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   4560篇
  免费   197篇
  国内免费   41篇
化学   3093篇
晶体学   47篇
力学   134篇
数学   443篇
物理学   1081篇
  2024年   19篇
  2023年   44篇
  2022年   238篇
  2021年   224篇
  2020年   170篇
  2019年   172篇
  2018年   169篇
  2017年   135篇
  2016年   205篇
  2015年   146篇
  2014年   216篇
  2013年   382篇
  2012年   317篇
  2011年   308篇
  2010年   240篇
  2009年   197篇
  2008年   218篇
  2007年   200篇
  2006年   150篇
  2005年   95篇
  2004年   114篇
  2003年   68篇
  2002年   68篇
  2001年   44篇
  2000年   42篇
  1999年   40篇
  1998年   32篇
  1997年   39篇
  1996年   44篇
  1995年   21篇
  1994年   30篇
  1993年   25篇
  1992年   22篇
  1991年   19篇
  1990年   30篇
  1989年   13篇
  1988年   22篇
  1987年   20篇
  1985年   25篇
  1984年   26篇
  1983年   17篇
  1982年   21篇
  1981年   13篇
  1980年   38篇
  1979年   11篇
  1977年   15篇
  1976年   10篇
  1973年   11篇
  1969年   9篇
  1968年   8篇
排序方式: 共有4798条查询结果,搜索用时 10 毫秒
101.
The preparation of glass-ionomer cements based on the composition of SiO2–Al2O3–CaO–SrO–F and evaluation of their properties is described. Cements were prepared via the sol–gel method and characterized by XRD, BET, SEM, and EDAX analysis. The effect of various concentrations of Sr on in vitro bioactivity of the glass speciments was investigated. In vitro bioactivity of the samples was evaluated by soaking them in simulated body fluid followed by structural characterization using SEM and atomic absorption analysis. A glass specimen with 0.5 mol of Sr exhibited appropriate bioactivity.  相似文献   
102.
A planar, polycyclic and aromatic hydrocarbon ligand, namely 9,10-phenanthrenequinone semicarbazone, and its transition metal complexes have been synthesized and structurally characterized. The in vitro antiproliferative activity of these compounds against five human cancer cell lines revealed that they were effective against androgen receptor-positive/negative prostate cancer cells as well as COX-positive pancreatic BxPC-3 cancer cell line. The driving force behind such antiproliferative activity seems to be the up-regulated COX expression in these cells, which was amenable for targeting through metal complexation. These structural motifs can, therefore, serve as a starting point for developing novel cytotoxic agents against the growing number of prostate and pancreatic cancers.  相似文献   
103.
Mesoporous nanocomposite membranes with vanadium oxide–carbon nanotubes (VxOy-CNTs) embedded in γ-Al2O3 were successfully synthesized using the dip coating method. The membranes were evaluated for styrene oxidation to determine the optimum styrene conversion and benzaldehyde selectivity. Several factors that influence the preparation of defect-free coatings, such as the type of binder, the binder addition time and surface support treatments, were investigated. The physico-chemical permeation properties of the membranes were characterized using scanning electron microscope, transmission electron microscope (TEM), X-ray Diffraction XRD, Nitrogen adsorption (BET) and Thermogravimetric TGA. Response surface methodology (RSM) was used to investigate the effects of oxidant (H2O2) concentration, temperature, contact time and catalyst loading on styrene conversion and the selectivity of benzaldehyde. Based on the RSM analysis, the optimal oxidation conditions included a reaction temperature of 45 °C, a differential pressure of 1.5 bars, a molar ratio of H2O2: styrene of 1.5:1 and a catalyst loading of 30 %. These conditions resulted in the maximal styrene conversion of 25.6 and 84.9 % benzaldehyde selectivity.  相似文献   
104.
In this study, biodiesel has been successfully produced by transesterification using non-catalytic supercritical methanol and methyl acetate. The variables studied, such as reaction time, reaction temperature and molar ratio of methanol or methyl acetate to oil, were optimised to obtain the optimum yield of fatty acid methyl ester (FAME). Subsequently, the results for both reactions were analysed and compared via Response Surface Methodology (RSM) analysis. The mathematical models for both reactions were found to be adequate to predict the optimum yield of biodiesel. The results from the optimisation studies showed that a yield of 89.4 % was achieved for the reaction with supercritical methanol within the reaction time of 27 min, reaction temperature of 358°C, and methanol-to-oil molar ratio of 44. For the reaction in the presence of supercritical methyl acetate, the optimum conditions were found to be: reaction time of 32 min, reaction temperature of 400°C, and methyl acetate-to-oil molar ratio of 50 to achieve 71.9 % biodiesel yield. The differences in the behaviour of methanol and methyl acetate in the transesterification reaction are largely due to the difference in reactivity and mutual solubility of Jatropha curcas oil and methanol/methyl acetate.  相似文献   
105.
An n-butyl bromide/sodium dodecyl sulfate/n-butanol/water microemulsion system was chosen as a model of an organohalide-containing microemulsion. Two systems were prepared using the Bourayne method: a water-rich system and an n-butyl-bromide-rich system. The destabilization of this micro-organized system and the phase separation were investigated. This microemulsion, in which the oil phase in the feed is the lower layer, was successfully destabilized using the pervaporation technique with polydimethylsiloxane and poly(vinyl alcohol) membranes. In this way, different factors governing the separation process were investigated such as the mass transfer and the effect of time and operating temperature on the microemulsion destabilization.  相似文献   
106.
The development of base metal catalysts for industrially important reactions continues to be an important goal of catalysis research. Herein, the effects of pyrolysis temperature on the textural, structural, surface, magnetics properties and catalytic properties of silica-supported nickel nanoparticles (NiNPs) were thoroughly investigated. Mono-dispersed NiNPs encapsulated in graphitic shells were first successfully obtained and were characterized using a variety of methods such as BET surface area measurement, CO-pulse chemisorption, X-ray diffraction (XRD), X-ray photoelectron spectroscopy (XPS), high resolution transmission electron microscopy (HR-TEM), and superconducting quantum interference device (SQUID) measurement. The findings showed that all catalysts’ properties were considerably altered with change in pyrolysis temperature. Hydrogenation of diphenylacetylene was then selected as the model reaction for the evaluation of the catalytic performance of the graphitic-shelled NiNPs. After testing, pyrolysis of a nickel at 800 °C (catalyst A) displayed tremendous activity and selectivity to produce >94% of stilbene with selectivities of 99% for the Z-isomer.  相似文献   
107.
This study describes our development of a microfluidic reaction scheme for the synthesis of fused indoline ring systems found in several bioactive compounds. We have utilized a continuous-flow microfluidic reactor for the reaction of hydrazines with latent aldehydes through the interrupted Fischer indolization reaction to form fused indoline and azaindoline products. We have identified optimal conditions and evaluated the scope of this microfluidic reaction using various hydrazine and latent aldehyde surrogates. This green chemistry approach can be of general utility to rapidly produce indoline scaffolds and intermediates in a continuous manner.  相似文献   
108.
Novel functionalized graphene adsorbent was prepared and characterized using different techniques. The prepared adsorbent was applied for the removal of cadmium ions from aqueous solution. A response surface methodology was used to evaluate the simple and combined effects of the various parameters, including adsorbent dosage, pH, and initial concentration. Under the optimal conditions, the cadmium removal performance of 70% was achieved. A good agreement between experimental and predicted data in this study was observed. The experimental results revealed of cadmium adsorption with high linearity follow Langmuir isotherm model with maximum adsorption capacity of 502 mg g?1, and the adsorption data fitted well into pseudo‐second order model. Thermodynamic studies showed that adsorption process has exothermic and spontaneous nature. The recommended optimum conditions are: cadmium concentration of 970 mg L?1, adsorbent dosage of 1 g L?1, pH of 6.18, and T = 25 °C. The magnetic recovery of the adsorbent was performed using a magnetic surfactant to form a noncovalent magnetic functionalized graphene. After magnetic recovery of the adsorbent both components (adsorbent and magnetic surfactant) were recycled by tuning the surface charges through changing the pH of the solution. Desorption behavior studied using HNO3 solution indicated that the adsorbent had the potential for reusability.  相似文献   
109.
TiO2‐ZrO2 (1/1)‐surf with Ti and Zr molar ratio of 1/1 was prepared with surfactant through a sol‐gel method. The optimum experimental condition was investigated for nitration of salicylic acid. Then, a number of nitration reactions were carried out with a variety of aromatic compounds in the optimum condition. The 25 wt% H3PO4/TiO2‐ZrO2 (1/1)‐surf catalyst showed good selectivity and yield in a short time for the nitration of salicylic acid and some other aromatic compounds.  相似文献   
110.
A novel and highly efficient approach for the synthesis of H2Me2bqb and H2Me2bpb using ionic liquid as an environmentally benign reaction medium has been developed, eliminating the need for the pyridine as a toxic solvent. The Ni(II) complex of the dianionic ligand Me2bqb2−, [Me2bqb2− = 1,2-bis(quinoline-2-carboxamide)-4,5-dimethyl-benzene dianion], has been synthesized and characterized by elemental analyses and spectroscopic methods, and the crystal and molecular structure of [Ni(Me2bqb)] (1), has been determined by X-ray crystallography. The complex exhibits distorted square-planar NiN4 coordination geometry with two short and two long Ni–N bonds (Ni–N ∼1.85 and ∼1.96 Å, respectively). The electrochemical behavior of [Ni(Me2bqb)] (1), has been studied by cyclic voltammetry and compared with the analogous complex, [Ni(Me2bpb)] (2).  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