This is different from the kinetics for the Nf/phthalocyanine zinc(II) (ZnPc) film, which gives a linear plot of v(0) vs c(0). This can be explained by the relatively slow diffusion of ZnTPP in the film compared to that of ZnPc because of steric factors: ZnTPP contains bulky tetraphenyl moieties attached perpendicular to a porphyrin ring, whereas ZnPc has higher planarity. The isotherm for the adsorption of ZnTPP into the Nf film was analyzed using a Langmuir isotherm equation, yielding an equilibrium constant of (3.6 +/- 1.1) x 10(6) M(-1) and a saturated amount of adsorbed ZnTPP of (1.8 +/- 0.1) x 10(-9) mol cm(-2), suggesting monolayer adsorption of ZnTPP on the hydrophobic polymer network interfacial with hydrophilic transport channels without significant intermolecular overlap. This is in contrast to the multilayer adsorption mode suggested for the ZnPc adsorption. The tetraphenyl moieties could prevent the stacking of ZnTPP for multilayer adsorption.  相似文献   
83.
Vibrational spectra of microsolvated benzonitrile radical anions (C6H5CN- -S; S = H2O and CH3OH) were measured by probing the electron detachment efficiency in the 3 microm region, representing resonance bands of autodetachment via OH stretching vibrations of the solvent molecules. The hydrogen-bonded OH band for both the cluster anions exhibited a large shift to the lower energy side with approximately 300 cm-1 compared to those for the corresponding neutral clusters. The solvent molecules are bound collinearly to the edge of the CN group of the benzonitrile anion in the cluster structures optimized with the density functional theory, in which the simulated vibrational energies are in good agreement with the observed band positions. Natural population analyses were performed for a qualitative implication in changes of solvent orientation upon electron attachment. Asymmetric band shapes depending on the vibrational modes are discussed with respect to dynamics of the autodetachment process from a theoretical aspect incorporated with density functional calculations.  相似文献   
84.
The Pd‐catalyzed polycondensation of 4‐octylaniline with various dibromoarylenes was carried out under microwave heating. Microwave heating led to a decrease in the reaction time and an increase in the molecular weight of the polymers as compared to conventional heating. Microwave heating also allowed the catalyst loading to be reduced to 1 mol %, yielding polymerization results that were comparable to those under conventional heating and 5 mol % catalyst. Investigations regarding field‐effect transistors and organic photovoltaic cells using the obtained poly(arylamine) with azobenzene units revealed that increasing the molecular weight of the polymer led to improved device performance, including hole mobility and power conversion efficiency. © 2014 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2015 , 53, 536–542  相似文献   
85.
For selective synthesis of linear polyester having a functional group at one end, polycondensation between 1,4‐butanediol ( 1a ) and sebacoyl chloride ( 2a ) and between 1,12‐dodecanediol ( 1b ) and isophthaloyl chloride ( 2b ) was conducted in the presence of oxime resin or oxime silica gel, followed by cleavage of the formed polyester from the solid‐phase support with aniline. Matrix‐assisted laser desorption ionization time‐of‐flight mass spectra and 1H NMR spectra of the cleaved polyester showed that the products contained not only polyester with anilide at one end ( poly 1 ), but also polyester with anilides at both ends ( poly 2 ). The product ratio of poly 1 to poly 2 ( poly 1 / poly 2 ) was dependent on monomers, monomer concentration, feed ratio of monomer to oxime moiety in the support, oxime content in the support, reaction solvent, and the nature of the support. Polyester with a high poly 1 / poly 2 ratio of 81/21 and moderate molecular weight (Mn = 1430 g/mol) was obtained by polycondensation of 1b and 2b in the presence of oxime silica gel in dichloromethane. © 2015 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2015 , 53, 1379–1386  相似文献   
86.
87.
In order to reduce the color quenching in the measurement of tritium in urine by liquid scintillation counting , UV irradiation was applied to decompose the organic substances in the sample. Urine was decolorized under UV irradiation in the presence of hydrogen peroxide. As a result, color quenching was considerably suppressed and higher counting efficiency of tritium was obtained. This UV treatment made it possible to increase the urine content in the sample from 2 to 40% (v/v) without significant decrease of counting efficiency. Either higher sensitivity or shorter analysis time was achieved in the tritium measurement by the augmentation of urine content. When the measurement time was 30 min, the detection limit of tritium defined as 3s was 0.03 Bq/ml. At the expense of some sensitivity (set at a detection limit of 0.3 Bq/ml), the measurement time was shortened to 0.5 min. These results will make a great improvement to routine tritium monitoring as well as to emergency monitoring in mass tritium exposure.   相似文献   
88.
We developed a highly sensitive electrochemical system for the sensing of ovalbumin (OVA). Lysozyme origin/tyrosine‐rich peptides (RNRCKGTDVQAWY4C) were immobilized on magnetic beads, and the competitive reaction between OVA and oligothreonine/OVA origin peptide probe (T8VLLPDEVSG) could then be measured. In a previous study, the detection of OVA at the 10?13 M level was achieved using RNRCKGTDVQAWY4C‐modified beads via a cross‐linker. To improve the sensitivity to OVA, this system uses T8VLLPDEVSG peptide probe to measure the interaction to RNRCKGTDVQAWY4C immobilized on magnetic beads. The peak of Y4C actually was an electron‐transfer peptide, which represented the oxidation of a phenolic hydroxyl group. First, we confirmed that the oxidation response of Y4C was increased based on an improvement in the electron transfer accessibility by oligothreonine. Next, T8VLLPDEVSG peptide probe was used for the electrochemical sensing of OVA in solutions that contained consistent amounts of RNRCKGTDVQAWY4C on magnetic beads. As a result, the peak current decreased as the concentration of OVA increased. The sensitivity to OVA was improved compared with the use of only RNRCKGTDVQAWY4C on magnetic beads. The OVA detection level was 10?14 M, which approximates the results from antibody‐antigen reactions. Consequently, the proposed system is a powerful new concept in protein sensing.  相似文献   
89.
We report the formation of icosahedral B(12)H(8) (+) through ion-molecule reactions of the decaborane ion [B(10)H(x)(+) (x=6-14)] with diborane (B(2)H(6)) molecules in an external quadrupole static attraction ion trap. The hydrogen content n of B(12)H(n)(+) is determined by the analysis of the mass spectrum. The result reveals that B(12)H(8)(+) is the main product. Ab initio calculations indicate that B(12)H(8)(+) preferentially forms an icosahedral structure rather than a quasiplanar structure. The energies of the formation reactions of B(12)H(14)(+) and B(12)H(12)(+) between B(10)H(x)(+) (x=6,8) ions, which are considered to be involved in the formation of B(12)H(n)(+), and a B(2)H(6) molecule are calculated. The calculations of the detachment pathway of H(2) molecules and H atoms from the product ions, B(12)H(14)(+) and B(12)H(12) (+), indicate that the intermediate state has a relatively low energy, enabling the detachment reaction to proceed owing to the sufficient reaction energy. This autodetachment of H(2) accounts for the experimental result that B(12)H(8)(+) is the most abundant product, even though it does not have the lowest energy among B(12)H(n)(+).  相似文献   
90.
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