全文获取类型
收费全文 | 2090篇 |
免费 | 120篇 |
国内免费 | 18篇 |
专业分类
化学 | 1630篇 |
晶体学 | 6篇 |
力学 | 21篇 |
数学 | 348篇 |
物理学 | 223篇 |
出版年
2024年 | 3篇 |
2023年 | 21篇 |
2022年 | 16篇 |
2021年 | 35篇 |
2020年 | 60篇 |
2019年 | 69篇 |
2018年 | 34篇 |
2017年 | 28篇 |
2016年 | 70篇 |
2015年 | 57篇 |
2014年 | 71篇 |
2013年 | 101篇 |
2012年 | 134篇 |
2011年 | 138篇 |
2010年 | 71篇 |
2009年 | 80篇 |
2008年 | 139篇 |
2007年 | 151篇 |
2006年 | 135篇 |
2005年 | 138篇 |
2004年 | 112篇 |
2003年 | 93篇 |
2002年 | 94篇 |
2001年 | 41篇 |
2000年 | 30篇 |
1999年 | 31篇 |
1998年 | 19篇 |
1997年 | 31篇 |
1996年 | 27篇 |
1995年 | 24篇 |
1994年 | 26篇 |
1993年 | 23篇 |
1992年 | 9篇 |
1991年 | 20篇 |
1990年 | 8篇 |
1989年 | 11篇 |
1988年 | 8篇 |
1986年 | 3篇 |
1985年 | 7篇 |
1984年 | 3篇 |
1983年 | 7篇 |
1982年 | 3篇 |
1981年 | 9篇 |
1980年 | 6篇 |
1978年 | 6篇 |
1977年 | 5篇 |
1976年 | 4篇 |
1974年 | 5篇 |
1967年 | 2篇 |
1931年 | 2篇 |
排序方式: 共有2228条查询结果,搜索用时 0 毫秒
71.
Simultaneous analysis of oxidized and reduced glutathione in cell extracts by capillary zone electrophoresis 总被引:1,自引:0,他引:1
Yang Q Krautmacher C Schilling D Pittelkow MR Naylor S 《Biomedical chromatography : BMC》2002,16(3):224-228
Glutathione (GSH) and glutathione disulfide (GSSG) levels in cells constitute a thiol redox system. They can be used as an indicator of oxidative stress of the cell. In this study, a capillary zone electrophoresis (CZE) method is described that enables quantitation of GSH and GSSG from cellular extracts. The CZE buffer used was 20 mM ammonium acetate containing 5% (v/v) acetic acid at pH 3.1 in conjunction with a polybrene coated capillary operated in reverse polarity mode. Effects of different acids used to prepare cell samples were investigated on CZE performance. The acids include meta phosphoric acid (MPA), trichloroacetic acid (TCA), phosphoric acid (PA) and sulfosalicylic acid (SSA) and are used to stabilize GSH and GSSG before performing CZE analysis. The method features a limit of detection of 4 microM and a limit of quantitation of 12 microM for both GSSG and GSH and recoveries of 94% for GSH and 100% for GSSG. Quantitative analysis of GSSG and GSH in HaCaT cell extracts (5% SSA, w/v) was performed with this method and changes in the ratio of GSH to GSSG in N-ethylmaleimide treated cell sample was observed by comparing with control cell samples. 相似文献
72.
Treatment of the phenyl-substituted silane 4 with lithium metal afforded the functionalized lithiosilane rac-2 by selective cleavage of one Si-C bond between silicon and a phenyl group. The resulting lithiosilane rac-2 crystallizes as the dimer (2.THF)2, which represents the first example of a dimeric organyl-substituted lithiosilane in the presence of THF. 相似文献
73.
Nussbaumer P Ettmayer P Peters C Rosenbeiger D Högenauer K 《Chemical communications (Cambridge, England)》2005,(40):5086-5087
The alkyl chain in the backbone of sphingosine derivatives can be exchanged with functionalised (labelled) side chains in a single step under cross-metathesis reaction conditions. 相似文献
74.
Angelovski G Costisella B Kolarić B Engelhard M Eilbracht P 《The Journal of organic chemistry》2004,69(16):5290-5294
Azamacrocyclic fluorophores containing piperazine units were synthesized using sequential rhodium-catalyzed regioselective hydroformylation-reductive amination. A piperazine unit is introduced into the macrocycles to act simultaneously as electron donor and binding site. The macrocycles chelate divalent cations, either Zn2+ or Co2+, which considerably enhanced fluorescence. Complexation with Zn2+ was additionally confirmed by NMR. 相似文献
75.
Maurer HH Tenberken O Kratzsch C Weber AA Peters FT 《Journal of chromatography. A》2004,1058(1-2):169-181
A liquid chromatographic-mass spectrometric assay with atmospheric pressure chemical ionization (LC-APCI-MS) is presented for screening for, library-assisted identification (both in scan mode) and quantification (selected-ion mode) of the beta-blockers acebutolol, diacetolol, alprenolol, atenolol, betaxolol, bisoprolol, bupranolol, carazolol, carteolol, carvedilol, celiprolol, esmolol, labetalol, metoprolol, nadolol, nebivolol, oxprenolol, penbutolol, propranolol, sotalol, talinolol and timolol in blood plasma after mixed-mode (HCX) solid-phase extraction (SPE) and separation by reverse-phase liquid chromatography with gradient elution. The validation data were within the required limits. The assay was successfully applied to authentic plasma samples allowing confirmation of diagnosis of overdose situations as well as monitoring of patients' compliance. 相似文献
76.
Polystyrene-bound cumulated ylide Ph3PCCO was prepared on a large scale in two steps. It reacts with Grignard compounds, amines and alcohols to give immobilized acyl, amide and ester ylides, respectively. Their Wittig reactions lead to alkenes free of phosphane oxide. Optically pure 5-substituted tetramates were obtained from reactions of resin-bound Ph3PCCO with alpha-ammonium esters in one step. The mycotoxin (-)-tenuazonic acid was accordingly prepared in just three steps. 相似文献
77.
Fauhl C Wittkowski R Lofthouse J Hird S Brereton P Versini G Lees M Guillou C 《Journal of AOAC International》2004,87(5):1179-1188
The aim of the present study was to provide the official wine control authorities with an internationally validated method for the determination of 3-methoxy-1,2-propanediol (3-MPD) and cyclic diglycerols (CycDs)-both of which are recognized as impurities of technical glycerol-in different types of wine. Because glycerol gives a sweet flavor to wine and contributes to its full-body taste, an economic incentive is to add glycerol to a wine to mask its poor quality. Furthermore, it is known that glycerol, depending on whether it is produced from triglycerides or petrochemicals, may contain considerable amounts of 3-MPD in the first case or CycDs in the second. However, because these compounds are not natural wine components, it is possible to detect glycerol added to wine illegally by determining the above-mentioned by-products. To this end, one of the published methods was adopted, modified, and tested in a collaborative study. The method is based on gas chromatographic/mass spectrometric analysis of diethyl ether extracts after salting out with potassium carbonate. The interlaboratory study for the determination of 3-MPD and CycDs in wine was performed in 11 laboratories in 4 countries. Wine samples were prepared and sent to participants as 5 blind duplicate test materials and 1 single test material. The concentrations covered ranges of 0.1-0.8 mg/L for 3-MPD and 0.5-1.5 mg/L for CycDs. The precision of the method was within the range predicted by the Horwitz equation. HORRAT values obtained for 3-MPD ranged from 0.8 to 1.7, and those obtained for CycDs ranged from 0.9 to 1.3. Average recoveries were 104 and 109%, respectively. 相似文献
78.
Kariuki NN Luo J Maye MM Hassan SA Menard T Naslund HR Lin Y Wang C Engelhard MH Zhong CJ 《Langmuir : the ACS journal of surfaces and colloids》2004,20(25):11240-11246
This paper reports findings of an investigation of the synthesis of monolayer-capped binary gold-silver (AuAg) bimetallic nanoparticles that is aimed at understanding the control factors governing the formation of the bimetallic compositions. The synthesis of alkanethiolate-capped AuAg nanoparticles was carried out using two related synthetic protocols using aqueous sodium borohydride as a reducing agent. One involves a two-phase reduction of AuCl(4)(-), which is dissolved in organic solution, and Ag(+), which is dissolved in aqueous solution. The other protocol involves a two-phase reduction of AuCl(4)(-) and AgBr(2)(-), both of which are dissolved in the same organic solution. AuAg nanoparticles of 2-3 nm core sizes with different compositions in the range of 0-100% Au have been synthesized. The two synthetic routes were compared in terms of bimetallic composition and size properties. Our new findings have allowed us to establish the correlation between synthetic feeding of metals and metal compositions in the bimetallic nanoparticles, which have important implications to the exploration of gold-based bimetallic nanoparticles for constructing sensing and catalytic nanomaterials. 相似文献
79.
Surface roughness has been considered as a passive means of enhancing species mixing in electroosmotic flow through microfluidic systems. It is highly desirable to understand the synergetic effect of three-dimensional (3D) roughness and surface heterogeneity on the electrokinetic flow through microchannels. In this study, we developed a three-dimensional finite-volume-based numerical model to simulate electroosmotic transport in a slit microchannel (formed between two parallel plates) with numerous heterogeneous prismatic roughness elements arranged symmetrically and asymmetrically on the microchannel walls. We consider that all 3D prismatic rough elements have the same surface charge or zeta potential, the substrate (the microchannel wall) surface has a different zeta potential. The results showed that the rough channel's geometry and the electroosmotic mobility ratio of the roughness elements' surface to that of the substrate, epsilon(mu), have a dramatic influence on the induced-pressure field, the electroosmotic flow patterns, and the electroosmotic flow rate in the heterogeneous rough microchannels. The associated sample-species transport presents a tidal-wave-like concentration field at the intersection between four neighboring rough elements under low epsilon(mu) values and has a concentration field similar to that of the smooth channels under high epsilon(mu) values. 相似文献
80.
Renner L Pompe T Salchert K Werner C 《Langmuir : the ACS journal of surfaces and colloids》2004,20(7):2928-2933
Desorption and exchange of preadsorbed fibronectin layers in pure buffer solution and solutions of human serum albumin or fibronectin, respectively, were studied in dependence on the physicochemical characteristics of maleic acid copolymer films used as substrates. Although the preadsorbed amount of fibronectin differed only slightly, the protein was found to exhibit a significantly enhanced anchorage at the more hydrophobic polymer surface as compared to the more hydrophilic and more negatively charged polymer surface. The preadsorbed fibronectin layer was most efficiently exchanged by fibronectin (i.e., in the homodisplacement process) while pure buffer solution and human serum albumin solutions induced desorption or exchange of fibronectin to lower and similar degrees. An increase of the total adsorbed amount of protein due to additional adsorption of fibronectin or human serum albumin accompanied the partial exchange of the preadsorbed fibronectin in the displacement experiments. Evaluation of the kinetics of desorption and exchange of fibronectin at any of the substrates revealed two kinds of surface-attached protein populations--a fast desorbing species and a species with a slow desorption and exchange rate. By a multivariate regression analysis the surface characteristics of the polymer substrate were confirmed to determine the degree of protein desorption and exchange while the dynamics of the layer alteration was found to solely depend on the diffusion behavior of the proteins. 相似文献