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   1108篇
  免费   37篇
  国内免费   2篇
化学   717篇
晶体学   5篇
力学   60篇
数学   117篇
物理学   248篇
  2024年   9篇
  2023年   13篇
  2022年   32篇
  2021年   21篇
  2020年   43篇
  2019年   40篇
  2018年   38篇
  2017年   31篇
  2016年   58篇
  2015年   25篇
  2014年   44篇
  2013年   89篇
  2012年   111篇
  2011年   132篇
  2010年   69篇
  2009年   50篇
  2008年   68篇
  2007年   54篇
  2006年   51篇
  2005年   41篇
  2004年   26篇
  2003年   16篇
  2002年   24篇
  2001年   4篇
  2000年   4篇
  1999年   3篇
  1998年   1篇
  1997年   5篇
  1996年   3篇
  1995年   4篇
  1994年   2篇
  1993年   2篇
  1992年   2篇
  1991年   1篇
  1986年   2篇
  1985年   3篇
  1984年   2篇
  1983年   1篇
  1982年   4篇
  1981年   1篇
  1980年   1篇
  1979年   2篇
  1978年   1篇
  1977年   2篇
  1976年   4篇
  1975年   1篇
  1974年   1篇
  1973年   4篇
  1965年   1篇
  1964年   1篇
排序方式: 共有1147条查询结果,搜索用时 15 毫秒
51.
A nonlinear (energy) stability analysis is performed for a rotating magnetized ferrofluid layer heated from below saturating a porous medium, in the stress-free boundary case. By introducing a generalized energy functional, a rigorous nonlinear stability result for a thermoconvective rotating magnetized ferrofluid is derived. The mathematical emphasis is on how to control the nonlinear terms caused by magnetic body force. It is found that the nonlinear critical stability magnetic thermal Rayleigh number does not coincide with that of linear instability analysis, and thus indicates that the subcritical instabilities are possible. However, it is noted that, in case of non-ferrofluid, global nonlinear stability Rayleigh number is exactly the same as that for linear instability. For lower values of magnetic parameters, this coincidence is immediately lost. The effect of magnetic parameter, M 3, medium permeability, D a , and rotation, , on subcritical instability region has also been analyzed. It is shown that with the increase of magnetic parameter, M 3, and Darcy number, D a , the subcritical instability region between the two theories decreases quickly while with the increase of Taylor number, , the subcritical region expands. We also demonstrate coupling between the buoyancy and magnetic forces in the presence of rotation in nonlinear energy stability analysis as well as in linear instability analysis.   相似文献   
52.
In this paper we study properties of numerical solutions of Burger’s equation. Burgers’ equation is reduced to the heat equation on which we apply the Douglas finite difference scheme. The method is shown to be unconditionally stable, fourth order accurate in space and second order accurate in time. Two test problems are used to validate the algorithm. Numerical solutions for various values of viscosity are calculated and it is concluded that the proposed method performs well.  相似文献   
53.
We report a C?C bond‐forming reaction between benzyl alcohols and alkynes in the presence of a catalytic amount of KOtBu to form α‐alkylated ketones in which the C=O group is located on the side derived from the alcohol. The reaction proceeds under thermal conditions (125 °C) and produces no waste, making the reaction highly atom efficient, environmentally benign, and sustainable. Based on our mechanistic investigations, we propose that the reaction proceeds through radical pathways.  相似文献   
54.
The combination of acebrophylline (ABP), levocetirizine (LCZ) and pranlukast (PRN) is used to treat allergic rhinitis, asthma, hay‐fever and other conditions where patients experience difficulty in breathing. This study was carried out with the aim of developing and validating a reverse‐phase high‐performance liquid chromatographic bioanalytical method to simultaneously quantitate ABP, LCZ and PRN in rat plasma. The objective also includes determination of the pharmacokinetic interaction of these three drugs after administration via the oral route after individual and combination treatment in rat. Optimum resolution between the analytes was observed with a C18 Kinetex column (250 mm × 4.6 mm × 5 μm). The chromatography was performed in a gradient elution mode with a 1 mL/min flow rate. The calibration curves were linear over the concentration range of 100–1600 ng/mL. The intra‐ and inter‐day precision and accuracy were found to be within acceptable limits as specified in US Food and Drug Administration guideline for bioanalytical method validation. The analytes were stable on the bench‐top (8 h), after three freeze–thaw cycles, in the autosampler (8 h) and as a dry extract (?80°C for 48 h). The statistical results of the pharmacokinetic study in Sprague–Dawley rats showed a significant change in pharmacokinetic parameters for PRN upon co‐administration of the three drugs.  相似文献   
55.
We have characterized a sulfobetaine stationary phase based on 1.7 μm ethylene-bridged hybrid organic–inorganic particles, which is intended for use in hydrophilic interaction chromatography. The efficiency of a column packed with this material was determined as a function of flow rate, demonstrating a minimum reduced plate height of 2.4. The batch-to-batch reproducibility was assessed using the separation of a mixture of acids, bases, and neutrals. We compared the retention and selectivity of the hybrid sulfobetaine stationary phase to that of several benchmark materials. The hybrid sulfobetaine material gave strong retention for polar neutrals and high selectivity for methyl groups, hydroxy groups, and configurational isomers. Large differences in cation and anion retention were observed among the columns. We characterized the acid and base stability of the hybrid sulfobetaine stationary phase, using accelerated tests at pH 1.3 and 11.0, both at 70°C. The results support a recommended pH range of 2–10. We also investigated the performance of columns packed with this material for metal-sensitive analytes, comparing conventional stainless steel column hardware to hardware that incorporates hybrid surface technology to mitigate interactions with metal surfaces. Compared to the conventional columns, the hybrid surface technology columns showed a greatly improved peak shape.  相似文献   
56.
Red‐shifted bioluminescent emitters allow improved in vivo tissue penetration and signal quantification, and have led to the development of beetle luciferin analogues that elicit red‐shifted bioluminescence with firefly luciferase (Fluc). However, unlike natural luciferin, none have been shown to emit different colors with different luciferases. We have synthesized and tested the first dual‐color, far‐red to near‐infrared (nIR) emitting analogue of beetle luciferin, which, akin to natural luciferin, exhibits pH dependent fluorescence spectra and emits bioluminescence of different colors with different engineered Fluc enzymes. Our analogue produces different far‐red to nIR emission maxima up to λmax=706 nm with different Fluc mutants. This emission is the most red‐shifted bioluminescence reported without using a resonance energy transfer acceptor. This improvement should allow tissues to be more effectively probed using multiparametric deep‐tissue bioluminescence imaging.  相似文献   
57.
The μ‐amino–borane complexes [Rh2(LR)2(μ‐H)(μ‐H2B=NHR′)][BArF4] (LR=R2P(CH2)3PR2; R=Ph, iPr; R′=H, Me) form by addition of H3B?NMeR′H2 to [Rh(LR)(η6‐C6H5F)][BArF4]. DFT calculations demonstrate that the amino–borane interacts with the Rh centers through strong Rh‐H and Rh‐B interactions. Mechanistic investigations show that these dimers can form by a boronium‐mediated route, and are pre‐catalysts for amine‐borane dehydropolymerization, suggesting a possible role for bimetallic motifs in catalysis.  相似文献   
58.
A novel Mitsunobu-based protocol has been developed for the synthesis of a variety of symmetrical and unsymmetrical trithiocarbonates from primary, secondary and tertiary thiols using carbon disulfide, in good to excellent yields. This protocol is mild and efficient compared to other reported methods.  相似文献   
59.
This work deals with water-swollen hydrogel membranes for potential CO2 separation applications, with an emphasis on elucidating the role of water in the membrane for gas permeation. A series of hydrogel membranes with a wide range of water contents (0.9–10 g water/g polymer) were prepared from poly(vinyl alcohol), chitosan, carboxyl methyl cellulose, alginic acid and poly(vinylamine), and the permeation of CO2, H2, He and N2 through the membranes at different pressures (200–800 kPa) was studied. The gas permeabilities through the dry dense membranes were measured as well to evaluate the resistance of the polymer matrix in the hydrogel membranes. It was shown that the gas permeability in water-swollen membrane is lower than the gas permeability in water, and the selectivity of the water-swollen membranes to a pair of gases is close to the ratios of their permeabilities in water. The permeability of the water-swollen membranes increases with an increase in the swelling degree of the membrane, and the membrane permeability tends to level off when the water content is sufficiently high. A resistance model was proposed to describe gas permeation through the hydrogel membranes, where the immobilized water retained in the polymer matrix was considered to form transport passageways for gas permeation through the membrane. It was shown that the permeability of hydrogel membranes was primarily determined by the water content in the membrane. The model predictions were consistent with the experimental data for various hydrogel membranes with a wide range of water contents (0.4–10 g water/g polymer).  相似文献   
60.
The adsorption of bovine serum albumin (BSA) and lysozyme (LYS) on siliceous SBA-15 with 24 nm pores was studied using flow microcalorimetry; this is the first attempt to understand the thermodynamics of protein adsorption on SBA-15 using flow microcalorimetry. The adsorption mechanism is a strong function of protein structure. Exothermic events were observed when protein–surface interactions were attractive. Entropy-driven endothermic events were also observed in some cases, resulting from lateral protein–protein interactions and conformational changes in the adsorbed protein. The magnitudes of the enthalpies of adsorption for primary protein–surface interactions decrease with increased surface coverage, indicating the possibility of increased repulsion between adsorbed protein molecules. Secondary exothermic events were observed for BSA adsorption, presumably due to secondary adsorption made possible by conformational changes in the soft BSA protein. These secondary adsorption events were not observed for lysozyme, which is structurally robust. The results of this study emphasize the influence of solution conditions and protein structure on conformational changes of the adsorbed protein and the value of calorimetry in understanding protein–surface interactions.  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