全文获取类型
收费全文 | 7261篇 |
免费 | 1313篇 |
国内免费 | 1400篇 |
专业分类
化学 | 7838篇 |
晶体学 | 129篇 |
力学 | 93篇 |
综合类 | 73篇 |
数学 | 76篇 |
物理学 | 1765篇 |
出版年
2024年 | 35篇 |
2023年 | 179篇 |
2022年 | 528篇 |
2021年 | 541篇 |
2020年 | 530篇 |
2019年 | 411篇 |
2018年 | 349篇 |
2017年 | 428篇 |
2016年 | 545篇 |
2015年 | 466篇 |
2014年 | 542篇 |
2013年 | 683篇 |
2012年 | 658篇 |
2011年 | 521篇 |
2010年 | 406篇 |
2009年 | 499篇 |
2008年 | 383篇 |
2007年 | 389篇 |
2006年 | 321篇 |
2005年 | 285篇 |
2004年 | 222篇 |
2003年 | 170篇 |
2002年 | 169篇 |
2001年 | 85篇 |
2000年 | 88篇 |
1999年 | 76篇 |
1998年 | 63篇 |
1997年 | 68篇 |
1996年 | 41篇 |
1995年 | 47篇 |
1994年 | 43篇 |
1993年 | 41篇 |
1992年 | 29篇 |
1991年 | 19篇 |
1990年 | 19篇 |
1989年 | 12篇 |
1988年 | 13篇 |
1987年 | 12篇 |
1986年 | 14篇 |
1985年 | 6篇 |
1984年 | 9篇 |
1983年 | 4篇 |
1982年 | 18篇 |
1981年 | 2篇 |
1980年 | 1篇 |
1979年 | 2篇 |
1978年 | 1篇 |
1977年 | 1篇 |
排序方式: 共有9974条查询结果,搜索用时 15 毫秒
61.
Summary For the title compounds 4,4-DADPM, MOCA, 3,3-DCB, 4-ADP and 4-ADPA listing on the EPA priority pollutant list, an analytical practicable, reliable, reproducible and sensitive procedure is required. Therefore a new method has been developed for the routine determination of these toxic aromatic amines in urine at the ppb level. The quantitative determination of amines is a suitable procedure of occupationally exposed persons. Urine sample preparation is done using simple liquid-liquid extraction followed by a precolumn enrichment (PRP1-material; Hamilton). Breakthrough measurements were done using an enrichment column packed with PRP1 material. The capacities of the studied amines ranged from 21.9mg/g to 96.6mg/g, while influent concentrations differed from 28.3mg/l to 332.0mg/l. The advantages of electrochemical detection regarding to selectivity and sensitivity are clearly indicated in this paper. Separation has been achieved applying reversed-phase-high-performance-liquid chromatography (LiChrosorb RP 18/5m) followed by electrochemical or UV-detection. The detection limits employing an electrochemical detector at a potential of 1 V range from 2.2ng to 12.1ng. UV detection at 254 nm and 280 nm is about 10–100 times less sensitive. Recoveries from spiked water samples at the 5ppb levels were 75% to 96% respectively. The standard deviation of the developed procedure varies from 5.3% to 14%. Day-to-day repeatability is good. 相似文献
62.
A. V. Kazakova N. D. Kushch L. I. Buravov E. B. Yagubskii S. V. Simonov L. V. Zorina S. S. Khasanov R. P. Shibaeva E. Canadell J. Yamada M. Umemiya 《Russian Chemical Bulletin》2007,56(1):49-55
New radical cation salts based on 2,5-bis(1,3-dithian-2-ylidene)-1,3,4,6-tetrathiapentalene (BDA-TTP) with copper(II) metal complex anions, β-(BDA-TTP)4Cu2Cl6 and (BDA-TTP)2CuCl4, were synthesized and structurally characterized. Single crystals were prepared by electrochemical oxidation of BDA-TTP under
galvanostatic conditions. X-ray diffraction study demonstrated that the salts have a layered structure, in which the conducting
BDA-TTP layers alternate with the [Cu2Cl6]2− or [CuCl4]2− anions. Both salts show the semiconductor-type temperature dependence of the conductivity.
Published in Russian in Izvestiya Akademii Nauk. Seriya Khimicheskaya, No. 1, pp. 48–54, January, 2007. 相似文献
63.
A direct, versatile method for the determination of ethyl glucuronide (EtG), a biomarker of ethanol consumption, in urine has been developed using reversed-phase liquid chromatography with pulsed electrochemical detection (PED). EtG and methyl glucuronide (MetG), which serves as an internal standard, are readily separated using a mobile phase consisting of 1% acetic acid/acetonitrile (98/2, v/v). Post-column addition of NaOH allows for the detection of all glucuronides using PED at a gold working electrode. Upon optimization, EtG was found to have a limit of detection of 0.03 μg/mL (7 pmol; 50 μL injection volume) and repeatability at the limit of quantitation of 1.7%R.S.D. (relative standard deviation). Solid-phase extraction (SPE) using an aminopropyl phase was used to remove interferents in urine samples prior to their analysis. Compound recovery following SPE was approximately 50 ± 2%. The forensic utility of this method was further validated by the analysis of 29 post-mortem urine specimens, whose results agreed strongly with certified determinations. 相似文献
64.
纳米TiO2膜用于光催化氧化测定化学需氧量的研究 总被引:4,自引:0,他引:4
A photocatalytic oxidation method for determination of chemical oxygen demand (COD) using nano-TiO2 film, based on the use of a nano-TiO2-Ce(SO4)2 system and electrochemical detection, was proposed. The technique was originated from the direct determination of the Ce(Ⅲ) concentration change resulting from photocatalytic oxidation of organic compounds. Ce(Ⅲ), which was produced by photocatalytic reduction of Ce(SO4)2, could be measured at a multi-walled carbon nanotubes (MWNT) chemically modified electrode (CME). The COD values by this method were calculated from the differential pulse voltammetry (DPV) current of Ce(Ⅲ) at the CME. Under the optimal operation conditions, the detection limit of 0.5 mg·L^-1 COD with the linear range of 1-600 mg·L^-1 was achieved. This method was also applied to determination of various COD of ground water and wastewater samples. The resuits were in good agreement with those from the conventional COD methods, i.e., permanganate and dichromate ones. 相似文献
65.
Halina Y. Neujahr 《Applied biochemistry and biotechnology》1982,7(1-2):107-111
The enzyme phenol 2-hydroxylase was immobilized on Sepharose and used in conjunction with an O2 electrode for quantitating phenol. Similarly, catechol 1,2-oxygenase was used for quantitating catechol. A third probe was
prepared by immobilization ofTrichosporon cutaneum cells rather than purified phenol 2-hydroxylase for phenol quantitation. The whole cell system gave results comparable to
the immobilized enzyme system. 相似文献
66.
Nusbaumer H Zakeeruddin SM Moser JE Grätzel M 《Chemistry (Weinheim an der Bergstrasse, Germany)》2003,9(16):3756-3763
A series of new cobalt complexes [Co(LLL)(2)X(2)] were synthesized and evaluated as redox mediators for dye-sensitized nanocrystalline TiO(2) solar cells. The structure of the ligand and the nature of the counterions were found to influence the photovoltaic performance. The one-electron-transfer redox mediator [Co(dbbip)(2)](ClO(4))(2) (dbbip = 2,6-bis(1'-butylbenzimidazol-2'-yl)pyridine) performed best among the compounds investigated. Photovoltaic cells incorporating this redox mediator yielded incident photon-to-current conversion efficiencies (IPCE) of up to 80%. The overall yield of light-to-electric power conversion reached 8 % under simulated AM1.5 sunlight at 100 W m(-2) intensity and more than 4% at 1000 W m(-2). Photoelectrodes coated with a 2 microm thick nanoporous layer and a 4 microm thick light-scattering layer, sensitized with a hydrophobic ruthenium dye, gave the best results. 相似文献
67.
米非司酮的吸附伏安特性 总被引:1,自引:0,他引:1
在PH7.0Britton-Robinson缓冲溶液中,米非司酮(Mifepristone,RU486)在汞电极上有2个不可逆的线性扫描还原峰,峰电位分别为-1.23V和-1.68V。本文探讨了第一峰的电化学行为。 相似文献
68.
A series of 2-benzyl-1,3-dicabonyl derivatives was synthesized.Their insulin-sensitizing activity was evaluated in 3T3-L1 preadipocyte cells.Compounds3,26 and 27 were found to possess strong insulin-sensitizing activity in vitro and were selected for further hypoglycemic evaluation in vivo. 相似文献
69.
A kind of inorganic‐organic hybrid 18‐molybdodiphosphate nanoparticles ([(C4H9)4N]6P2Mo18Q62·4H2O) was firstly used as a bulk‐modifier to fabricate a three‐dimensional chemically modified carbon paste electrode (CPE) by direct mixing. The electrochemical behavior of the solid nanoparticles dispersed in the CPE in acidic aqueous solution was characterized by cyclic and square‐wave voltammetry. The hybrid 18‐molybdodiphosphate nanoparticles bulk‐modified CPE (MNP‐CPE) displayed a high electrocatalytic activity towards the reduction of nitrite, bromate and hydrogen peroxide. The remarkable advantages of the MNP‐CPE over the traditional polyoxometalates‐modified electrodes are their excellent reproducibility of surface‐renewal and high stability owing to the insolubility of the hybrid 18‐molybdodiphosphate nanoparticles. 相似文献
70.
《Electroanalysis》2005,17(11):953-958
An electron transfer reaction between ascorbic acid (H2A) in an aqueous solution and oxidizing agent in an organic solution immiscible with water has been studied by thin‐layer cyclic voltammetry (TLCV) for charge transfer at the interface between two immiscible electrolyte solutions (ITIES). As an antioxidant, H2A provide electrons through the aqueous/organic interface to reduce Fc+ and the procedure has been proved to be a one electron process again. In this work, the first combination of TLCV and scanning electrochemical microscopy (SECM) was achieved and showed a reasonable agreement between the results from the two different approaches. Otherwise, lower concentration ratios Kr of aqueous to organic reactants was adopted, which is given as evidence to the proposed procedure of Barker. 相似文献