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   262篇
  免费   20篇
  国内免费   3篇
化学   176篇
晶体学   2篇
力学   17篇
数学   39篇
物理学   51篇
  2024年   1篇
  2023年   2篇
  2022年   4篇
  2021年   7篇
  2020年   8篇
  2019年   13篇
  2018年   11篇
  2017年   10篇
  2016年   22篇
  2015年   22篇
  2014年   24篇
  2013年   27篇
  2012年   33篇
  2011年   23篇
  2010年   11篇
  2009年   13篇
  2008年   7篇
  2007年   11篇
  2006年   6篇
  2005年   5篇
  2004年   8篇
  2003年   4篇
  2002年   5篇
  2001年   3篇
  2000年   1篇
  1994年   1篇
  1982年   1篇
  1932年   1篇
  1925年   1篇
排序方式: 共有285条查询结果,搜索用时 31 毫秒
41.
Ternary monomer reactivity ratios of triisopropylsilyl acrylate (SiA), methyl methacrylate (MMA), and n‐butyl acrylate (BA), as common monomers in self‐polishing coatings (SPCs) binders are obtained using experimental data collected from free radical bulk polymerization at 70 °C. Different terpolymerizations at low and medium‐high conversions are performed at optimized feed compositions. Estimations are made using the error‐in‐variables model (EVM) framework, applying the recast form of the Alfrey–Goldfinger (AG) model and a direct numerical integration (DNI) approach to the collected data. Estimations from individual low and medium‐high conversion data are compared to those found with the combined data (full conversion range data). The highest certainty in point estimates are obtained with analysis of the full conversion range data. Furthermore, the reactivity ratios determined from the combined data fall between those found with analysis of individual low and medium‐high conversion data, another corroboration of reliable data collection. Reactivity ratios determined from analysis of the combined data (rSiA/MMA = 0.4185, rMMA/SiA = 1.3754, rSiA/BA = 0.8739, rBA/SiA = 0.5736, rBA/MMA = 0.3692, rMMA/BA = 1.7919) are used in the recast AG model to predict cumulative terpolymer composition as a function of conversion. The experimental data and model prediction show satisfactory agreement.  相似文献   
42.
Steam reforming of methanol was carried out on the copper-silica aerogel catalyst.The effects of reaction temperature,feed rate,water to methanol molar ratio and carrier gas flowrate on the H_2 production rate and CO selectivity were investigated.M ethanol conversion was increased considerably in the range of about 240-300,after which it increased at a slightly lower rate.The used feed flowrate,steam to methanol molar ratio and carrier gas flowwere 1.2-9.0 m L/h,1.2-5.0 and 20-80 m L/min,respectively.Reducing the feed flowrate increased the H_2 production rate.It was found that an increase in the water to methanol ratio and decreasing the carrier gas flowrate slightly increases the H2production rate.Increasing the water to methanol ratio causes the lowest temperature in which CO formation was observed to rise,so that for the ratio of 5.0 no CO formation was detected in temperatures lower than 375℃.In all conditions,by approaching the complete conversion,increasing the main product concentration,increasing the temperature and contact time,and decreasing the steam to methanol ratio,the CO selectivity was increased.These results suggested that CO was formed as a secondary product through reverse water-gas shift reaction and did not participate in the methanol steam reforming reaction mechanism.  相似文献   
43.
In this work, multi-walled carbon nanotubes (MWCNTs)-coated cellulose acetate membrane was used for on-line extraction and pre-concentration of uranium from aqueous samples prior to inductively coupled plasma optical emission spectrometry (ICP-OES) determination. Sample solutions containing the U(VI)-2-(5-bromo-2-pyridylazo)-5-diethylaminophenol (Br-PADAP) complex were passed through the membrane. The adsorbed analyte was subsequently eluted from the membrane with acid, which was directly introduced into the ICP-OES nebuliser. The main variables affecting the pre-concentration and determination steps of uranium were studied and optimised. Under the optimised conditions, the enrichment factor of 150 and the detection limit of 0.16 μg L–1 were obtained. This method was successfully used for determination of uranium in environmental water samples.  相似文献   
44.
Chemical hybrid of nanoclay (NC)/carbon nanotube (CNT) was synthesized via growth of CNTs by chemical vapor deposition. The cure kinetics of epoxy resin in the presence of novel chemical hybrid of NC/CNT (CNC) was studied by non-isothermal differential scanning calorimetry. The effect of the CNC on cure kinetics was compared with conventional nanofillers such as CNTs, NC, and physical mixture of them (PNC). The kinetic parameters of the cure reaction were determined by iso-conversional method. The accelerating effect of CNT, CNC, and PNC in initial stage of cure reaction was related to the high thermal conductivity of CNTs, while the decelerating effect of nanofillers as the cure proceeded can be attributed to the reduction of polymer molecules motion caused by enhanced viscosity. The apparent activation energy (E α) as the function of conversion (α) was calculated by five methods categorized into two different types: (1) conversion-dependent methods: Kissinger–Akahira–Sunose (KAS), Ozawa–Flynn–Wall (OFW), and Friedman; (2) conversion-independent methods: Kissinger and Augis. The accelerating effect of CNT, PNC, and CNC was observable as the reduced E α values in low conversion only with KAS and OFW methods. The reverse trend of E α values was observed with the introduction of these nanofillers at high conversions. The uniqueness of the CNC was more marked in increasing E α values of epoxy after initial stage due to its special 3D structure of CNC. Calculated data using KAS and OFW methods showed the best agreement with the obtained experimental data.  相似文献   
45.
The pulsed intense ion beam, emitted from a dense plasma focus (DPF) discharges performed with hydrogen gas, has been used to ablate the graphite target depositing diamond-like carbon (DLC) films on Si substrates. The substrates were mounted on a holder, which allowed for deposition at positions between normal and 20° off-normal to the target. The samples were removed for analysis after 10 and 20 shots. Nano-particles were observed in the films by a field-emission scanning electron microscope. Raman spectra indicate that sample deposited at 20° off-normal with 20 shots possesses the highest sp3 content among the samples. The film deposited at this position was also found has the highest hardness.  相似文献   
46.
We investigate the QCD ghost model of dark energy in the framework of RS II braneworld. We assume there is an energy flow between the brane and bulk, and hence the continuity equation for the ghost dark energy is violated, while it is still preserved for the dark matter on the brane. We find that with the brane-bulk interaction, the equation of state parameter of ghost dark energy on the brane, can cross the phantom line w D =?1 at the present time, which confirms by some cosmological evidences. This result is in contrast to the standard cosmology where w D of ghost dark energy never cross the phantom line and the universe enters a de Sitter phase at the late time.  相似文献   
47.
One new triterpenoid olean-18-ene-1β, 2α, 3β-triol (1) along with four known compounds were isolated from the chloroform extract of the aerial part of Salvia atropatana Bunge. The known compounds were two flavonoids, 5-hydroxy-7,4'-dimethoxyflavone (2) and 5-hydroxy-6,7,4'-trimethoxyflavone (3), an abietane-type diterpene namely taxodione (4) and a phytosterol namely γ -sitosterol (5). The structure of (1) was elucidated by comprehensive spectroscopic analysis including electron ionization-mass spectra (EI-MS), (1)H NMR, (13)C NMR, distortionless enhancement by polarization transfer (DEPT), H,H correlation spectroscopy (COSY), heteronuclear multiple quantum coherence (HMQC) and heteronuclear multiple bond correlation (HMBC). The structure of known compounds 2-5 were identified by comparison of their spectral data with those reported in the literature.  相似文献   
48.
Plant nonspecific lipid transfer proteins are small basic proteins that transport phospholipids between membranes and are subdivided into two subfamilies, nsLTP1 (9 kDa) and nsLTP2 (7 kDa). LTPs have potential application in the defense reactions against pathogens and the drug delivery systems. Many efforts have been made for purification of different nsLTPs from various plants; however, most of them used successive purification procedures. We have developed a relatively simple and efficient method for the purification of rice nsLTP1, based on the proteolytic activity of kiwifruit actinidin on the rice seed extract and one‐step chromatographic procedure on a CM‐Sepharose column. The purity of protein was determined by reversed‐phase high‐performance liquid chromatography (RP‐HPLC) and sodium dodecyl sulfate polyacrylamide gel electrophoresis (SDS‐PAGE). The isolated LTP1 migrated as a homogenous polypeptide with molecular mass of 9 kDa that confirms the efficiency of actinidin on the digestion of major contaminations present in the rice seed extract without any harmful effect on the LTP1. The advantages of using proteolytic activity of actinidin in purifying rice LTP1 includes the reduced separation time allowing the purification of LTP1 in one‐step chromatographic procedure, low costing, high efficiency, and the relative simplicity of the method.  相似文献   
49.
Density functional theory (DFT) calculations have been performed to investigate the availabilities and properties of boron nitride nanotubes (BNNTs) with quadrangular cross sections. To achieve the purposes, the original structure of a representative BNNT was individually decorated by the carbon and silicon atoms to make the C-BNNT and Si-BNNT models. The sp3 hybridizations were set for the C and Si atoms to make possible the formation of the quadrangular cross sections for the BNNTs. The optimized results indicated that the investigated models could be stabilized; however, they showed different properties. The atomic scale properties based on computations of quadrupole coupling constants (CQ) also approved different properties for the C-BNNT and Si-BNNT models. Moreover, the CQ parameters indicated that the properties of C-BNNT could be considered similar to the original BNNT; however, more discrepancies were observed for the Si-BNNT.  相似文献   
50.
The development of resistance and unwanted harmful interaction with other biomolecules instead of DNA are the major drawbacks for application of platinum (Pt) complexes in cancer chemotherapy. To conquer these problems, much works have been done so far to discover innovative Pt complexes. The objective of the current study was to evaluate the anti cancer activities of a series of four and five-coordinated Pt(II) complexes, having deprotonated 2-phenyl pyridine (abbreviated as C^N), biphosphine moieties, i.e., dppm?=?bis(diphenylphosphino) methane (Ph2PCH2PPh2) and dppa?=?bis(diphenylphosphino)amine (Ph2PNHPPh2), as the non-leaving carrier groups. The growth inhibitory effect of the Pt complexes [Pt(C^N)(dppm)]PF6: C 1 , [Pt(C^N)(dppa)]PF6: C 2 , and [Pt(C^N)I(dppa)]: C 3 , toward the cancer cell lines was measured using 3-(4,5-dimethylthiazol-2-yl)-2,5-diphenyl tetrazolium bromide assay. In addition, the florescence quenching experiments of the interaction between human serum albumin (HSA) and the Pt complexes were performed in order to obtain the binding parameters and to evaluate the denaturing properties of these complexes upon binding to the general carrier protein of blood stream. The structure?Cactivity relationship studies reveal that four-coordinated Pt complexes C 1 and C 2 with both significant hydrophobic and charge characteristics, not only exhibit strong antiproliferation activity toward the cancer cell lines, but also they display lower denaturing effect against carrier protein HSA. On the other hand, five-coordinated C 3 complex with the unusual intermolecular NH??Pt hydrogen binding and the intrinsic ability for oligomerization, exhibits poor anticancer activity and strong denaturing property. The current study reveals that the balance between charge and hydrophobicity of the Pt complexes, also their hydrogen binding abilities and coordination mode are important for their anticancer activities. Moreover, this study may suggest C 1 and C 2 as the potential template structures for synthesis of new generation of four-coordinated Pt complexes with strong anticancer activities and weak denaturing effects against proteins.  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