全文获取类型
收费全文 | 2916篇 |
免费 | 1363篇 |
国内免费 | 236篇 |
专业分类
化学 | 1144篇 |
晶体学 | 9篇 |
力学 | 140篇 |
综合类 | 36篇 |
数学 | 83篇 |
物理学 | 3103篇 |
出版年
2024年 | 6篇 |
2023年 | 24篇 |
2022年 | 57篇 |
2021年 | 60篇 |
2020年 | 78篇 |
2019年 | 62篇 |
2018年 | 53篇 |
2017年 | 107篇 |
2016年 | 111篇 |
2015年 | 108篇 |
2014年 | 270篇 |
2013年 | 228篇 |
2012年 | 305篇 |
2011年 | 293篇 |
2010年 | 237篇 |
2009年 | 253篇 |
2008年 | 255篇 |
2007年 | 247篇 |
2006年 | 223篇 |
2005年 | 203篇 |
2004年 | 191篇 |
2003年 | 165篇 |
2002年 | 140篇 |
2001年 | 117篇 |
2000年 | 106篇 |
1999年 | 107篇 |
1998年 | 84篇 |
1997年 | 76篇 |
1996年 | 71篇 |
1995年 | 47篇 |
1994年 | 45篇 |
1993年 | 35篇 |
1992年 | 32篇 |
1991年 | 37篇 |
1990年 | 14篇 |
1989年 | 20篇 |
1988年 | 11篇 |
1987年 | 15篇 |
1986年 | 2篇 |
1985年 | 3篇 |
1984年 | 2篇 |
1983年 | 3篇 |
1982年 | 3篇 |
1981年 | 1篇 |
1980年 | 2篇 |
1979年 | 2篇 |
1977年 | 1篇 |
1975年 | 1篇 |
1972年 | 1篇 |
1957年 | 1篇 |
排序方式: 共有4515条查询结果,搜索用时 437 毫秒
141.
The spectrum change of a Gaussian pulse in the far field is studied with the Fresnel diffraction integral when it is incident on an aperture with Gaussian form transmittance. It is found that the side-lobes of the diffracted spectral intensity, which exist in a normal circular aperture with unit transmittance, can be eliminated completely under such a condition. Also, the red shift and blue shift of the spectral intensity maximum of the incident pulse are presented. 相似文献
142.
In this paper, we investigate a generalized nonautonomous nonlinear equation which describes the ultrashort optical pulse propagating in a nonlinear inhomogeneous fiber. By virtue of the generalized Darboux transformation, the first- and second-order rogue-wave solutions for the generalized nonautonomous nonlinear equation are obtained, under some variable–coefficient constraints. Properties of the first- and second-order rogue waves are graphically presented and analyzed: When the coefficients are all chosen as the constants, we can observe the some functions, the shapes of wave crests and troughs for the first- and second-order rogue waves change. Oscillating behaviors of the first- and second-order rogue waves are observed when the coefficients are the trigonometric functions. 相似文献
143.
In this study, interaction of tetracycline (TC) and DNA in the Britton? Robinson buffer solution (BR) was studied by cyclic voltammetry. The experimental results reveal that TC can bind strongly to DNA and the association constant and binding number between TC and DNA was obtained. Then DNA was immobilized on a glassy carbon electrode by UV‐irradiation. Through this process, water‐soluble DNA was converted into insoluble materials, and a stable DNA film was formed on the electrode. The electrochemical oxidation behavior of TC was studied at UV‐irradiated DNA film modified glassy carbon electrode (UV‐DNA‐GCE). The response of modified electrode was optimized with respect to pH, accumulation time, ionic strength, drug concentration and other variables. TC at the surface of modified electrode showed a linear dynamic range of 0.30–90.00 µM and a detection limit of 0.27 µM. To demonstrate the applicability of the modified electrode, it was used for the analysis of real samples such as pharmaceutical formulations and milk. 相似文献
144.
A poly(4‐bromoaniline) (PBA) film is electrochemically synthesized on a gold electrode for the recognition of amino acids enantiomers. Scanning electron microscopy measurements show that the porous PBA films are made up of nano‐ribbons. At the PBA modified Au electrode differential pulse voltammograms of L ‐ and D ‐glutamic acids not only have very different current densities, but also produce different waveforms, providing an intuitive way to differentiate the two chiral molecules. Similar results are obtained in analyzing L ‐ and D ‐aspartic acids. Control experiments suggest that the observed sensing behavior arises from synergistic interactions between Au and the PBA film, where polymerization at the meta‐position creates a steric structure needed for differentiating chiral molecules. 相似文献
145.
Saied Saeed Hosseiny Davarani Hamid Reza Moazami Ali Reza Keshtkar Mohammad Hossein Banitaba Saeed Nojavan 《Analytica chimica acta》2013
A novel method for the selective electromembrane extraction (EME) of U6+ prior to fluorometric determination has been proposed. The effect of extraction conditions including supported liquid membrane (SLM) composition, extraction time and extraction voltage were investigated. An SLM composition of 1% di-2-ethyl hexyl phosphonic acid in nitrophenyl octyl ether (NPOE) showed good selectivity, recovery and enrichment factor. The best performance was achieved at an extraction potential of 80 volts and an extraction time of 14 minutes Under the optimized conditions, a linear range from 1 to 1000 ng mL−1 and LOD of 0.1 ng mL−1 were obtained for the determination of U6+. The EME method showed good performance in sample cleanup and the reduction of the interfering effects of Mn2+, Zn2+, Cd2+, Ni2+, Fe3+, Co2+, Cu2+, Cl− and PO43− ions during fluorometric determination of uranium in real water samples. The recoveries above 54% and enrichment factors above 64.7 were obtained by the proposed method for real sample analysis. 相似文献
146.
J. Albaiges 《International journal of environmental analytical chemistry》2013,93(9):671-680
Inorganic mercury ions (Hg2+) in laboratory prepared solutions were determined with a screen-printed carbon electrode (SPCE) coated with a polyaniline-methylene blue (PANI-MB) polymer layer. The structure and properties of the PANI-MB polymer layer were compared to that of normal polyaniline (PANI) in order to elucidate the structure of the PANI-MB layer. The electrically-conducting polymers were prepared by electrochemical polymerisation of monomer solutions of aniline, and mixed solutions of aniline with methylene blue onto respective screen-printed carbon electrodes (SPCEs). Scanning Electron Microscopy (SEM) analyses of the SPCE polymer coated electrodes have shown that nanostructured materials have formed with the diameters of the PANI nanoclusters and PANI-MB nanorods at approximately 200 nm. Anodic stripping voltammetry (ASV) was used to evaluate a solution composed of 1 × 10?6 M Hg2+, in the presence of the SPCE/PANI-MB polymer sensor electrode. The Hg2+ ions were determined as follows: (i) pre-concentration and reduction on the modified electrode surface and (ii) subsequent stripping from the electrode surface during the positive potential sweep. The experimental conditions optimised for Hg2+ determination included the supporting electrolyte concentration and the accumulation time. The results obtained have shown that the SPCE/PANI-MB polymer sensor electrode operates optimally at a pH 2, with the supporting electrolyte concentration at 0.5 M HCl. A linear calibration curve was found to be in the range of 1 × 10?8 M to 1 × 10?5 M Hg2+ after 120 s of pre-concentration. The detection limit was calculated and found to be 54.27 ± 3.28 µg L?1 of Hg2+. The results have also shown that a conducting polymer modified SPCE sensor electrode can be used as an alternative transducer for the voltammetric stripping and analysis of inorganic Hg2+ ions. 相似文献
147.
Vinay M M Purushothama H T Yathisha R O Basavarajappa K V Manjunatha P 《International journal of environmental analytical chemistry》2013,93(15):1553-1564
ABSTRACTThe rapid electrochemical determination of Aceclofenac (ACF) has been employed by cyclic voltammetry (CV), differential pulse voltammetry (DPV) using developed OH-functionalised multiwalled carbon nanotube carbon paste electrode (OH-MWCNT/CPE). Modified electrode was characterised by scanning electron microscopy (SEM), energy dispersive X-ray spectroscopy (EDAX), X-ray diffraction spectroscopy (XRD), electrochemical impedance spectroscopy (EIS) and cyclic voltammetry (CV). The ACF exhibits two oxidation peaks at +0.4 V, +0.66 V and one reduction peak at +0.3 V. The active surface area of the bare carbon paste electrode (BCPE) and modified electrode have been characterised by using K3[Fe(CN)6] solution containing 0.1 M KCl. In DPV mode, variation of ACF gave the limit of detection (LOD = 3s/m) 0.246 μM over the concentration range 1.0 to 190.0 μM (R2 = 0.9994). The developed electrode has good stability, reproducibility and could be successfully validated for the detection of ACF in pharmaceutical samples and biological fluids. 相似文献
148.
Min Lu Michael A. Phillips 《International journal of environmental analytical chemistry》2013,93(2):213-227
Antimony is an element of significant environmental concern, yet has been neglected relative to other heavy metals in electroanalysis. As such very little research has been reported on the electroanalytical determination of antimony at unmodified carbon electrodes. In this paper we report the electrochemical determination of Sb(III) in HCl solutions using unmodified carbon substrates, with focus on non-classical carbon materials namely edge plane pyrolytic graphite (EPPG), boron doped diamond (BDD) and screen-printed electrodes (SPE). Using differential pulse anodic stripping voltammetry, EPPG was found to give a considerably greater response towards antimony than other unmodified carbon electrodes, allowing highly linear ranges in nanomolar concentrations and a detection limit of 3.9?nM in 0.25?M HCl. Furthermore, the sensitivity of the response from EPPG was 100 times greater than for glassy carbon (GC). Unmodified GC gave a comparable response to previous results using the bare substrate, and BDD gave an improved, yet still very high limit of detection of 320?nM compared to previous analysis using an iridium oxide modified BDD electrode. SPEs gave a very poor response to antimony, even at high concentrations, observing no linearity from standard additions, as well as a major interference from the ink intrinsic to the working electrode carbon material. Owing to its superior performance relative to other carbon electrodes, the EPPG electrode was subjected to further analytical testing with antimony. The response of the electrode for a 40?nM concentration of Sb(III) was reproducible with a mean peak current of 1.07?µA and variation of 8.4% (n?=?8). The effect of metals copper, bismuth and arsenic were investigated at the electrode, as they are common interferences for stripping analysis of antimony. 相似文献
149.
根据GJB冲击环境试验测试要求,介绍LABVIEW平台下两类典型冲击信号分析模块的设计方法,主要讲述利用多图层叠加编程技术实现GJB150.18-1986标准规定的半正弦波与后峰锯齿波动态套容差曲线分析模块的设计以及利用递归算法实现冲击响应谱分析模块的设计。其次,采用资源DLL封装技术对LABVIEW编程实现的冲击信号分析模块进行封装,在其他编程语言中调用DLL实现冲击信号分析模块在其他编程语言中的功能链接。实践表明,LABVIEW图形化编程技术可快速实现两类冲击信号分析模块的设计,将高速数据采集模块与冲击信号分析模块集成,可有效完成冲击试验测试与信号分析处理任务。 相似文献
150.
Brian N. DiMarco Dmitry E. Polyansky David C. Grills Ping Wang Yutaka Kuwahara Xuan Zhao Etsuko Fujita 《Chemphyschem》2021,22(14):1478-1487
In this work, the differences in catalytic performance for a series of Co hydrogen evolution catalysts with different pentadentate polypyridyl ligands (L), have been rationalized by examining elementary steps of the catalytic cycle using a combination of electrochemical and transient pulse radiolysis (PR) studies in aqueous solution. Solvolysis of the [CoII−Cl]+ species results in the formation of [CoII(κ4-L)(OH2)]2+. Further reduction produces [CoI(κ4-L)(OH2)]+, which undergoes a rate-limiting structural rearrangement to [CoI(κ5-L)]+ before being protonated to form [CoIII−H]2+. The rate of [CoIII−H]2+ formation is similar for all complexes in the series. Using E1/2 values of various Co species and pKa values of [CoIII−H]2+ estimated from PR experiments, we found that while the protonation of [CoIII−H]2+ is unfavorable, [CoII−H]+ reacts with protons to produce H2. The catalytic activity for H2 evolution tracks the hydricity of the [CoII−H]+ intermediate. 相似文献