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   685篇
  免费   12篇
  国内免费   3篇
化学   405篇
晶体学   1篇
力学   17篇
数学   137篇
物理学   140篇
  2023年   6篇
  2022年   11篇
  2021年   10篇
  2020年   14篇
  2019年   13篇
  2017年   7篇
  2016年   15篇
  2015年   9篇
  2014年   20篇
  2013年   31篇
  2012年   21篇
  2011年   36篇
  2010年   25篇
  2009年   14篇
  2008年   28篇
  2007年   28篇
  2006年   20篇
  2005年   23篇
  2004年   22篇
  2003年   25篇
  2002年   21篇
  2001年   13篇
  2000年   16篇
  1999年   8篇
  1998年   9篇
  1997年   8篇
  1996年   12篇
  1995年   6篇
  1994年   5篇
  1993年   7篇
  1992年   7篇
  1990年   6篇
  1989年   6篇
  1988年   5篇
  1987年   8篇
  1986年   10篇
  1985年   9篇
  1984年   12篇
  1983年   12篇
  1982年   6篇
  1981年   12篇
  1980年   9篇
  1979年   16篇
  1978年   4篇
  1977年   7篇
  1976年   7篇
  1975年   8篇
  1974年   9篇
  1973年   8篇
  1959年   6篇
排序方式: 共有700条查询结果,搜索用时 15 毫秒
51.
We define cheat sensitive cryptographic protocols between mistrustful parties as protocols which guarantee that, if either cheats, the other has some nonzero probability of detecting the cheating. We describe an unconditionally secure cheat sensitive nonrelativistic bit commitment protocol which uses quantum information to implement a task which is classically impossible; we also describe a simple relativistic protocol.  相似文献   
52.
A Rayleigh-Faber-Krahn type inequality is used to derive bounds for boundary value problems appearing in reaction-diffusion problems where the reactant is consumed. Interesting quantities are the minimum of the solution and the measure of the set where it vanishes. The proofs are rather elementary and apply to problems possessing solutions in a weak sense.  相似文献   
53.
A new in situ electrochemical method of functionalizing an oxide-free Ni surface is demonstrated using octanethiol. Initial adsorption results in a multilayer molecular film, which blocks both the hydrogen evolution reaction (HER) and re-oxidation of the Ni by ambient oxygen. However, excess octanethiol can be removed by rinsing with ethanol, leaving behind a monolayer that continues to protect against re-oxidation but gives rise to an unexpected enhancement in the HER, with a greater enhancement for longer film formation times. The presence of an octanethiol monolayer on the surface was confirmed by spectroscopic observation of the CH(2), CH(3) and thiolate groups using infra red spectroscopy, while X-ray photo-electron spectroscopy demonstrated the effectiveness of the thiol layer as a barrier to surface oxidation. The electrochemically prepared octanethiol film impedes oxidation of the Ni in air more effectively than a film formed by immersion in a solution of octanethiol in ethanol.  相似文献   
54.
Anti-virulence strategy is currently considered a promising approach to overcome the global threat of the antibiotic resistance. Among different bacterial virulence factors, the biofilm formation is recognized as one of the most relevant. Considering the high and growing percentage of multi-drug resistant infections that are biofilm-mediated, new therapeutic agents capable of counteracting the formation of biofilms are urgently required. In this scenario, a new series of 18 thiazole derivatives was efficiently synthesized and evaluated for its ability to inhibit biofilm formation against the Gram-positive bacterial reference strains Staphylococcus aureus ATCC 25923 and S. aureus ATCC 6538 and the Gram-negative strain Pseudomonas aeruginosa ATCC 15442. Most of the new compounds showed a marked selectivity against the Gram-positive strains. Remarkably, five compounds exhibited BIC50 values against S. aureus ATCC 25923 ranging from 1.0 to 9.1 µM. The new compounds, affecting the biofilm formation without any interference on microbial growth, can be considered promising lead compounds for the development of a new class of anti-virulence agents.  相似文献   
55.
Guided by theoretical predictions, the rotational spectrum of fluoroiodomethane, CH(2)FI, has been recorded and assigned. Accurate values are reported for the ground-state rotational constants, all quartic, sextic, and two octic centrifugal-distortion constants. The hyperfine structure of the rotational spectrum was thoroughly investigated using a Fourier-transform microwave spectrometer and the Lamb-dip technique in the millimeter-/submillimeter-wave region, thus allowing the accurate determination of the complete iodine quadrupole-coupling tensor and of the diagonal elements of the iodine spin-rotation tensor. Relativistic effects turned out to be essential for the accurate theoretical prediction of the dipole moment and quadrupole-coupling constants and were accounted for by direct perturbation theory and a spin-free four-component treatment based on the Dirac-Coulomb Hamiltonian. The relativistic corrections to the dipole moment amount to up to 34% and to the iodine quadrupole-coupling tensor to about 15-16% of the total values.  相似文献   
56.
The Hexagallane [Ga6{SiMe(SiMe3)2}6] and the closo‐Hexagallanate [Ga6{Si(CMe3)3}4 (CH2C6H5)2]2— — the Transition to an Unusual precloso‐Cluster The closo hexagallanate [Ga6R4(CH2Ph)2]2— (R = SitBu3) as well as the hexagallane Ga6R6 (R = SiMe(SiMe3)2) with only six cluster electron pairs were isolated from reactions of “GaI” with the corresponding silanides. The structure of the latter is derived from an octahedron by a Jahn‐Teller‐distortion and is different from the capped trigonal bipyramidal one expected by the Wade‐Mingos rules. Both compounds were characterized by X‐ray crystallography. The bonding is discussed with simplified Ga6H6 and Ga6H62— models via DFT methods.  相似文献   
57.
A mass spectrometer was coupled to high-performance ligand-exchange liquid chromatography (HPLEC) for simultaneous analysis of stress associated solutes such as proline, hydroxyproline, methylproline, glycine betaine and trigonelline extracted from leaves of drought stressed oaks and an internal standard namely N-acetylproline. Methanol/chloroform/water extracts were analyzed using an Aminex HPX-87C column and specifically quantified by the positive ion mode of an electrospray ionisation-mass spectrometry (ESI-MS) in single ion monitoring (SIM) mode. The recovery of N-acetyl proline added to oak leaf extracts ranged from 85.2 to 122.1% for an intra-day study. Standard calibration curves showed good linearity in the measured range from 0.3125 to 10 μmol L−1 with the lowest correlation coefficient of 0.99961 for trigonelline. The advantages of this alternative procedure, compared to previously published methods using fluorescence or amperometric detections, are the simultaneous and direct detection of osmoprotectants in a single chromatographic run, a minimal sample preparation, a good specificity and reduced limits of quantification, ranging from 0.1 to 0.6 μmol L−1. Fifty-six days of water deficit exposure resulted in increased foliar free proline levels (2.4-fold, P < 0.001, 155 μmol g−1 FW) and glycine betaine contents (2.5-fold, P < 0.05, 175 μmol g−1 FW) of drought stressed oak compared to control.  相似文献   
58.
Capillary zone electrophoresis (CZE) with indirect UV detection was used in developing a method for the simultaneous determination of inorganic anions, aliphatic and heterocyclic organic acids in various processed samples. The analytes were determined simultaneously in 10 min using an electrolyte containing 20 mM 2,3-pyrazine dicarboxylic acid, 65 mM tricine, 2 mM BaCl2, 0.5 mM cetyltrimethylammonium bromide, and 2 M urea at pH 8.06. Linear plots for the analytes were obtained in the concentration range of 2–150 mg L−1. Relative standard deviations (RSDs) of peak areas during a 3-day analysis period varied from 5.5% for glycolate to 9.5% for oxalate. RSDs of migration times varied between 0.4% and 1.1%. The detection limit (at S/N 3) was 1 mg L−1 for all the analytes studied. The proposed method was successfully demonstrated for the determination of carboxylic acids in eight oxygen treated samples of commercial softwood and hardwood kraft lignin and two red wine samples of Pinot Noir grapes. In the kraft lignin samples the concentrations of carboxylic acids correspond to the oxidation time. The acid concentrations of wine varied considerable.  相似文献   
59.
The coordination chemistry of the new pyridine-based, N2S2-donating 12-membered macrocycle 2,8-dithia-5-aza-2,6-pyridinophane (L1) towards Cu(II), Zn(II), Cd(II), Hg(II), and Pb(II) has been investigated both in aqueous solution and in the solid state. The protonation constants for L1 and stability constants with the aforementioned metal ions have been determined potentiometrically and compared with those of ligand L2, which contains a N-aminopropyl side arm. The measured values show that Hg(II) in water has the highest affinity for both ligands followed by Cu(II), Cd(II), Pb(II), and Zn(II). For each metal ion considered, 1:1 complexes with L1 have also been isolated in the solid state, those of Cu(II) and Zn(II) having also been characterised by X-ray crystallography. In both complexes L1 adopts a folded conformation and the coordination environments around the two metal centres are very similar: four positions of a distorted octahedral coordination sphere are occupied by the donor atoms of the macrocyclic ligand, and the two mutually cis-positions unoccupied by L1 accommodate monodentate NO3- ligands. The macrocycle L1 has then been functionalised with different fluorogenic subunits. In particular, the N-dansylamidopropyl (L3), N-(9-anthracenyl)methyl (L4), and N-(8-hydroxy-2-quinolinyl)methyl (L5) pendant arm derivatives of L1 have been synthesised and their optical response to the above mentioned metal ions investigated in MeCN/H2O (4:1 v/v) solutions.  相似文献   
60.
Reversed phase high performance liquid chromatography (RPLC) is currently the method of choice for the analysis of basic compounds. However, with traditional silica materials, secondary interactions between the analyte and residual silanols produce peak tailing which can negatively affect resolution, sensitivity, and reproducibility. In order to reduce these secondary interactions, which comprise ion exchange, hydrogen bonding, and London forces interactions, chromatographic analyses can be carried out at low or high pH values where silanol groups and basic compounds are mostly uncharged. The chromatographic behaviour of a particular bidentate stationary phase, Zorbax Extend C18, was studied with a set of basic and neutral compounds. Thanks to a higher chemical stability than traditional silica based supports, analyses were carried out with a high pH mobile phase, which represents a good alternative to the acidic mobile phases generally used to reduce ion exchange interactions. The performance of this bidentate stationary phase was also compared with that of other supports and it was proved that it is advantageous to work with high pH mobile phases when analyzing basic compounds.  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