全文获取类型
收费全文 | 35853篇 |
免费 | 1203篇 |
国内免费 | 117篇 |
专业分类
化学 | 23405篇 |
晶体学 | 227篇 |
力学 | 675篇 |
综合类 | 2篇 |
数学 | 6606篇 |
物理学 | 6258篇 |
出版年
2023年 | 231篇 |
2022年 | 406篇 |
2021年 | 568篇 |
2020年 | 605篇 |
2019年 | 574篇 |
2018年 | 1055篇 |
2017年 | 815篇 |
2016年 | 1251篇 |
2015年 | 975篇 |
2014年 | 1033篇 |
2013年 | 2154篇 |
2012年 | 2183篇 |
2011年 | 2283篇 |
2010年 | 1402篇 |
2009年 | 1317篇 |
2008年 | 1991篇 |
2007年 | 2038篇 |
2006年 | 1829篇 |
2005年 | 1729篇 |
2004年 | 1454篇 |
2003年 | 1187篇 |
2002年 | 1029篇 |
2001年 | 718篇 |
2000年 | 709篇 |
1999年 | 511篇 |
1998年 | 368篇 |
1997年 | 362篇 |
1996年 | 449篇 |
1995年 | 315篇 |
1994年 | 354篇 |
1993年 | 299篇 |
1992年 | 287篇 |
1991年 | 268篇 |
1990年 | 269篇 |
1989年 | 233篇 |
1988年 | 210篇 |
1987年 | 207篇 |
1986年 | 201篇 |
1985年 | 272篇 |
1984年 | 287篇 |
1983年 | 199篇 |
1982年 | 208篇 |
1981年 | 219篇 |
1980年 | 203篇 |
1979年 | 140篇 |
1978年 | 158篇 |
1977年 | 153篇 |
1976年 | 144篇 |
1975年 | 128篇 |
1973年 | 107篇 |
排序方式: 共有10000条查询结果,搜索用时 15 毫秒
971.
A polypyrrole electrode modified with a tetrasulfonated nickel(II) phthalocyanine complex (GCE/PPy/NiPcTs) was used as amperometric electrochemical detector in a flow injection system, in order to determine some antioxidants in foods. The lather were separated by HPLC and detected at the modified electrode. Previous investigations carried out in our laboratory employed this electrode and cyclic voltammetry (CV), obtaining excellent results, due to an electrocatalytic effect on the oxidation of certain alimentary antioxidants, such tert-butylhydroquinone (TBHQ), 3-tert-butyl-4-hydroxyanisole (BHA) and propylgallate (PG). In order to obtain good separation, the chromatographic conditions were optimised. The geometry of the flow injection analysis (FIA) circuit and the reproducibility of the results were also optimised and, finally, the linear relationship between the signal and the concentration was verified. The proposed procedure is more precise and accurate than the conventional voltammetry methods. These results offer new analytical possibilities to this type of modified electrodes. The developed methods were applied to the determination of these antioxidants in commercial food. 相似文献
972.
Attwood D Boitard E Dubès J Tachoire H 《Journal of colloid and interface science》2000,227(2):356-362
Relative apparent molar enthalpies have been determined as a function of concentration (0.0001 to 0.2 mol kg(-1)) by heat conduction calorimetry for aqueous solutions of the structurally related antidepressant drugs imipramine and clomipramine in water over the temperature range 288 to 308 K. Critical concentrations determined from inflections in these plots for both drugs had minimum values at 298 K. The concentration dependence of the relative apparent molar enthalpy could be quantitatively described using a mass action model of association based on the Guggenheim equations for the activity coefficients of mixed electrolytes. Derived values of the monomer-counterion interaction coefficient for imipramine became increasingly negative with an increase in temperature over the temperature range 293 to 303 K, indicative of an increasing degree of premicellar association. In contrast, negative monomer-counterion interaction coefficients were obtained for clomipramine at only 303 and 308 K, suggesting an absence of premicellar association at lower temperatures. Values derived for the molar enthalpy of micellization of both drugs from the mass action model indicate an increasingly exothermic process with increase in temperature; positive values at 288 and 293 K arise from hydrophobic interactions while the negative values at higher temperatures suggest the importance of London dispersion interactions as the major driving force for aggregation. Copyright 2000 Academic Press. 相似文献
973.
Rodrigues e Silva AA da Silva Góes AJ de Lima WT de Souza Maia MB 《Chemical & pharmaceutical bulletin》2003,51(12):1351-1355
The search for new anti-inflammatory drugs has been constant in several research centers. The use of the Bioisostery concept allows the elaboration of new bioactive compounds with different properties through the introduction of substitute groups in one or more positions of a main molecule with known biological activity. Preliminary works accomplished at our laboratory with 2,4-thiazolidinedione isosters demonstrated inhibitory activity on edema formation for N-tryptophyl-5-(3,5-di-tert-butyl-4-hydroxybenzylidene)-2,4-thiazolidinedione (GS28) and N-tryptophyl-5-(3,5-di-tert-butyl-4-hydroxybenzylidene) rhodanine (GS26). We verified the antiedematogenic and ulcerogenic activity of these two compounds in Wistar rats. The carrageenan induced paw edema suffered significant (p<0.05) inhibition (28.36% on average) for GS28 (100 mg/kg; v.o.) during the entire time of the experiment. GS26 (50 and 100 mg/kg; v.o.) significantly inhibited (p<0.05) the paw edema dextran induced (22.1 and 27.8%, for the respective doses) after 180 min. The compounds GS26 and GS28 did not show ulcerogenic activity on gastric mucous. The results suggest antiedematogenic action for both compounds without the appearance of gastric lesions. 相似文献
974.
Carballo R Casas JS García-Martínez E Pereiras-Gabián G Sánchez A Sordo J Vázquez-López EM 《Inorganic chemistry》2003,42(20):6395-6403
The reactions of methylacetoacetate and ethyl 2-methylacetoacetate thiosemicarbazones (H(2)L(A) and H(2)L(B), respectively) with [ReX(CO)(5)] and [ReX(CO)(3)(CH(3)CN)(2)] (X = Cl, Br) were explored under various experimental conditions. Besides the adducts fac-[ReX(CO)(3)(H(2)L)], in which the rhenium is coordinated to three carbonyl groups, the X anion, and the N,S-bidentate thiosemicarbazone ligand, the following complexes were also isolated: fac-[ReBr(CO)(3)(Hpyz(B))], the tetrameric complexes fac-[Re(pyz(A))(CO)(3)](4) and fac-[Re(pyz(B))(CO)(3)](4), and fac-[Re(pyz(B))(CO)(3)(H(2)O)] (where Hpyz(A) and Hpyz(B) are pyrazolones derived by cyclization of H(2)L(A) and H(2)L(B), respectively). The cyclization reactions were monitored by (1)H NMR spectroscopy and the complexes isolated were identified by elemental analysis, mass spectrometry, IR and (1)H NMR spectroscopy, and in some cases by X-ray diffractometry. The isolation and the full structural identification of the rather unusual fac-[ReBr(CO)(3)(Hpyz(B))], which contains the enol form of the pyrazolone ligand, affords new insight into the cyclization of thiosemicarbazones derived from beta-keto esters. 相似文献
975.
976.
López-Blanco MC Reboreda-Rodríguez B Cancho-Grande B Simal-Gándara J 《Journal of chromatography. A》2002,950(1-2):293-299
The electrophoretic behaviour of ionizable and neutral alkylxanthines commonly used in pharmaceutical preparations was studied. The performance of various separation modes including capillary zone electrophoresis (CZE), cyclodextrin electrokinetic chromatography, and micellar electrokinetic chromatography (MEKC) with either sodium dodecyl sulfate (SDS) or bile salts as surfactants, was assessed. CZE in an alkaline medium successfully separates ionizable xanthines and dyphylline. The addition of carboxymethyl-β-cyclodextrin to the background electrolyte allows only partial resolution of neutral xanthines. Based on MEKC results, bile salts exhibit more discrimination ability than SDS to separate similar xanthines. The best results are provided by taurodeoxycholic acid, which ensures baseline separation of xanthines. 相似文献
977.
J. López-Cervantes D.I. Sánchez-Machado J. Simal-Lozano P. Paseiro-Losada 《Chromatographia》2003,58(5-6):321-326
Summary A high-performance liquid-chromatographic method with UV detection (HPLC–UV) has been developed for quantification of ethylene terephthalate oligomers in olive oil, from which they were extracted with acetonitrile. Oligomers, from monomers (M1) to pentamers (M5), were jointly and/or individually identified by liquid chromatography with mass spectrometry (electron-impact mass spectrometry (EIMS) low- and high-resolution) and were quantified by HPLC–UV using an acetonitrile solution of the major oligomer (the trimer M3) as standard. For M3 recovery was 98.9%, the detection limit was 60 g L–2, and method precision was 2.03% (RSD). Migration of oligomers M1–M5 into 50 mL olive oil sealed in each of two brands of 10 cm × 10 cm poly(ethylene terephthalate) roasting bag was evaluated under two sets of conditions that approached but remained below the limit at which the bag material became physically deformed – heating for 7 min at 850 W in a microwave oven, or for 60 min at 200 °C in a conventional oven. Total migration was approximately 2.7 mg dm–2 under the former conditions and 3.5–4.1 mg dm–2 under the latter.Presented at the International Symposium on Separation and Characteristics of Natural and Synthetic Macromolecules, Amsterdam, The Netherlands, February 5–7, 2003 相似文献
978.
On the structure formation of hydrophobed particles in the boundary layer of water and octane phases
Two-dimensional aggregation of the surface modified glass beads was carried out in the boundary layer of water and octane phases. The effect of particles' hydrophobicity was investigated on the structure of forming aggregates and the growth process. The structure of the aggregates and their growth were characterized by a density function which demonstrates the change of mean particle density as a function of aggregate size. The growth yielded fractal or nonfractal structures in the investigated systems. The fractal structure of the aggregates was observed to be dependent on restructuring processes controlled by the surface properties of the beads.The experimental results are compared with earlier findings for aggregation of hydrophobic beads in the boundary layer of water and air phases.On leave from Loránd Eötvös University, Budapest, Hungary 相似文献
979.
Summary Reinvestigation by HPLC of the petals ofLilium tigrinum and the isolation of some minor compounds is reported. Using HPLC-controlled, preparative-column chromatography, 5,6-diakarpoxanthin
(6), 6-epikarpoxanthin (2), 5,6-diacapsokarpoxanthin (8), and 9Z-antheraxanthin (9Z-13) were isolated and characterized. Based on spectroscopic data the absolute configurations of6 and8 were identical with those originating from paprika, thus the 5,6-diakarpoxanthin (6) and 5,6-diacapsokarpoxanthin (8) have the 3S, 5S, 6S configuration and 6-epikarpoxanthin (2) has the 3S, 5R, 6S configuration.
Presented at: Balaton Symposium on High-Performance Separation Methods, Siófok, Hungary, September 3–5, 1997. 相似文献
980.
Mínguez JM Castellote MI Vaquero JJ García-Navio JL Alvarez-Builla J Castaño O Andrés JL 《The Journal of organic chemistry》1996,61(14):4655-4665
A new synthesis of the pyrrolo[1,2-a]pyrazine system from pyrrole is described. In light of the ab initio calculations carried out on this heterocyclic system some of its basic chemistry was investigated and included electrophilic substitution, addition of organolithium reagents, metalation with lithium diisopropylamide and subsequent reaction with electrophiles, and formation of salts by quaternization of the nonbridgehead nitrogen. N-ylides obtained from these salts undergo 1,3-dipolar cycloaddition with suitable dipolarophiles to give dipyrrolo[1,2-a]pyrazines, pyrazolo[1,5-a]-pyrrolo[2,1-c]pyrazines, and heterobetaines. Examples of intramolecular 1,3-dipolar cycloadditions are also reported. 相似文献