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   3319篇
  免费   185篇
  国内免费   83篇
化学   2492篇
晶体学   15篇
力学   177篇
数学   393篇
物理学   510篇
  2024年   1篇
  2023年   17篇
  2022年   66篇
  2021年   87篇
  2020年   116篇
  2019年   146篇
  2018年   203篇
  2017年   150篇
  2016年   270篇
  2015年   167篇
  2014年   237篇
  2013年   449篇
  2012年   286篇
  2011年   255篇
  2010年   203篇
  2009年   171篇
  2008年   183篇
  2007年   137篇
  2006年   74篇
  2005年   70篇
  2004年   74篇
  2003年   52篇
  2002年   41篇
  2001年   17篇
  2000年   19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3587条查询结果,搜索用时 15 毫秒
201.
This work describes the promising activity of silver nanoparticles on the surface of a poly(2-amino diphenylamine) modified carbon paste electrode (CPE) towards formaldehyde oxidation. Electrodeposition of the conducting polymer film on the CPE was carried out using consecutive cyclic voltammetry in an aqueous solution of 2-aminodiphenylamine and HCl. Nitrogen groups in the polymer backbone had a Ag ion accumulating effect, allowing Ag nanoparticles to be electrochemically deposited on the surface of the electrode. The electrochemical and morphological characteristics of the modified electrode were investigated. The electro-oxidation of formaldehyde on the surface of electrode was studied using cyclic voltammetry and chronoamperometry in aqueous solution of 0.1 mol/L NaOH. The electro-oxidation onset potential was found to be around -0.4 V, which is unique in the literature. The effect of different concentrations of formaldehyde on the electrocatalytic activity of the modified electrode was investigated. Finally, the diffusion coefficient of formaldehyde in alkaline media was calculated to be 0.47 × 10-6 cm2/s using chronoamperometry.  相似文献   
202.
Bioconversion of cellulosic material into glucose needs cellulase enzymes. One of the most important organisms that produces cellulases is Trichoderma reesei, whose cellulose enzymes are probably the most widely used in the industry. However, these enzymes are not stable enough at high pH and temperatures. The optimized synthetic endoglucanase II gene with Pichia pastoris codon preferences was secretary expressed in P. pastoris. Recombinant enzyme characterization showed maximum activity at pH 4.8 and temperature 75 °C, and it demonstrated increasing thermal stability in high temperature. The enzyme maintained its activity in a wide pH range from 3.5 to 6.5. The optimization of fermentation medium was carried out in shaking flasks. Recombinant protein expression at optimum conditions (pH 7, temperature 25 °C, and 1 % methanol induction) for 72 h demonstrated 2,358.8 U/ml endoglucanase activity units. To our knowledge, this is the highest acidic thermophilic endoglucanase activity that is reported in crude intracellular medium in P. pastoris. We conclude that P. pastoris is an appropriate host for high-level expression of optimized endoglucanase gene with improved thermal stability.  相似文献   
203.
The relationship between the rheological properties of nylon-6,6 solutions and the morphology of their electrospun nanofibers was established. The viscosity of nylon-6,6 in formic acid(90%) was measured in the concentration range of 5 wt%-25 wt% using a programmable viscometer. Electrospinning of nylon-6,6 solutions was carried out under controlled parameters. The chemical structure, morphology and thermal properties of the obtained nanofibers were investigated using Fourier transform infrared spectroscopy(FTIR), scanning electron microscopy(SEM) and differential scanning calorimetry(DSC), respectively. Entanglement concentration(ce) was found to be 15 wt% and a power law relationship between specific viscosity and solution concentration was observed with exponents of 2.0 and 3.3 for semi-dilute unentangled(c ce) and semi-dilute entangled(c ce) regimes, respectively. The diameter and uniformity of the nanofibers were found to be dependent on the viscosity. Moreover, the average diameter of electrospun nanofibers was found to be dependent on zero shear rate viscosity and normalized concentration(c/ce) in a power law relationship with exponents of 0.298 and 0.816, respectively. For nylon-6,6 solutions, the entanglement concentration(ce = 15 wt%) provides the threshold viscosity required for the formation of a stable polymeric jet during electrospinning and producing uniform beadless fibers. For concentrations less than ce, beaded fibers with some irregularities are formed. DSC analysis showed an increase in crystallinity of all electrospun samples compared to original polymer. Furthermore, Based on FTIR spectroscopy, α phase is dominant in electrospun nanofibers and minor amount of β and γ phases is also available.  相似文献   
204.
Polyaniline nanofibers are readily synthesized by bulk polymerization; ammonium per sulphate (APS) is used as oxidizing agent and hydrochloric acid as dopant without any hard or soft templates. A detailed study was conducted on the effect of a variety of synthetic conditions on the size and morphology of the polyaniline nanostructure. These conditions include the concentration of dopant, and the APS-to-aniline and acid-to-aniline molar ratios. The morphology of the nanofibers was confirmed by SEM and TEM. XRD and FT-IR and UV–visible spectroscopy were used for structural characterization of nanofibers. The results showed that not only the microstructure of the polyaniline product, but also other characteristics, for example conductivity, crystallinity, and, more importantly, the efficiency of the process are strongly affected by the synthetic conditions.  相似文献   
205.
A convenient and efficient solvent-free procedure is described for preparation of 6-amino-4-aryl-3-methyl-1,4-dihydropyrano[2,3-c]pyrazole-5-carbonitriles by four-component reaction of hydrazine hydrate, ethyl acetoacetate, aryl aldehyde, and malononitrile in the presence of a catalytic amount of titanium dioxide nano-sized particles. Short reaction times, high yields under ambient conditions, simple reaction, clean work-up, and reusability of the nano heterogeneous catalyst are the advantages of this method.  相似文献   
206.
Uncatalyzed one-pot pseudo-four-component reaction of ethyl pyruvate, anilines, and aldehydes in n-hexane as solvent, under reflux, affords a variety of 3-amino-1,5-dihydro-2H-pyrrol-2-ones in high yield. n-Hexane is an excellent driving force in preparation of the desired products. These compounds have biological and pharmacological properties and are also used in medicinal chemistry. Use of a non-toxic and inexpensive solvent, simple and efficient synthesis, clean work-up, and high yields of the products are the advantages of this method. We report the first catalyst-free method for synthesis this class of compounds.  相似文献   
207.
In this study, CoFe2O4/Sawdust and NiFe2O4/Sawdust magnetic nanocomposites were synthesized using a hydrothermal method, and then characterized using X-ray powder diffraction, Infrared, scanning electron microscopy, Brunauer–Emmett–Teller/Barrett–Joyner–Halenda, and vibrating-sample magnetometer techniques. In this study, unmodified sawdust (US), modified sawdust (MS), unmodified CoFe2O4/sawdust (UCS), modified CoFe2O4/sawdust (MCS), unmodified NiFe2O4/sawdust (UNS), and modified NiFe2O4/Sawdust (MNS) magnetic nanocomposites, which are inexpensive, economical, environmentally friendly absorbents, and have a high selective hydrophobic, were used for the removal of oil from the water surface. The results show that the UCS, MCS, UNS, and MNS magnetic nanocomposites can selectively absorb the oil spreading on the water surface, due to its superhydrophobicity and superoleophilicity, and can be easily collected from water under the influence of a magnetic field. In addition, the results showed that the absorbents reach their equilibrium at the 30-min mark. Among all the absorbents, the MNS magnetic nanocomposite showed the maximum absorption capacity (18.172 g/g) at the 40-min mark. The results of the kinetic studies showed that the second-order kinetic equation with the highest correlation coefficient had the best fit with the experimental results.  相似文献   
208.
A new, green, and highly efficient protocol for the expeditious preparation of some α,α′-bis[(aryl or allyl)idene]cycloalkanones and 2-[(aryl or allyl)idene]-1-indanones via a simple microwave-assisted Claisen–Schmidt condensation reaction catalyzed by MoCl5 was successfully developed. Outstanding features of the current methodology include the use of solvent-free conditions, simple operation, use of a very inexpensive and available catalyst, low catalyst loading, short reaction times, high yields of the pure products, no harmful by-products, easy workup, and also the applicability of microwave irradiation as a clean source of energy. Furthermore, a gram-scale reaction was successfully conducted, proving the scalability of this current Claisen–Schmidt condensation reaction.  相似文献   
209.
Substituent effect on the structure and electronic properties of H2Si=SiHAr (Ar = p-C6H4X; X = NH2, OH, Me, H, F, Cl, CHO, COOH, CN, NO2) molecules are studied at the CAM-B3LYP/6-311G(d,p) level of theory. Energy decomposition analysis (EDA) is used as a useful tool for illustrating the interaction between H2Si and SiHAr fragments in HArSi=SiH2 molecules. Energetic analysis reveals that the singlet state of the fragments is more stable than triplet state. Also, interactions are stronger in the presence of electron-withdrawing groups (EWGs) in comparison to electron donating groups (EDGs). EDG and EDG effects are investigated on the stability of fragments, frontier orbital energy, distortion, HOMO–LUMO gap, electron-donating (ω) and electron-accepting (ω+) powers of the studied molecules. Then, the correlations between these calculated parameters with the Hammett and Brown constants (σp and σp+, respectively) are provided. Also, time-dependent density functional theory method (TD-DFT) is employed for the determination of the strongest absorption band values (λmax,el) of these molecules. This absorption band is attributed to the HOMO →LUMO transition.  相似文献   
210.
Ag2Cr2O7 nanoparticles were found to be an exceedingly effective catalyst for the mild and green synthesis of aminobenzochromenes. The reaction was performed under ultrasonic irradiation as an innocuous tool and in water as a green solvent at room temperature. This method encompasses several sustainable and economic benefits.  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