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   2003篇
  免费   112篇
  国内免费   355篇
化学   2243篇
晶体学   7篇
力学   46篇
综合类   13篇
数学   23篇
物理学   138篇
  2024年   3篇
  2023年   17篇
  2022年   65篇
  2021年   66篇
  2020年   64篇
  2019年   46篇
  2018年   58篇
  2017年   66篇
  2016年   68篇
  2015年   70篇
  2014年   92篇
  2013年   148篇
  2012年   140篇
  2011年   110篇
  2010年   117篇
  2009年   134篇
  2008年   134篇
  2007年   138篇
  2006年   137篇
  2005年   131篇
  2004年   139篇
  2003年   101篇
  2002年   66篇
  2001年   44篇
  2000年   57篇
  1999年   33篇
  1998年   43篇
  1997年   30篇
  1996年   32篇
  1995年   34篇
  1994年   17篇
  1993年   13篇
  1992年   17篇
  1991年   7篇
  1990年   8篇
  1989年   4篇
  1988年   6篇
  1987年   5篇
  1985年   1篇
  1983年   1篇
  1982年   2篇
  1981年   1篇
  1980年   2篇
  1976年   1篇
  1975年   1篇
  1970年   1篇
排序方式: 共有2470条查询结果,搜索用时 15 毫秒
91.
王树青  陈峻  林祥钦 《中国化学》2004,22(4):360-364
IntroductionAmperometricbiosensorofhydrogenperoxideisofpracticalimportancebecauseofitswideapplicationsinchemical,biological,clinical,environmentalandmanyotherfields.Forimprovementofsensor抯quality,vari-ouskindsofchemicalmodificationmethodshavebeendevelopedforreducingredoxoverpotentialsofH2O2atelectrodesurfaces,increasingthedetectionsensitivity,linearrange,stabilityandlivetime.Ithasbeenshownthattheuseofsub-micrometersizedmetalparticlessuchasPt-blackcansignificantlyimprovethequalityofthebiosens…  相似文献   
92.
The inhibition of lingninase by hydrogen peroxide in the presence of cationic surfactant CTAB was studied by kinetic speetrophotometdc technique. Results showed that addition of CTAB enhanced the inhibition by H202, but it did not alter the inhibition pattern and the inhibition constant changed little with theco-ncentration of CTAB. Modification of the enzymic protein by the surfactant monomer may be responsible for the above mentioned results.  相似文献   
93.
The epoxidation of alkenylphosphorus compounds with hydrogen peroxide was systematically studied, revealing that while alkenylphosphine oxides failed to produce the corresponding epoxides, alkenylphosphonates, or phosphinates having a phenyl group at α-position reacted with H2O2/K2CO3 or alkenylphosphonic acids or phosphinic acids having an aliphatic group at α- or β-positions reacted with H2O2/Na2WO4/Et3N to produce high yields of the corresponding epoxides.  相似文献   
94.
The First Polyiodo Complex – Triethylsulfoniumtriiodomercurate(II)-tris(diiodine), (Et3S)[Hg2I6]1/2 · 3 I2 After Raman spectroscopic investigation of the system HgI2/Et3SIx, x = 3, 5, 7, triethylsulfoniumtriiodomercuratetris(diiodine), (Et3S)[Hg2I6]1/2 · 3 I2 was synthesized by reacting of HgI2 and liquid Et3SI7. The compound crystallizes at room temperature triclinically in the space group P1 with a = 879.4(7), b = 1 209.1(5), c = 1 291.5(5) pm, α = 96.16(3)°, β = 103.82(6)°, γ = 99.05(5)° and Z = 2. The crystal structure is composed of disordered Et3S+ cations, the centrosymmetric complex anion [HgI2/2I2]22? and three connecting iodine molecules I2.  相似文献   
95.
A new H2O2 enzymeless sensor has been fabricated by incorporation of thionin onto multiwall carbon nanotubes (MWCNTs) modified glassy carbon electrode. First 50 μL of acetone solution containing dispersed MWCNTs was pipetted onto the surface of GC electrode, then, after solvent evaporations, the MWCNTs modified GC electrode was immersed into an aqueous solution of thionin (electroless deposition) for a short period of time <5–50 s. The adsorbed thin film of thionin was found to facilitate the reduction of hydrogen peroxide in the absence of peroxidase enzyme. Also the modified electrode shows excellent catalytic activity for oxygen reduction at reduced overpotential. The rotating modified electrode shows excellent analytical performance for amperometric determination of hydrogen peroxide, at reduced overpotentials. Typical calibration at ?0.3 V vs. reference electrode, Ag/AgCl/3 M KCl, shows a detection limit of 0.38 μM, a sensitivity of 11.5 nA/μM and a liner range from 20 μM to 3.0 mM of hydrogen peroxide. The glucose biosensor was fabricated by covering a thin film of sol–gel composite containing glucose oxides on the surface of thionin/MWCNTs modified GC electrode. The biosensor can be used successfully for selective detection of glucose based on the decreasing of cathodic peak current of oxygen. The detection limit, sensitivity and liner calibration rang were 1 μM, 18.3 μA/mM and 10 μM–6.0 mM, respectively. In addition biosensor can reach 90% of steady currents in about 3.0 s and interference effect of the electroactive existing species (ascorbic acid–uric acid and acetaminophen) is eliminated. The usefulness of biosensor for direct glucose quantification in human blood serum matrix is also discussed. This sensor can be used as an amperometric detector for monitoring oxidase based biosensors.  相似文献   
96.
A novel flow-injection amperometric method was proposed for the sensitive and enzymeless determination of hydrogen peroxide based on its electrocatalytic reduction at a palladium nanoparticle-modified pretreated pencil graphite electrode in a laboratory-constructed electrochemical flow cell. Cyclic voltammograms of the unmodified and modified electrodes were recorded in pH 7.0 phosphate buffer containing 0.10 M KCl at a scan rate of 50?mV s?1 for the investigation of electrocatalytic reduction of hydrogen peroxide at the palladium nanoparticle-modified pretreated pencil graphite electrode. Cyclic voltammograms of the pretreated pencil graphite electrode revealed an irreversible oxidation peak and a weak reduction peak of hydrogen peroxide at +1100?mV and –450?mV vs. an Ag/AgCl/KCl saturated reference electrode. However, the reduction of hydrogen peroxide was observed at –100?mV with an increase in current in the cyclic voltammograms of the palladium nanoparticle-modified pretreated pencil graphite electrode compared to the unmodified electrode. These results indicate that the palladium nanoparticle-modified pretreated pencil graphite electrode exhibits efficient electrocatalytic activity for the reduction of hydrogen peroxide. A linear concentration range was obtained between .01 and 10.0?mM hydrogen peroxide with a detection limit of 3.0 µM from flow injection amperometric current–time curves recorded in pH 7.0 phosphate buffer at –100?mV and a 2.0?mL min?1 flow rate. The novelty of this work relies on its use of a laboratory-constructed flow cell constructed for the pencil graphite electrode using these inexpensive, disposable, and electrochemically reactive modified electrodes for the amperometric determination of hydrogen peroxide in a flow injection analysis system.  相似文献   
97.
Campuzano S  Pedrero M  Pingarrón JM 《Talanta》2005,66(5):1310-1319
The construction and performance under flow-injection conditions of an integrated amperometric biosensor for hydrogen peroxide is reported. The design of the bioelectrode is based on a mercaptopropionic acid (MPA) self-assembled monolayer (SAM) modified gold disk electrode on which horseradish peroxidase (HRP, 24.3 U) was immobilized by cross-linking with glutaraldehyde together with the mediator tetrathiafulvalene (TTF, 1 μmol), which was entrapped in the three-dimensional aggregate formed.

The amperometric biosensor allows the obtention of reproducible flow injection amperometric responses at an applied potential of 0.00 V in 0.05 mol L−1 phosphate buffer, pH 7.0 (flow rate: 1.40 mL min−1, injection volume: 150 μL), with a range of linearity for hydrogen peroxide within the 2.0 × 10−7–1.0 × 10−4 mol L−1 concentration range (slope: (2.33 ± 0.02) × 10−2 A mol−1 L, r = 0.999). A detection limit of 6.9 × 10−8 mol L−1 was obtained together with a R.S.D. (n = 50) of 2.7% for a hydrogen peroxide concentration level of 5.0 × 10−5 mol L−1. The immobilization method showed a good reproducibility with a R.S.D. of 5.3% for five different electrodes. Moreover, the useful lifetime of one single biosensor was estimated in 13 days.

The SAM-based biosensor was applied for the determination of hydrogen peroxide in rainwater and in a hair dye. The results obtained were validated by comparison with those obtained with a spectrophotometric reference method. In addition, the recovery of hydrogen peroxide in sterilised milk was tested.  相似文献   

98.
99.
High‐level incorporation of Ag in Au nanoclusters (NCs) is conveniently achieved by controlling the concentration of Ag+ in the synthesis of bovine serum albumin (BSA)‐protected Au NCs, and the resulting structure is determined to be bimetallic Ag28Au10‐BSA NCs through a series of characterizations including energy‐dispersive X‐ray spectroscopy, mass spectroscopy, and X‐ray photoelectron spectroscopy, together with density functional theory simulations. Interestingly, the Ag28Au10 NCs exhibit a significant fluorescence redshift rather than quenching upon interaction with hydrogen peroxide, providing a new approach to the detection of hydrogen peroxide through direct comparison of their fluorescence peaks. Furthermore, the Ag28Au10 NCs are also used for the sensitive and selective detection of herbicide through fluorescence enhancement. The detection limit for herbicide (0.1 nm ) is far below the health value established by the U.S. Environmental Protection Agency; such sensitive detection was not achieved by using AuAg NCs with low‐level incorporation of Ag or by using the individual metal NCs.  相似文献   
100.
Benzoyl peroxide has been used as a mild and efficient reagent for the preparation of benzoyl ester of oxime in moderate to good yields.  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