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   3337篇
  免费   187篇
  国内免费   83篇
化学   2500篇
晶体学   16篇
力学   181篇
数学   399篇
物理学   511篇
  2024年   1篇
  2023年   17篇
  2022年   56篇
  2021年   89篇
  2020年   118篇
  2019年   148篇
  2018年   203篇
  2017年   150篇
  2016年   275篇
  2015年   167篇
  2014年   239篇
  2013年   453篇
  2012年   289篇
  2011年   257篇
  2010年   205篇
  2009年   172篇
  2008年   184篇
  2007年   139篇
  2006年   74篇
  2005年   70篇
  2004年   74篇
  2003年   52篇
  2002年   41篇
  2001年   18篇
  2000年   20篇
  1999年   17篇
  1998年   10篇
  1997年   3篇
  1996年   7篇
  1995年   7篇
  1994年   1篇
  1993年   4篇
  1992年   7篇
  1991年   3篇
  1990年   3篇
  1989年   4篇
  1988年   2篇
  1987年   1篇
  1986年   1篇
  1985年   5篇
  1984年   4篇
  1983年   4篇
  1982年   3篇
  1981年   1篇
  1980年   1篇
  1979年   1篇
  1977年   3篇
  1975年   3篇
  1963年   1篇
排序方式: 共有3607条查询结果,搜索用时 15 毫秒
931.

Alumina nanofluids are one of the most useful nanofluids, especially for increasing the thermal conductivity. Due to importance of porous media in the improvement of heat transfer, this study investigates the transport and retention of gamma alumina/water nanofluid in the water-saturated porous media. For this purpose, alumina nanofluids were introduced to the porous media consisting of water-saturated glass beads possessing various pH values (4, 7 and 10) and different ionic strengths (0.001 M of KCl, CaCl2, AlCl3, K2SO4, CaSO4, Al2(SO4)3, K2CO3 and CaCO3). Then the break through curve of each experiment was drawn and modeled by combining classical filtration theory with advection–dispersion equation. Single collector efficiency (η0) and attachment efficiency (α) were calculated by classical filtration theory. Also curve fitting of experiments and modeling was achieved by minimizing the sum of squared residuals, to calculate retardation factor (R) and hydrodynamic dispersion coefficient (D) of each experiment. According to the results, in general, increase in pH and ionic strength will enhance the removal rate coefficient, retardation factor and retention while decreasing the steady-state break through concentration and the hydrodynamic dispersion coefficient. The opposite of this rule was observed and analyzed for aluminum salts. The lowest retention of nanoparticles at 31.04% can be related to their transport in background solution with pH = 4 [α = \(3.87 \times 10^{ - 2}\), Katt = \(3.33 \times 10^{ - 3}\) (min−1), R = 3.93, D = 0.91 (cm2 min−1)], and the highest retention in nanoparticle content of 94.29% was observed in background solution containing CaCO3 [α = \(14.33 \times 10^{ - 2}\), Katt = \(137.82 \times 10^{ - 3}\) (min−1), R = 12.02, D = 0.62 (cm2 min−1)]. Therefore, chemistry of water plays an important role in transport and retention parameters. The classical filtration theory and the advection–dispersion model are able to perfectly model and quantify the parameters of the alumina nanofluid transport in saturated porous media.

  相似文献   
932.
The environment-friendly one-pot three-component condensation reactions of 4-hydroxycoumarin or 4-hydroxy-6-methylpyrone, p-substituted benzaldehyde, and alkyl or aryl isocyanides to afford furocoumarines or furopyranones in water in good yields after about one hour at 75°C are reported.  相似文献   
933.
The preparation and electrocatalytic behavior of glassy carbon electrodes modified with three different cobalt porphyrin complexes were investigated. The electrocatalytic ability of the modified electrodes for the reduction of dioxygen to hydrogen peroxide and water in air‐saturated aqueous solutions was examined by cyclic voltammetry and chronoamperometry techniques. The porphyrin‐adsorbed glassy carbon electrodes possess excellent electrocatalytic abilities for dioxygen reduction with overpotential about 0.5 V lower than that at a plain glassy carbon electrode. The experimental parameters were optimized and the mechanism of the catalytic process was discussed. The possible effects of the electron‐donating properties of groups in the meso‐position of the porphyrin ring were investigated.  相似文献   
934.
Summary. Acetylation of primary, secondary, and tertiary alcohols was carried out in some refluxing alkyl acetates and in two carboxylic acids with the participation of catalytic amounts of H3PW12O40, H3PMo12O40, and H14P5W30O110 with good yields and high stereo(regio)specificity under mild reaction condition. H3PW12O40 and H3PMo12O40 have also shown excellent reactivity in the formylation of 1-butanol with ethyl formate at room temperature and in short reaction times. Heteropolyacid catalysts could be separated after a simple work up and reused for several times.  相似文献   
935.
The NMR spectral data including high resolution 1H, 13C and 2D NMR for butrin, 3,4,7-trihydroxyflavanone 3,7-di-O--D-glucopyranoside, isolated from flowers of Butea monosperma, are reported here for the first time. Butrin was hydrolyzed using b-glucosidase to butin in high yield. They were subjected to free radical scavenging test using 2,2-diphenyl-1-picrylhydrazyl (DPPH) spectrophotometric assay. At a dose of 4 × 10-8 mol of tested compounds, the percentage of reduced DPPH for butin was 14.5% while no reduction was observed for butrin (0%).  相似文献   
936.
This study presents for the first time development of a highly selective and sensitive thulium(III) micro‐sensor. Theoretical calculations were conducted on a S‐N Schiff base [thiophene‐2‐carbaldehyde‐(7‐methyl‐1,3‐benzothiazol‐2‐yl) hydrazone] (TCMH) in order to obtain a clue about the tendency of TCMH to Tm(III) and some other metal ions. Then, TCMH was used as a membrane‐active component to prepare a Tm(III)‐selective polymeric membrane microelectrode. In line with the resulting data, the electrode exhibits a Nernstian response toward Tm(III) ions for a very wide concentration range (1.0×10?11–4.0×10?6 M) with a detection limit of 1.0×10?11 (ca. 1.5 ppt) and a very fast response time in the whole concentration range (<5 s). In addition, the results showed that the certain microelectrode could be applied in the pH range of 4.0–11.0 with a usage of more than one month without any considerable potential divergence.  相似文献   
937.
The catalytic effect of manganese(II) on the oxidation of barium diphenylamine sulfonate (BDAS) with potassium bromate in sulfuric acid was studied. Progress of the reaction was monitored, spectrophotometrically, by measuring absorbance changes at 547.5 nm. A highly sensitive, selective and simple method was accordingly developed for the determination of trace amounts of Mn(II), with no need for a separation or pre‐concentration step. Effects of reaction time, concentration of reagents, temperature and ionic strength on the reaction rate were studied. In the optimized conditions, manganese could be determined in a range of 1 to 60 ng mL?1 with a detection limit of 0.2 ng mL?1. The proposed method was successfully applied to the determination of manganese in tea leaves.  相似文献   
938.
A novel PVC-based membrane sensor based on the Co(II)-salophen complex (CSC) is described. The electrode revealed a Nernstian response over a wide nitrite ion concentration range (1.0×10–6–1.0×10–1M). The detection limit of the sensor is 8.0×10–7M. The best performance was obtained with a membrane composition of 33% PVC, 61% ortho-nitrophenyloctyl ether, 3% cobalt(II)-salophen, and 3% hexadecyltrimethylammonium bromide. The potentiometric response of the sensor is independent of the pH of solution in the pH range 4.5–11.9. The electrode exhibits a very fast response time and good selectivity over a variety of common inorganic and organic anions, including fluoride, bromide, iodide, sulfite, nitrate, thiocyanate, thriiodide and perchlorate. The selectivity behavior of the proposed sensor shows substantial improvements compared to the previously reported electrodes for nitrite ion. The membrane sensor can be used for at least 2 months without any divergence in potential. The electrode was successfully applied to the monitoring of nitrite ion in water, sausage, flour, wheat, cheese and milk.  相似文献   
939.
The electrochemical properties of hydrazine studied at the surface of a carbon paste electrode spiked with p‐bromanil (tetrabromo‐p‐benzoquinone) using cyclic voltammetry (CV), double potential‐step chronoamperometry and differential pulse voltammetry (DPV) in aqueous media. The results show this quinone derivative modified carbon paste electrode, can catalyze the hydrazine oxidation in an aqueous buffered solution. It has been found that under the optimum conditions (pH 10.00), the oxidation of hydrazine at the surface of this carbon paste modified electrode occurs at a potential of about 550 mV less positive than that of a bar carbon paste electrode. The electrocatalytic oxidation peak current of hydrazine showed a linear dependent on the hydrazine concentrations and linear analytical curves were obtained in the ranges of 6.00×10?5 M–8.00×10?3 M and 7.00×10?6 M–8.00×10?4 M of hydrazine concentration with CV and differential pulse voltammetry (DPV) methods, respectively. The detection limits (3σ) were determined as 3.6×10?5 M and 5.2×10?6 M by CV and DPV methods. This method was also used for the determination of hydrazine in the real sample (waste water of the Mazandaran wood and paper factory) by standard addition method.  相似文献   
940.
The electrochemical behavior of L ‐cysteine studied at the surface of ferrocenedicarboxylic acid modified carbon paste electrode (FDCMCPE) in aqueous media using cyclic voltammetry, differential pulse voltammetry and double potential step chronoamperometry. It has been found that under optimum condition (pH 8.00) in cyclic voltammetry, the oxidation of L ‐cysteine occurs at a potential about 200 mV less positive than that of an unmodified carbon paste electrode. The kinetic parameters such as electron transfer coefficient, α, and catalytic reaction rate constant, kh were also determined using electrochemical approaches. The electrocatalytic oxidation peak current of L ‐cysteine showed a linear dependent on the L ‐cysteine concentration and linear analytical curves were obtained in the ranges of 3.0×10?5 M–2.2×10?3 M and 1.5×10?5 M–3.2×10?3 M of L ‐cysteine concentration with cyclic voltammetry (CV) and differential pulse voltammetry (DPV) methods respectively. The detection limits (3σ) were determined as 2.6×10?5 M and 1.4×10?6 M by CV and DPV methods.  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