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   333篇
  免费   9篇
  国内免费   2篇
化学   224篇
力学   4篇
数学   34篇
物理学   82篇
  2023年   1篇
  2022年   2篇
  2021年   10篇
  2020年   6篇
  2019年   10篇
  2018年   11篇
  2017年   11篇
  2016年   14篇
  2015年   8篇
  2014年   13篇
  2013年   36篇
  2012年   32篇
  2011年   33篇
  2010年   13篇
  2009年   17篇
  2008年   19篇
  2007年   22篇
  2006年   11篇
  2005年   15篇
  2004年   13篇
  2003年   8篇
  2002年   12篇
  2001年   4篇
  2000年   1篇
  1999年   1篇
  1998年   1篇
  1996年   2篇
  1995年   2篇
  1994年   2篇
  1993年   3篇
  1990年   1篇
  1986年   1篇
  1985年   1篇
  1984年   3篇
  1980年   2篇
  1977年   2篇
  1975年   1篇
排序方式: 共有344条查询结果,搜索用时 500 毫秒
61.
Journal of Thermal Analysis and Calorimetry - The natural gas entering the liquefaction cycle usually consists of nitrogen, ethane, propane and also heavier hydrocarbons which are economically...  相似文献   
62.
Alpha-PW(12)O(40)(3-) (PW(12)) supported on the surface of silica gel derivatized by 3-aminopropyl(triethoxy)silane (devoted briefly as SiNH(3)PW(12)) was synthesized and used as bulk modifier to fabricate a renewable three-dimensional chemically modified electrode. The electrochemical behavior of the modified electrode was characterized by cyclic voltammetry. There is an ionic bonding character between PW(12) and the surface amino groups of modified silica, which greatly improves the stability of SiNH(3)PW(12)-modified carbon paste electrode due to insolubility of silica gel in water. The SiNH(3)PW(12) bulk-modified carbon paste electrode not only maintains the electrochemical activity of PW(12), but also exhibits remarkable advantages of renewability, as well as simple preparation and inexpensive material. The modified electrode offers an excellent and stable electrocatalytic response for the reduction of IO(3)(-) and hydrogen peroxide. The SiNH(3)PW(12)-CPE is successfully applied as an electrochemical detector to monitor IO(3)(-) in flow injection analysis (FIA). The catalytic peak current was found to be linear with the IO(3)(-) concentration in the range 5x10(-6) to 1x10(-3)molL(-1). The detection limit of the proposed method was found to be 3.1x10(-6)molL(-1) for IO(3)(-) determination.  相似文献   
63.
Central composite design (CCD) and response surface methodology (RSM) were developed as experimental strategies for modeling and optimization of the influence of some variables on the performance of a new PVC membrane triiodide ion-selective electrode. This triiodide sensor is based on triiodide-clozapine ion-pair complexation. PVC, plasticizers, ion-pair amounts and pH were investigated as four variables to build a model to achieve the best Nernstian slope (59.9 mV) as response. The electrode is prepared by incorporating the ion-exchanger in PVC matrix plasticized with 2-nitrophenyl octal ether, which is directly coated on the surface of a graphite electrode. The influence of foreign ions on the electrode performance was also investigated. The optimized membranes demonstrate Nernstian response for triiodide ions over a wide linear range from 5.0 x 10(-6) to 1.0 x 10(-2)mol L(-1) with a limit of detection 2.0 x 10(-6) mol L(-1) at 25 degrees C. The electrodes could be used over a wide pH range 4-8, and have the advantages of easy to prepare, good selectivity and fast response time, long lifetime (over 3 months) and small interferences from hydrogen ion. The proposed electrode was successfully used as indicator electrode in potentiometric titration of triiodide ions and ascorbic acid.  相似文献   
64.
Annihilation of the contribution of one chemical component from the original data matrix is a general method in rank annihilation factor analysis (RAFA). However, RAFA is not applicable for studying the protonation equilibria of multiprotic acids. In this work, a two-rank annihilation factor analysis (TRAFA) method was proposed for determination of the acidity constants of diprotic acids. After recording the electronic absorbance spectra of the acids at different pH, the contributions of both H2A and A2− were annihilated from the absorbance data, which made feasible the determination of two successive acidity constants. The method was validated by analysis of simulated data and its application to the determination of the acidity constants of calmagite, as a reference compound. A close agreement was obtained between the resulted values by TRAFA and the declared values. Indeed, the method was used for determination of the acidity constants of two new chromenone derivatives in binary solvents mixtures of methanol and water. The effects of changing solvent composition on acidity constant data were explained by linear solvation free energy relationships (LSFER) utilizing solvatochromic parameters.  相似文献   
65.
To find metal ion recognition by L (L = O2N2-donor naphthodiaza-crown macrocyclic ligand), the complexes [ML]2+ (M = Cd, Hg and Pb) were synthesized and characterized by IR, 1H, 13C NMR, and mass spectrometry, as well as elemental microanalysis. Hg(II) showed perceptible enhancement of the fluorescence of L in which ultra-low limit of detection for Hg(II) by L was determined as 1 nM in ethanol and DMSO. L reserved selectivity of Hg(II) in its binary mixtures with metal cations in solution. A 1 : 1 stoichiometry was found for the interaction of Hg(II) with L while Benesi–Hildebrand method was applied to calculate its complexation binding constant (KBH) employing fluorescence spectrophotometry. The monitoring of the chemical shifts in 1H NMR spectra of these complexes demonstrated that the central macrocycle of L was tailored for the size of Hg(II). Density functional theory calculations using B3LYP/6–31G* basis set demonstrated that the macrocycle cavity of L was properly fitted for complex formation with Hg(II) cation, while both Cd(II) and Pb(II) cations did not form strong bonds with L from inadequate cation size. The present study shows detection method of Hg(II) and also possible application of naphthodiaza as an appropriate fluorophore macrocyclic ligand for detecting other metal ions.  相似文献   
66.
A new convenient colorimetric sensor for fructose based on anti-aggregation of citrate-capped gold nanoparticles(Au NPs) is presented. 4-Mercaptophenylboronic acid(MPBA) induces the aggregation of Au NPs, leading to a color change from red to blue. Fructose as a potent competitor has strong affinity for MPBA and a borate ester is formed between MPBA and fructose. There is an obvious color change from blue to red with increasing the concentration of fructose. The anti-aggregation effect of fructose on Au NPs was seen by the naked eye and monitored by UV–vis spectra. Our results showed that the absorbance ratio(A_(519)/A_(640)) was linear with fructose concentration in the range of 0.032–0.96 μmol/L(R~2= 0.996), with a low detection limit of 0.01 μmol/L(S/N = 3). Notably, a highly selective recognition of fructose was shown against other monosaccharide and disaccharide(glucose, mannose, galactose,lactose and saccharose). With anti-aggregation assays higher selectivity is achievable. The results of this work provide a rapid method for evaluating the quantitative analysis of fructose in human plasma at physiologically meaningful concentrations and at neutral pH. The proposed procedure can be used as an efficient method for the precise and accurate determination of fructose.  相似文献   
67.
The black-and-white travelling salesman problem (BWTSP) is an extension to the well-known TSP by partitioning the set of vertices into black and white vertices, and imposing cardinality and length constraints between two consecutive black vertices in a Hamiltonian tour. BWTSP has various applications in aircraft routing, telecommunication network design and logistics. In this paper, we develop several tabu search (TS) heuristics for solving the BWTSP. Our TS is built upon a new efficient neighbourhood structure, which exploits both the permutation and knapsack features of BWTSP. We also embed our TS as a heuristic procedure to improve the upper bound in a mixed-integer linear programming method. Extensive computational experiment on both benchmark and randomly generated instances shows effectiveness and efficiency of our algorithms. Our algorithms are able to obtain optimal and near optimal solutions to small instances in seconds, and find feasible solutions to large instances that have not been solved by the existing methods in the literature.  相似文献   
68.
The retention of histidine-containing peptides in immobilized metal-affinity chromatography is studied using several hundred modeled peptides. Retention is driven primarily by the number of histidine residues; however, the amino acid composition in the immediate vicinity plays a significant role. Specifically, the arginine and tryptophan content has to be taken into consideration. During the course of this study, an alternative tag that can be used similarly to a polyhistidine tag is discovered.  相似文献   
69.
Flexible and economic sensor devices are the focus of increasing interest for their potential and wide applications in medicine, food analysis, pollution, water quality, etc. In these areas, the possibility of using stable, reproducible, and pocket devices can simplify the acquisition of data. Among recent prototypes, sensors based on laser-induced graphene (LIGE) on Kapton represent a feasible choice. In particular, LIGE devices are also exploited as electrodes for sensing in liquids. Despite a characterization with electrochemical (EC) methods in the literature, a closer comparison with traditional graphite electrodes is still missing. In this study, we combine atomic force microscopy with an EC cell (EC-AFM) to study, in situ, electrode oxidation reactions when LIGE or other graphite samples are used as anodes inside an acid electrolyte. This investigation shows the quality and performance of the LIGE electrode with respect to other samples. Finally, an ex situ Raman spectroscopy analysis allows a detailed chemical analysis of the employed electrodes.  相似文献   
70.
The interaction of Love waves with square array of pillars deposited on a cavity defined in a 2D holey phononic crystal is numerically investigated using Finite Element Method. First, the existence of SH surface modes is demonstrated separately for phononic crystals that consist of square arrayed holes, or rectangular arrayed Ni pillars, respectively in, or on, a SiO2 film deposited on a ST-cut quartz substrate. The coupling between SH modes and torsional mode in pillars induces a transmission dip that occurs at a frequency located in the range of the band-gap of the holey phononic crystal. Second, a cavity is constructed by removing lines of holes in the holey phononic crystal and results in a transmission peak that matches the dip. The optimal geometrical parameters enable us to create a coupling of the cavity mode and the localized pillar mode by introducing lines of pillars into the cavity, which significantly improved the efficiency of the cavity without increasing the crystal size. The obtained results will pave the way to implement advanced designs of high-performance electroacoustic sensors based on coupling modes in phononic crystals.  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