全文获取类型
收费全文 | 30784篇 |
免费 | 333篇 |
国内免费 | 516篇 |
专业分类
化学 | 11925篇 |
晶体学 | 286篇 |
力学 | 1462篇 |
综合类 | 51篇 |
数学 | 9243篇 |
物理学 | 8666篇 |
出版年
2022年 | 61篇 |
2021年 | 88篇 |
2020年 | 86篇 |
2019年 | 101篇 |
2018年 | 1244篇 |
2017年 | 1502篇 |
2016年 | 794篇 |
2015年 | 626篇 |
2014年 | 567篇 |
2013年 | 791篇 |
2012年 | 3235篇 |
2011年 | 2411篇 |
2010年 | 1874篇 |
2009年 | 1635篇 |
2008年 | 657篇 |
2007年 | 690篇 |
2006年 | 670篇 |
2005年 | 4510篇 |
2004年 | 4010篇 |
2003年 | 2397篇 |
2002年 | 622篇 |
2001年 | 417篇 |
2000年 | 175篇 |
1999年 | 238篇 |
1998年 | 131篇 |
1997年 | 88篇 |
1996年 | 64篇 |
1995年 | 64篇 |
1994年 | 65篇 |
1993年 | 37篇 |
1992年 | 192篇 |
1991年 | 165篇 |
1990年 | 151篇 |
1989年 | 113篇 |
1988年 | 112篇 |
1987年 | 65篇 |
1986年 | 47篇 |
1985年 | 56篇 |
1984年 | 35篇 |
1983年 | 36篇 |
1979年 | 36篇 |
1976年 | 88篇 |
1975年 | 42篇 |
1974年 | 48篇 |
1973年 | 51篇 |
1972年 | 43篇 |
1970年 | 36篇 |
1969年 | 38篇 |
1968年 | 39篇 |
1966年 | 39篇 |
排序方式: 共有10000条查询结果,搜索用时 15 毫秒
81.
This work describes a study of the underpotential deposition (UPD) of Sn2+ on a polycrystalline gold disc electrode using cyclic voltammetry (CV) and chronocoulometry (CC). Sn2+ ions showed well-defined peaks from UPD and UPD stripping (UPD-S) in 1 mol/L HCl solutions, while bulk deposition (BD) and BD stripping (BD-S) of the ions were also observed. The measured UPD shifts, EUPD, between the UPD-S and the BD-S peaks were more than 200 mV. The UPD charge and the surface coverage of tin were measured by CC. A new method for determining Sn2+ was therefore developed, based on the excellent electrochemical properties of the Au/Sn UPD system. A plot of the UPD-DPASV (differential pulse anodic stripping voltammetry) signal versus the Sn(II) concentration was obtained for [Sn(II)] of 1.98×10–7 to 3.64×10–5 M. The method developed here has been applied to determine the tin in a tin plate sample. 相似文献
82.
Ballou S Goodpaster J MacCrehan W Reeder D 《Analytical and bioanalytical chemistry》2003,376(8):1149-1150
83.
Fa Jie Yang Da Ling Yang Shou Hai Zhang Xi Gao Jian 《中国化学快报》2007,18(8):966-968
A new interfacial polymerization (IP) procedure is developed in order to synthesize polypiperazine-amide thin-film membrane on the inner surface of poly(phthalazinone ether sulfone ketone) (PPESK) hollow fiber ultrafiltration (UF) membrane.A hollow fiber composite membrane with good performance was prepared and studied by FT-IR and scanning electron microscopy. 相似文献
84.
Mycotoxins are secondary metabolites, formed by the action of fungi on agricultural crops in the field or during storage. These metabolites are highly toxic to animals and humans and high levels have been measured in agricultural crops. In order to evaluate human risks due to ingestion of mycotoxin-contaminated food different methods have been developed for analysis of mycotoxins in cereals and maize. In this project the focus was on mycotoxins in agricultural soil and the fate of these toxins in the soil-water-plant system. Two different mycotoxins were selected in the study: zearalenone (ZON) produced by species of Fusariumor Aspergillusand ochratoxin A (OTA) produced by species of Penicillium. We developed a method for analysis of these toxins in soil. Soil samples were extracted with methanol-water (9:1) and purified by solid-phase extraction (SPE, C8-columns). The final extract was analysed using high-pressure liquid chromatography (HPLC) with fluorescence detection. A Phenyl Hexyl column was used to separate the toxins. The detection limits obtained were 0.1 and 1.0 microg kg(-1) dry weight (dw) for OTA and ZON, respectively. The developed method has been used for analysis of different soils in connection with growth chamber experiments. The soil types used in the growth chamber experiments were a sandy soil, a sandy clay soil, and a soil with high content of organic matter. The recovery was determined as 85.8 and 93.4% and the repeatability to 5.1 and 12.8% for OTA and ZON, respectively. The reproducibility obtained was 8.5 and 15.0% for soil samples, representing concentration levels from 0.2-30 microg kg(-1) dw (OTA) and from 1.0-100 microg kg(-1) dw (ZON). 相似文献
85.
S Çak?r E Co?kunP Naumov E Biçer? Bulut H ?çbudakO Çak?r 《Journal of Molecular Structure》2002,608(1):101-107
Aspartame adduct of copper(II) chloride Cu(Asp)2Cl2·2H2O (Asp=aspartame) is synthesized and characterized by elemental analysis, FT IR, UV/vis, ESR spectroscopies, TG, DTG, DTA measurements and molecular mechanics calculations. Aqueous solution of the green solid absorbs strongly at 774 and 367 nm. According to the FT IR spectra, the aspartame moiety coordinates to the copper(II) ion via its carboxylate ends, whereas the ammonium terminal groups give rise to hydrogen bonding network with the water, the chloride ions or neighboring carboxylate groups. The results suggest tetragonally distorted octahedral environment of the copper ions. 相似文献
86.
The molecular complex formation reactions of uridine (Urd) with adenosine (Ado), cytidine (Cyd), thymidine (Thd), adenosine 5-monophosphate (AMP) and cytidine 5-monophosphate (CMP) have been studied at 20°C. It was found that the main positive noncovalent centers of ion–dipole and dipole–dipole type interactions are the protonated N(3) atoms of Urd, whereas the negative centers are the endocyclic atoms of the bases characterized by high electron density from the second molecule involved in the reaction. Moreover, NMR results indicate the occurrence of stacking in the complex (Urd)H(Cyd), whereas in the complex, (Urd)H2(Thd), it is the only type of interaction. Deprotonation of the latter species brings about a change in the character of the reaction and ion–dipole interactions have been detected in the adduct, (Urd)H(Thd). Interestingly, no involvement of the phosphate groups in the formation of AMP and CMP adducts has been evidenced and the main centers of the reactions were found to be the N(7)and N(1) atoms of AMP, or the N(3) atoms of CMP and Urd. Moreover, in the Urd/CMP system the NMR results suggest stacking-type interactions. 相似文献
87.
Nicole Fietkau Fran?ois G Chevallier Li Jiang Timothy G J Jones Richard G Compton 《Chemphyschem》2006,7(10):2162-2167
The size of a glass sphere positioned in the center of a microdisk electrode is determined by using a simple electrochemical procedure and is confirmed, additionally, by a microscopical measurement of the sphere at the time of the electrochemical measurement. The cyclic voltammetric response of the naked electrode and of the electrode with the sphere positioned in its center is recorded over a wide range of scan rates (0.002-1.5 V s(-1)). The size of the sphere is then determined by comparison of the experimental voltammogram with simulations for each individual scan rate. 相似文献
88.
Selenomethionine contents of NIST wheat reference materials 总被引:1,自引:0,他引:1
Values of the total selenium and selenomethionine (Semet) content of four wheat-based reference materials have been obtained by gas chromatography-stable isotope dilution mass spectrometry methods. The total Se method is an established one, and the results obtained with it are consistent with previously-assigned values. The Semet method (previously reported by our laboratory) is based on reaction with CNBr. Our data indicate that the four wheat samples (wheat gluten, durum wheat, hard red spring wheat, and soft winter wheat), though having a 30-fold range in total Se content, all have about 45% of their total Se values in the form of selenomethionine. Investigation of the CNBr-based method suggests that additional experiments are needed to verify that all selenomethionine in the wheat samples is accounted for, but also indicates that the values obtained are within 15% of the true values. As the form in which Se occurs in foods and dietary supplements is important from a nutritional perspective, adding information about Se speciation to total Se values in appropriate reference materials makes these materials more valuable in relevant analytical work. 相似文献
89.
Michael Schaefer Christian N?ther Wolfgang Bensch 《Monatshefte für Chemie / Chemical Monthly》2004,27(7):461-470
Yellow crystals of the title compound were obtained under solvothermal conditions reacting elemental Zn, Sb, and S in a solution of tris(2-aminoethyl)amine (=tren) and water. The compound crystallises in the monoclinic space group P21/c with a=13.0247(7), b=22.308(2), c=12.1776(6) Å, and =105.352(6)°. In the structure of [Zn(tren)]2Sb4S8·0.75 H2O two [Zn(tren)]2+ cations are bound to the [Sb4S8]4– anion via S atoms. The Zn2+ ions are in a trigonal bipyramidal environment of four N atoms of the tetradentate tren ligand and one S atom of the [Sb4S8]4– anion. The anion is formed by SbS3 and SbS4 units which share common corners and edges. The interconnection mode yields three different non-planar Sb2S2 heterorings. The shortest intermolecular Sb–S distance amounts to about 3.7Å, and taking this long separation into account undulated chains running along [001] are formed with the water molecules residing in the pocket-like cavities. Upon heating the compound decomposes in one step starting at about 240°C. The final decomposition product was identified as ZnS and Sb2S3 by X-ray powder diffractometry. Additionally, spectroscopic data as well as synthetic procedures for [Zn(tren)]2Sb4S8·0.75 H2O are reported. 相似文献
90.
Shuang‐Jun Lin Chang‐Heng Tan Shan‐Hao Jiang Yi‐Ming Li Da‐Yuan Zhu 《Helvetica chimica acta》2006,89(11):2789-2793
Four new iridoids, buergerinins B–E ( 1 – 4 ), along with three known iridoids, were isolated from the roots of Scrophularia buergeriana. Their structures were identified on the basis of spectroscopic analysis. 相似文献