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   1610篇
  免费   167篇
  国内免费   75篇
化学   1700篇
晶体学   5篇
力学   5篇
综合类   1篇
数学   1篇
物理学   140篇
  2024年   4篇
  2023年   25篇
  2022年   26篇
  2021年   43篇
  2020年   39篇
  2019年   50篇
  2018年   33篇
  2017年   51篇
  2016年   58篇
  2015年   61篇
  2014年   65篇
  2013年   97篇
  2012年   129篇
  2011年   61篇
  2010年   74篇
  2009年   99篇
  2008年   86篇
  2007年   116篇
  2006年   105篇
  2005年   100篇
  2004年   100篇
  2003年   56篇
  2002年   46篇
  2001年   40篇
  2000年   31篇
  1999年   23篇
  1998年   37篇
  1997年   24篇
  1996年   17篇
  1995年   27篇
  1994年   18篇
  1993年   10篇
  1992年   11篇
  1991年   39篇
  1990年   26篇
  1989年   3篇
  1988年   7篇
  1987年   3篇
  1986年   1篇
  1985年   3篇
  1984年   1篇
  1983年   2篇
  1981年   2篇
  1979年   1篇
  1976年   1篇
  1970年   1篇
排序方式: 共有1852条查询结果,搜索用时 15 毫秒
191.
M.A. Alonso-Lomillo 《Talanta》2010,82(5):1629-1636
Disposable screen-printed biosensors have been successfully employed in the development of analytical methods that respond to the growing need to perform rapid “in situ” analyses. Thus, the early detection of microorganisms, which plays an important role in the prevention of human health problems, animals and plants epidemics, has been carried out using this kind of devices. Moreover, microorganisms have been used as biological sensing elements in the development of sensitive microbial biosensors for the analysis of different analytes of interest. This review presents the electrochemical application of disposable screen-printed biosensors in the microbiology field.  相似文献   
192.
We report the comparison of electron transfer kinetic parameters of the ferrocene redox couple in both acetonitrile and in room temperature ionic liquid (RTIL) 1‐butyl‐3‐methylimidiazonium hexafluorophosphate ([C4mim] [PF6]), using edge plane pyrolytic graphite (EPPG), basal plane pyrolytic graphite (BPPG) and glassy carbon (GC) electrodes. Each electrode surface was characterized using SEM and AFM and the surface morphology was analyzed in terms of surface heterogeneity including the distribution of edge plane defects. The experimental data were modeled using both one and two dimensional simulations to correlate the electron transfer parameters obtained with the different surface structure of each electrode. Furthermore, we show that the diffusion domain approximation (commonly used to accurately simulate electron transfer kinetics at graphitic surfaces) breaks down when a BPPG electrode is used in RTIL and demonstrate the near impossibility of assigning rate constant to the basal plane surface.  相似文献   
193.
Gold ensembles for the trace level sensing of arsenic(III) in the presence of copper(II) are reported. The gold ensembles are fabricated using citrate capped gold nanoparticles which are chemically synthesised in an aqueous solution with an aliquot of this simply cast onto an economical and disposable screen printed electrode. After drying at room temperature, the gold ensembles are ready for use. The gold ensembles are explored towards the sensing of arsenic(III) in the presence of copper(II) using anodic stripping voltammetry where the corresponding stripping peaks are well resolved and using this protocol it is possible to readily detect 3 µg L?1 (3 ppb) with a detection limit of 0.4 µg L?1 (0.4 ppb). Proof‐of‐concept is also shown for the sensing of arsenic(III) in a canal water sample. Given the low cost of the sensor and ease of fabrication, the gold ensembles hold promise for the sensing of arsenic(III) in water samples where copper(II) may be present.  相似文献   
194.
A new composite electrode based on multiwall carbon nanotubes (MWCNT) and silicone‐rubber (SR) was developed and applied to the determination of propranolol in pharmaceutical formulations. The effect of using MWCNT/graphite mixtures in different proportions was also investigated. Cyclic voltammetry and electrochemical impedance spectroscopy were used for electrochemical characterization of different electrode compositions. Propranolol was determined using MWCNT/SR 70 % (m/m) electrodes with linear dynamic ranges up to 7.0 µmol L?1 by differential pulse and up to 5.4 µmol L?1 by square wave voltammetry, with LODs of 0.12 and 0.078 µmol L?1, respectively. Analysis of commercial samples agreed with that obtained by the official spectrophotometric method. The electrode is mechanically robust and presented reproducible results and a long useful life.  相似文献   
195.
This study examines the influence of textile substrates upon the behavior of wearable screen‐printed electrodes and demonstrates the attractive sensing properties of these sensors towards the detection of nitroaromatic explosives. Compared to electrodes printed on common cotton or polyester substrates, GORE‐TEX‐based electrochemical sensors display reproducible background cyclic voltammograms, reflecting the excellent water‐repellant properties of the GORE‐TEX fabric. The wetting properties of different printed textile electrodes are elucidated using contact angle measurements. The influence of laundry washing and mechanical stress is explored. The GORE‐TEX‐based printed electrodes exhibit favorable detection of 2,4‐dinitrotoluene (DNT) and 2,4,6‐trinitrotoluene (TNT) explosives, including rapid detection of DNT vapor.  相似文献   
196.
The cellulose acetate covered Prussian blue modified glassy carbon electrode (GCE/PB/CA) was fabricated as a novel hydrogen peroxide sensor. It was shown by scanning electron microscope (SEM) and atomic force microscope (AFM) that Prussian blue was covered and protected by cellulose acetate perfectly. The modified electrode showed a good electrocatalytic activity for H2O2 reduction in neutral aqueous solution. H2O2 was detected amperometrically in 0.05 mol/L phosphate buffer solutions (pH 7.0, containing 0.1 mol/L KCl as supporting electrolyte) at an applied potential of ?0.2 V (vs. SCE). The response current was proportional to the concentration of H2O2 in the range of 1.0×10?5 mol/L to 2.5×10?4 mol/L with the detection limit of 2.2×10?6 mol/L at a signal to noise ratio 3.  相似文献   
197.
A detailed study of the electrochemical oxidation of Benzo[a]pyrene (BaP) at the glassy carbon and pencil graphite electrodes was carried out in aqueous and nonaqueous media. Using square‐wave stripping mode, the compound yielded a well‐defined voltammetric response at pencil graphite electrode in acetate buffer, pH 4.8 at +1.13 V (vs. Ag/AgCl) (a preconcentration step being carried out at a fixed potential of +0.70 V for 180 s). The process could be used to determine BaP concentrations in the range 0.25–1.25 μM, with a detection limit of 0.027 μM (6.82 μg L?1). The applicability to assay of spiked human urine samples was also illustrated.  相似文献   
198.
This work describes the electrochemical properties of glassy carbon electrodes (GCE) modified with chromium(III) hexacyanoferrate(II) (Crhf) nanoparticles attached multiwalled carbon nanotube (MWNTs). The morphological characterization of Crhf/MWNTs nanocomposites was examined by scanning electron microscopy (SEM), UV‐vis spectroscopy, and Fourier transform infrared spectrometry (FT‐IR). The electrocatalytic activity of these nanocomposites was investigated and showed a good electrocatalytic effect for oxidation of L ‐cysteine (L ‐Cys) in 0.1 M phosphate buffer solution (pH 3.0). Under optimum conditions linear calibration graphs were obtained over the L ‐Cys concentration range 5.0×10?7 to 6.0×10?5 M with a correlation coefficient of 0.9998 and a detection limit (signal‐to‐noise ratio was 3) of 1.0×10?8 M. The proposed method is simple and it also showed excellent sensitivity and stability. The excellent electrocatalytic ability of the modified electrode towards L ‐Cys manifests that the Crhf/MWNTs can provide a new platform for biosensors and other biology.  相似文献   
199.
A screen‐printed silver strip with a built‐in three‐in‐one electrode (SPAgE) configuration of Ag‐working, Ag‐counter and Ag/AgxO (silver oxides) pseudoreference electrodes has been developed for sensitive and selective electrochemical flow injection analysis (FIA) of aluminum chlorohydrate (ACH) present in antiperspirants, through the free Cl? ion liberated from ACH in aqueous medium, as a redox signal at Ag‐working electrode in pH 6 phosphate buffer solution (PBS). The solution phase and instrumental parameters were systematically optimized. The calibration graph was linear in the window 1–200 ppm concentration of ACH and the lowest detection limit (S/N=3) was 295 ppb with a slope of 0.0989 μA/ppm and regression coefficient of 0.998. Calculated relative standard deviation (RSD) values for the detection of 5 and 50 ppm ACH by this method are 2.21 % and 2.16 %, respectively. Four different antiperspirant deodorants real samples with and without ACH content were successfully analyzed and the detected values obtained were found to be in good agreement with the product labeled values.  相似文献   
200.
A comparative study of two Sn-based composite materials as negative electrode for Li-ion accumulators is presented. The former SnB0.6P0.4O2.9 obtained by in-situ dispersion of SnO in an oxide matrix is shown to be an amorphous tin composite oxide (ATCO). The latter Sn0.72[BPO4]0.28 obtained by ex-situ dispersion of Sn in a borophosphate matrix consists of Sn particles embedded in a crystalline BPO4 matrix. The electrochemical responses of ATCO and Sn0.72[BPO4]0.28 composite in galvanostatic mode show reversible capacities of about 450 and 530 mAh g−1, respectively, with different irreversible capacities (60% and 29%). Analysis of these composite materials by 119Sn Mössbauer spectroscopy in transmission (TMS) and emission (CEMS) modes confirms that ATCO is an amorphous SnII composite oxide and shows that in the case of Sn0.72[BPO4]0.28, the surface of the tin clusters is mainly formed by SnII in an amorphous interface whereas the bulk of the clusters is mainly formed by Sn0. The determination of the recoilless free fractions f (Lamb-Mössbauer factors) leads to the effective fraction of both Sn0 and SnII species in such composites. The influence of chemical composition and especially of the surface-to-bulk tin species ratio on the electrochemical behaviour has been analysed for several Snx[BPO4]1−x composite materials (0.17<x<0.91). The cell using the compound Sn0.72[BPO4]0.28 as active material exhibits interesting electrochemical performances (reversible capacity of 500 mAh g−1 at C/5 rate).  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