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   987篇
  免费   41篇
  国内免费   16篇
化学   516篇
晶体学   6篇
力学   48篇
数学   177篇
物理学   297篇
  2023年   9篇
  2022年   10篇
  2021年   18篇
  2020年   19篇
  2019年   24篇
  2018年   26篇
  2017年   26篇
  2016年   30篇
  2015年   37篇
  2014年   44篇
  2013年   82篇
  2012年   79篇
  2011年   81篇
  2010年   58篇
  2009年   35篇
  2008年   63篇
  2007年   52篇
  2006年   37篇
  2005年   24篇
  2004年   23篇
  2003年   12篇
  2002年   19篇
  2001年   16篇
  2000年   13篇
  1999年   6篇
  1998年   8篇
  1997年   5篇
  1996年   5篇
  1995年   11篇
  1994年   10篇
  1993年   7篇
  1992年   5篇
  1991年   8篇
  1990年   11篇
  1989年   5篇
  1987年   5篇
  1985年   11篇
  1984年   12篇
  1983年   12篇
  1982年   5篇
  1981年   13篇
  1980年   4篇
  1979年   4篇
  1978年   4篇
  1976年   4篇
  1974年   4篇
  1972年   4篇
  1968年   4篇
  1956年   5篇
  1954年   6篇
排序方式: 共有1044条查询结果,搜索用时 550 毫秒
51.
Adsorption isotherms of nonionic polyvinylpyrrolidone (PVP) and anionic ionized polyacrylic acid (PAA) polymers on single Na-montmorillonite clay and γ-alumina adsorbents in 0.01M NaCl and pH 5.6 are reported and compared to results obtained with aqueous adsorbent mixtures. Microeiectrophoretic behaviours of adsorbents are also observed.

It can be shown that antagonistic effects due to interactions between oppositely charged adsorbent surfaces largely limit the nonionic PVP adsorption.  相似文献   
52.
Simple cyclic renewable silver amalgam film electrode (Hg(Ag)FE), applied for the determination of gallium(III) using differential pulse anodic stripping voltammetry (DP ASV), is presented. The effects of various factors such as: preconcentration potential and time, pulse height, step potential and supporting electrolyte composition are optimised. The calibration graph is linear from 5?nM (0.35?µg?L?1) to 80?nM (5.6?µg?L?1) for a preconcentration time of 60?s, with correlation coefficient of 0.995. For a Hg(Ag)FE with a surface area of 9.9?mm2 the detection limit for a preconcentration time of 120?s is as low as 0.1?µg?L?1. The repeatability of the method at a concentration level of the analyte as low as 3.5?µg?L?1, expressed as RSD is 3.2% (n?=?5). The proposed method was successfully applied by studying the synthetic samples and simultaneously recovery of Ga(III) from spiked aluminium samples.  相似文献   
53.
Amidoxime modified hydroxypropyl methylcellulose (HPMC) films (HPMC-g-AO) were used for the recovery of uranium from aqueous solutions by a complexation process. The adsorption experiments were carried out by immersion of a certain amount of films in UO2 2+ solutions (resultant pH 4.1) ranging in concentration from 100 to 1,000 ppm. The effect of temperature (25–50 °C) on the adsorption capacity of HPMC-g-AO was investigated at the optimized time. The adsorption kinetics and the thermodynamics as well as the adsorption capacity of HPMC-g-AO films were investigated. The adsorption capacity was found as 765 mg UO2 2+/g dry film. The kinetic and the thermodynamic parameters (i.e. activation energy, enthalpy, entropy and Gibbs free energy) for the interaction of UO2 2+ with HPMC-g-AO were calculated based on known basic relations. The results showed that adsorption occurred through strong electrostatic interactions with an enthalpy of ?36.5 kJ/mol. The desorption of UO2 2+ were investigated using different desorption agents such as EDTA, HCl, NaHCO3, and NaOH. After the 2 weeks treatment period, the highest desorption yield were found as 23 % with NaHCO3.  相似文献   
54.
The inhibition efficiency of 2-Pyrrolidin-1-yl-1,3-thiazole-5-carboxylic acid (PTCA) against mild steel (MS) corrosion was investigated in acidic solution by using quantum chemical calculations based on Density Functional Theory (DFT) method and electrochemical measurements. The electrochemical impedance spectroscopy (EIS), potentiodynamic, potential zero charge (pzc) analysis and electrochemical noise (EN) measurements at various concentrations (from 0.1 to 10 mM) and immersion times were utilized in experimental part. The surface analysis was achieved scanning electron microscope (SEM) and contact angle measurements in the absence and presence of 10 mM PTCA. According to DFT results, PTCA exhibited 3.737 eV band gap and 8.130 Debye dipole moment which were a signal of potentially convenient corrosion inhibitor properties. PTCA has a remarkable corrosion inhibition capability to mild steel, which inhibited both anodic and cathodic corrosion rates, relying on it's physically adsorption on the metal solution interface and protection ability was increased with increasing PTCA concentration. The obtained adsorption equilibrium constant was 11.11 × 103 M-1 and calculated standard free energy of adsorption was ?33.03 kJ mol?1. The determined activation energy values were 55.58 kJ mol?1 and 96.86 kJ mol?1 in 0.5 M HCl in the absence and presence of 10 mM PTCA, respectively. PTCA demonstrated a strong inhibition efficiency of 98.3%, after 168 h immersion, according to the EIS results. As a consequently, we recommend that PTCA is a convenient inhibitor in 0.1 M HCl for mild steel protection against corrosion.  相似文献   
55.
56.
The carbohydrate compounds have interesting stereochemical properties and can be used as chiral building blocks in the production of more complex derivatives. L-Rhamnose has been reported to participate in the synthesis of cytotoxic α-pyrones owing to the stereochemistry of the hydroxy groups. To study the conformational properties of acetyl derivatives of L-rhamnose, it was tosylated with the subsequent reduction and acetylation. These series of reactions produced an interesting mixture of poly-acetylated compounds. The mixture was separated by HPLC, characterized by 1D and 2D NMR techniques and compared with models obtained on DFT/B3LYP/DGDZVP theory level of calculation, taking into account the effect of pyridine as solvent in the transformation of this carbohydrate. The results show a mixture of three pyranoside products with tosyl group in positions 2, 3, and 4. These latter compounds after reduction with aluminum hydride and acetylation yielded two main products, one triacetate pyranoside and an open-chain mannositol tretraacetate.  相似文献   
57.
A novel carboxymethylcellulose (CMC)–hydroxyethylcellulose (HEC)-based hydrogel with sensitivity to environmental changes, pH and salts was synthesized by using fumaric acid and malic acid at various concentrations. Water uptake capacity of hydrogels was investigated in distilled water, various salt and pH solutions. From pH-dependent studies, it was found that greater water uptake values were observed at greater pH values (7.4), and reversible pH responsiveness of CMC–HEC based hydrogels was obtained. Decreasing the water uptake capacity with increasing of the charge of the metal cation (Al3+ < Ca2+ < Na+) demonstrated metal ion responsiveness of CMC–HEC-based hydrogels. From tensile tests of the hydrogels, a greater crosslinker concentration led to greater tensile strength values. Thermogravimetric analysis and scanning electron microscopy images were used to determine the thermal stability and to observe morphological properties of the samples, respectively.  相似文献   
58.
59.
As one of the newly emerged nanomaterials, graphene quantum dots (GQDs) have shown great application potential as tracking probes and drug carriers in biological areas. The GQDs synthesized via the nitric acid reflux method in this study turned out to quench the fluorescence of human serum albumin (HSA) and gamma globulin (γ-globulin) in two different functional ways. The fluorescence quenching effect of GQDs on HSA is a static pattern and the predominant interaction forces are hydrogen bonds and van der Waals forces. Distinct from HSA, the interaction between GQDs and γ-globulins belongs to dynamic quenching and is driven by electrostatic forces. Ultraviolet–visible (UV–vis) differential spectrometry and transient state fluorescence spectrometry were also utilized to further confirm their quenching types. Also, thermodynamics parameters, the enthalpy change (ΔH) and entropy change (ΔS) of reaction between GQDs and proteins were obtained through a series of calculations from the van’t Hoff equation. Furthermore, the effect of GQDs on the conformational structure of proteins was characterized by synchronous fluorescence spectra (SFS), three-dimensional (3D) fluorescence and circular dichroism (CD) spectra. In addition, the binding mechanism of GQDs with HSA and γ-globulins were proposed based on the obtained experimental results. The research on the reaction between GQDs with HSA and γ-globulins offers promising insight for the further application of nanomaterials in biomedical fields.  相似文献   
60.
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