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   1078篇
  免费   38篇
  国内免费   21篇
化学   842篇
晶体学   20篇
力学   28篇
数学   52篇
物理学   195篇
  2024年   6篇
  2023年   10篇
  2022年   64篇
  2021年   109篇
  2020年   41篇
  2019年   45篇
  2018年   65篇
  2017年   40篇
  2016年   65篇
  2015年   50篇
  2014年   66篇
  2013年   71篇
  2012年   109篇
  2011年   106篇
  2010年   67篇
  2009年   39篇
  2008年   25篇
  2007年   32篇
  2006年   22篇
  2005年   23篇
  2004年   9篇
  2003年   12篇
  2002年   7篇
  2001年   4篇
  2000年   4篇
  1999年   2篇
  1997年   2篇
  1996年   2篇
  1994年   4篇
  1993年   4篇
  1992年   2篇
  1991年   3篇
  1990年   1篇
  1989年   1篇
  1988年   3篇
  1987年   3篇
  1986年   2篇
  1985年   3篇
  1984年   1篇
  1983年   1篇
  1981年   3篇
  1980年   3篇
  1977年   1篇
  1975年   2篇
  1936年   1篇
  1935年   1篇
  1933年   1篇
排序方式: 共有1137条查询结果,搜索用时 31 毫秒
31.
In this study, the ionic conductivity of a nanocomposite polymer electrolyte system (PEO-LiPF6-EC-CNT), which has been produced using solution cast technique, is obtained using artificial neural networks approach. Several results have been recorded from experiments in preparation for the training and testing of the network. In the experiments, polyethylene oxide (PEO), lithium hexafluorophosphate (LiPF6), ethylene carbonate (EC) and carbon nanotubes (CNT) are mixed at various ratios to obtain the highest ionic conductivity. The effects of chemical composition and temperature on the ionic conductivity of the polymer electrolyte system are investigated. Electrical tests reveal that the ionic conductivity of the polymer electrolyte system varies with different chemical compositions and temperatures. In neural networks training, different chemical compositions and temperatures are used as inputs and the ionic conductivities of the resultant polymer electrolytes are used as outputs. The experimental data is used to check the system’s accuracy following the training process. The neural network is found to be successful for the prediction of ionic conductivity of nanocomposite polymer electrolyte system.  相似文献   
32.
This work describes the synthesis and coordination behavior of a new mixed-donor ligand PhC(NtBu)2SiC6H4PPh2 ( 1 ) containing both silylene and phosphine donor sites. Ligand 1 was synthesized from a reaction of ortho-lithiated diphenylphosphinobenzene (LiC6H4PPh2) with chlorosilylene (PhC(NtBu)2SiCl). Treatment of 1 with Se and GeCl2 resulted in SiIV compounds 2 and 3 by selective oxidation of the silylene donor. This strong σ-donor ligand induces dissociation of CuCl and PhBCl2 leading to formation of ionic complexes 4 and 5 respectively. The reaction of 1 with ZnCl2 and AlCl3 resulted in the formation of chelate complexes 5 and 7 , respectively, while treatment with EtAlCl2 and GaCl3 forms monodentate complexes 8 and 9 . X-ray analysis of 4 showed that the copper is in the spiro center of the two five-membered rings. Moreover, the copper(I)chloride has not been oxidized but dissociates to Cu+ and [CuCl2]. All the compounds are well characterized by mass spectrometry, elemental analysis, NMR spectroscopy, and single-crystal X-ray diffraction studies.  相似文献   
33.
Abstract

Various sulfides are easily oxidized selectively to the corresponding sulfoxides in quantitative yields by iodosylarene (ArIO) catalyzed by metalloporphyrin (TPPM(III)Cl (M [dbnd] Fe, Mn)). The oxidation system is demonstrated to be a possible model for monooxygenase in the study of the stereochemistry of these sulfoxides. Metalloporphyrin-iodosylarene can initially equilibrate with the oxometalloporphyrin (TPPM(V)=O·Cl) formed in situ. The initial process may involve one-electron transfer from the sulfide to the intermediate oxometalloporphyrin followed by coupling of two resulting charged products, and/or nucleophilic attack of sulfide on oxometalloporphyrin oxygen. The overall reactions are depicted by paths with different electron demands from the results of Hammett plots.  相似文献   
34.
Triphenylantimony (V) (O-alkyl,O-cycloalkyl and O-aryltrithiophosphates) of the type Ph 3 Sb[S 2 (S)P(OR)] (R = Me, Et, Pr n , Pr i , Bu n , Bu s , Bu i , Am i , Ph and C.h. = cyclohexyl) have been synthesized for the first time by the reaction of triphenylantimony (V) dibromide with potassium trithiophosphates in 1:1 molar ratio in methanol. These new compounds have been characterized by elemental analysis, molecular weight determinations, and spectroscopic (IR,13C and 31P NMR) studies. On the basis of these data trigonal bipyramidal geometry has been proposed for these compounds.  相似文献   
35.
A simple adsorption/desorption procedure using a mixed matrix membrane (MMM) as extraction medium is demonstrated as a new miniaturized sample pretreatment and preconcentration technique. Reversed-phase particles namely polymeric bonded octadecyl (C18) was incorporated through dispersion in a cellulose triacetate (CTA) polymer matrix to form a C18-MMM. Non-steroidal anti-inflammatory drugs (NSAIDs) namely diclofenac, mefenamic acid and ibuprofen present in the environmental water samples were selected as targeted model analytes. The extraction setup is simple by dipping a small piece of C18-MMM (7 mm × 7 mm) in a stirred 10 mL sample solution for analyte adsorption process. The entrapped analyte within the membrane was then desorbed into 100 μL of methanol by ultrasonication prior to high performance liquid chromatography (HPLC) analysis. Each membrane was discarded after single use to avoid any analyte carry-over effect. Several important parameters, such as effect of sample pH, salting-out effect, sample volume, extraction time, desorption solvent and desorption time were comprehensively optimized. The C18-MMM demonstrated high affinity for NSAIDs spiked in tap and river water with relative recoveries ranging from 92 to 100% and good reproducibility with relative standard deviations between 1.1 and 5.5% (n = 9). The overall results obtained were found comparable against conventional solid phase extraction (SPE) using cartridge packed with identical C18 adsorbent.  相似文献   
36.
A simple solid phase extraction (SPE) method coupled with high performance liquid chromatography (HPLC) using UV detector and microemulsion electrokinetic chromatography (MEEKC) has been developed and compared for the quantitative determination of miconazole nitrate in pharmaceutical formulation. For HPLC method, two parameters were optimized, namely, the wavelength and the mobile phases. The optimized condition was at the 225 nm wavelength and the mobile phase of ACN:MeOH (90:10 v/v). There are seven MEEKC parameters that were optimized, in this research, which were applied to voltage, temperature, wavelength, sodium dodecyl sulfate (SDS) concentration, buffer pH, buffer concentration and butan-1-ol concentration. The optimum MEEKC condition was obtained using 86.35 % (w/w) 2.5 mM borate buffer pH 9, 0.25 % (w/w) SDS, 0.8 % (w/w) ethyl acetate, 6.6 % w/w butan-1-ol and 6.0 % (w/w) acetonitrile. The combination of SPE using a diol column with HPLC–UV and the MEEKC methods were successfully applied for the determination of miconazole nitrate in a pharmaceutical formulation with the recovery percentage of 98.35 and 92.50 %, respectively.  相似文献   
37.
In the present work, the behavior of mixed drug–surfactant systems has been studied by surface tension measurements. The drug used in this work is adiphenine hydrochloride (ADP) and the surfactants are of m-s-m type geminis, i.e., alkanediyl-α,ω-bis(dimethylalkylammonium bromide), with m = (14, 16), s = (4, 5, 6), and conventional alkyltrimethylammonium bromides (CTAB, TTAB). The excess surface concentration (Γ max ) increases and the minimum head group area at the air/water interface (A min) decreases with increasing concentration of surfactant in the drug solution. Both the critical micelle concentration (cmc) and ideal cmc (cmc*) values decrease with mole fraction of surfactants. Also, the cmc values are lower than cmc*, indicating attractive interactions are present in the mixed micelles. The mole fractions of surfactant in the micelles $ \left( {X_{1}^{m} } \right) $ and monolayers $ \left( {X_{1}^{\sigma } } \right) $ , as well as the respective interaction parameters ( $ \beta^{m} $ , $ \beta^{\sigma } $ ), indicate that monolayer formation is easier than micelle formation due to the rigid hydrophobic part of the drug.  相似文献   
38.
The paper aims to study blend properties of biodegradable polymers of poly(3-hydroxybutyrate-co-3-hydroxyvalerate) (PHBV) and polylactide (PLA) prepared by melt mixing. Blend compositions based on PHBV/PLA were investigated according to the following weight ratios, i.e. 100/0, 75/25, 50/50, 25/75 and 0/100 wt%. The study showed through scanning electron microscopy (SEM) that blends of PHBV/PLA are not miscible. This is consistent with differential scanning calorimetry (DSC) data which indicate the presence of two distinct glass transition temperatures (Tg) and melting temperatures (Tm), attributed to the neat polymers, over all the range of blend compositions. Water and oxygen barrier properties of PHBV/PLA blends are significantly improved with increasing the PHBV content in the blend. Further, morphological analyzes indicated that increasing the PHBV content in the polymer blends results in increasing the PLA crystallinity due to the finely dispersed PHBV crystals acting as a filler and a nucleating agent for PLA. On the other hand, the addition of PLA to the blend results in a very impressive increase in the complex viscosity of PHBV. Moreover, the rheological data showed that, excluding the specific behavior of the neat polymers at low frequencies, i.e. less than 0.1 Hz, the complex viscosity of PHBV/PLA blends fits the mixing law well.  相似文献   
39.
The effect of cationic micelles of cetyltrimethyl ammonium bromide (CTAB) on the observed pseudo-first-order rate constant for the interaction of nickel dipeptide complex [Ni(II)-Gly-Gly]+ with ninhydrin has been studied spectrophotometrically. At constant temperature and pH, increase in the [CTAB] from 0.0 to 60.0 × 10?3 mol dm?3 caused nearly three-fold increase of the rate constant. The micellar catalysis is explained in terms of the pseudophase model. From the observed kinetic data, binding constants of micelle–[Ni(II)-Gly-Gly]+ (K S), and micelle–ninhydrin (K N) are evaluated, respectively, to be 5.3 mol?1 dm3 and 84.0 mol?1 dm3. The role of added inorganic (NaCl, NaBr, Na2SO4) and organic salts (NaBenz, NaSal) on the reaction rate has also been examined.  相似文献   
40.
A stable palm-based anti-wrinkle lotion enriched with tocotrienols was successfully prepared. The stability of the product was due to the presence of liquid crystalline structure in the emulsion system. It helps in bringing the active to the dermis layer. Functionality active ingredients such as tocotrienols and anti-wrinkle were added in the formulation. A commercial plant extract was used to strengthen the collagen seated at the dermis layer. The product was formulated to pH 5.5 which is suitable for the skin. The mean droplet size is 10.2 µm with a monomodal distribution pattern which prevents agglomeration. This will decrease Brownian motion, thus prolonging its stability. Long-term acute moisturizing tests show a significant increase of between 24% and 17% hydration for five and six weeks respectively. The efficacy testing on 12 subjects confirmed a reduction in natural fine wrinkles on faces during aging or premature aging at ?7.6%.  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