全文获取类型
收费全文 | 689篇 |
免费 | 14篇 |
国内免费 | 92篇 |
专业分类
化学 | 697篇 |
晶体学 | 7篇 |
力学 | 49篇 |
数学 | 2篇 |
物理学 | 40篇 |
出版年
2023年 | 10篇 |
2022年 | 10篇 |
2021年 | 13篇 |
2020年 | 20篇 |
2019年 | 13篇 |
2018年 | 8篇 |
2017年 | 16篇 |
2016年 | 20篇 |
2015年 | 12篇 |
2014年 | 15篇 |
2013年 | 45篇 |
2012年 | 46篇 |
2011年 | 44篇 |
2010年 | 35篇 |
2009年 | 45篇 |
2008年 | 54篇 |
2007年 | 56篇 |
2006年 | 30篇 |
2005年 | 29篇 |
2004年 | 33篇 |
2003年 | 24篇 |
2002年 | 16篇 |
2001年 | 22篇 |
2000年 | 15篇 |
1999年 | 22篇 |
1998年 | 12篇 |
1997年 | 10篇 |
1996年 | 11篇 |
1995年 | 20篇 |
1994年 | 19篇 |
1993年 | 13篇 |
1992年 | 12篇 |
1991年 | 7篇 |
1990年 | 6篇 |
1989年 | 6篇 |
1988年 | 6篇 |
1987年 | 8篇 |
1986年 | 4篇 |
1985年 | 2篇 |
1984年 | 1篇 |
1982年 | 1篇 |
1980年 | 1篇 |
1979年 | 1篇 |
1978年 | 1篇 |
1972年 | 1篇 |
排序方式: 共有795条查询结果,搜索用时 156 毫秒
31.
M. Jochum R. Bakry I. Wartusch C. W. Huck H. Engelhardt G. K. Bonn 《Chromatographia》2002,56(5-6):263-268
Summary This paper reports on the use of a polymer-based, strong anion-exchange stationary phase for rapid, selective and sensitive
analysis of physiological important mono-, di- and oligosaccharides by high-performance anion-exchange chromatography (HPAEC)
with pulsed amperometric detection (PAD) under alkaline conditions. The adsorbent was obtained by direct nitration of 3 and
5 μm, spherical non-porous highly cross-linked, styrene-divinylbenzene copolymer (PS-DVB) beads, followed by reduction of
superficially introduced nitro groups with nascent hydrogen and quaternization of the resultant amino groups with iodomethane.
Extended exposure to high pressure and strong alkaline conditions did not have any untoward effect on mechanical stability
and chromatographic performance. A comparison of the 3 and 5 μm beads showed, that the synthesized 3 μm highly cross-linked
PS-DVB particles are the preferred phases for the separation of monosaccharides and the 5 μm particles are preferable for
the separation of oligosaccharides. To demonstrate the suitability for the analysis of complex samples, the optimized and
validated system was used for the determination of glucose, fructose and sucrose in apple juice and other soft drinks such
as Coca Cola. Finally, analysis within a few minutes without sample pretreatment down to a lower limit of detection of 0.174–0.504
μg mL−1 at a linearity with R2>0.994 and a repooducibility higher than 98% further confirmed the efficiency of these polymeric sorbents. 相似文献
32.
Ya CaoHuilin Li 《European Polymer Journal》2002,38(7):1457-1463
A novel series of polymeric surfactants based on carboxy methyl cellulose and alkyl poly(etheroxy) acrylate were synthesized by ultrasonic irradiation. These polymeric surfactants have exhibit excellent surface activity due to their unique structure. The influences of salt, alcohol and alkali on the interfacial activity of these polymeric surfactants were studied by interfacial tensiometery, dynamic laser scattering (DLS), UV spectroscope and environmental scanning electrical microscope (ESEM). The surface tension and interfacial tension (IFT) properties change little with NaCl added. The formed micelles shrink, their size becomes smaller. Alcohols cause the IFT to decrease a little because a small amount of free chains present in solution. Under the influence of added alkali, the IFT of the polymeric surfactants, in aqueous solution, decreases so much that sometimes it is less than 10−2 mN/m. Using data from the equivalent alkane scan, one cannot draw the conclusion that the action of alkali with the acidic components in crude oil leads to the ultra-low IFT. The analyses by UV, DLS and ESEM show that the micelles formed by polymeric surfactants could be disaggregated or destroyed sharply by the action of alkali. So the size of micelles decreases greatly and the number of free chains increases. That more polymeric surfactants molecules move to the interface of oil/water and rearrange at the interface of oil/water is believed to be the main reason of the ultra-low IFT (10−3 mN/m) that is obtained. 相似文献
33.
Liu LX Huang ZL Zhao YD 《Spectrochimica acta. Part A, Molecular and biomolecular spectroscopy》2005,62(4-5):1039-1044
A detailed approach is described for the vibrational spectroscopic encoding of polystyrene-based resin beads by converting the infrared absorption peaks suitable for encoding (encoding peaks) into barcodes. Based on combining the FT-IR measurements and the quantum-chemical computations, the vibrational characteristics of p-tert-butylstyrene monomer, polystyrene and poly(p-tert-butylstyrene) resin beads are analyzed, which are helpful for the selection of encoding peaks. The vibrational spectroscopic encoding of polystyrene-based resin beads could be obtained by converting the wavenumber, intensity and full width at half maximum (FWHM) of the encoding peaks into barcodes automatically through a computer program designed in our laboratory. 相似文献
34.
Jeng-Shong Shih 《中国化学会会志》1994,41(3):309-314
Artificial macrocyclic polyethers were synthesized and applied as neutral carriers for ion-selective PVC membrane electrodes, ion-chromatographic packing materials, extractants and adsorbents for ion separation, coating materials for piezoeletrical membrane sensors for organic species, and ion-transport carriers through liquid membranes. Ion-selective electrodes such as those for K+ Na+, UO22+, Cs+, Pb2+, Fe3+, Hg2+ and Ag+ ions based on crown ether-phosphotungstic acid (PW) precipitates and dithio crown ethers respectively were prepared and showed good sensitivity and selectivity. Crown ether-PW precipitates were applied as adsorbents of rare-earth ions and some common heavy-metal ions. Some rare-earth ions were easily extracted with crown ethers, especially 15-crown-5. Poly(stytene/divinyl benzene) cryptand-22 resin was synthesized and applied as a bifunctional stationary phase of ion chromatography to separate bom cations and anions, even some organic carboxylate geometric isomers. Crown ethers such as mono-benzo-15-crown-5 was successfully applied as a coating material on piezoelectric quartz membrane sensors for some organic species. The oscillation frequency of the crown-ether quartz-membrane sensor was sensitive to organic vapours such as amines and alcohols. Upon adsorption of organic species on the crown-ether quartz membrane, the oscillation frequency of the sensor decreased obviously. Special crown ether such as dibenzo-16-crown-5-oxyacetic acid, decyl-cryptand-22 and 1, 4-dihydro-pyridine-18-crown-5 were synthesized and successfully applied as ion-transport carriers (ionophores) for transport of Na+ K+ and Mg2+ ions through liquid membranes. 相似文献
35.
36.
Abstract Persulfate-initiated graft copolymerizations of glutaraldehyde crosslinked gelatin with acrylic acid, acrylamide, vinyl acetate, and methyl methacrylate in the aqueous phase were investigated. It was observed that percentage grafting, molecular weights of the grafts, and grafting efficiencies were greatly influenced by the nature of the monomers. Hydrophilic monomers gave a higher frequency of grafting but lower molecular weights. While the frequency of grafting with hydrophobic monomers was low, the molecular weights of the grafts were comparatively high. The results are explained in terms of microdomain kinetics, similar to those encountered in emulsion or suspension polymerizations. 相似文献
37.
Polymer-Mercury Coated Screen-Printed Sensors for Electrochemical Stripping Analysis of Heavy Metals
Ilaria Palchetti Sanaa Majid Alessandra Kicela Giovanna Marrazza Marco Mascini 《International journal of environmental analytical chemistry》2013,93(7-8):701-711
In the perspective of in-field stripping analysis of heavy metals, the use and disposal of toxic mercury solutions (necessary to plate a mercury film on a carbon electrode surface) presents a problem. The aim of this work was the development of mercury coated screen-printed electrodes previously prepared in the lab and ready to use in-field. Thus some commercially available polymers like Nafion®, Eastman Kodak AQ29®, and Methocel® were investigated as mercury entrapping systems for electrochemical stripping analysis of heavy metals. Screen-printed disposable cells with a silver pseudo-reference electrode, a graphite counter electrode, and a graphite working electrode were used. To modify the sensor, the polymer solution was cast onto the carbon working electrode surface. Detection limits of 0.8 and 1 μg/L were obtained for lead and cadmium respectively. Since Methocel® based electrodes showed the best performance, they were used for the analysis of real samples. The results were compared with those obtained using a classical thin mercury film electrode and ICP spectroscopy. All the experiments reported here were performed in un-deareated solutions as required for in-field analysis. 相似文献
38.
Abstract The binding of pyrenesulfonic acid and pyrenebutyric acid to poly(vinyl benzyl trimethylammonium) chloride was investigated by UV and fluorescence spectroscopy. It was found that the binding constant was 7.5 × 104 and 3.5 × 104M?1, respectively. The addition of the polyelectrolyte quenches the fluorescence of the pyrene group, and at the same time the typical excimer emission appears. This emission originates in pre-formed ground state aggregates of the pyrene derivatives incorporated into the polyion domain. Similar effects were observed when anionic polyelectrolytes, poly(styrene sulfonic), and poly(vinyl sulfonic) acids were added to cationic pyrene derivatives. The binding constants depend on the length of the aliphatic sidechain of the derivatives. 相似文献
39.
《高分子科学杂志,A辑:纯化学与应用化学》2013,50(5-6):591-604
Polymerization of methyl methacrylate (MMA) with diphenyl diselenide (DPDSE) in the presence of AIBN at 60°C was investigated. DPDSE was worked as a chain transfer agent (CTA). The chain transfer constant (Ctr) of DPDSE for MMA was estimated to be 1.43. On the other hand, DPDSE was functioned as a photoiniferter for the photopolymerization of MMA. In a limited range of conversion, both the polymer yield and number average of molecular weight ([Mbar]n) increased with the reaction time, and the [Mbar]n linearly increased with the yield. The terminal structure of poly(MMA) was investigated by the 77Se NMR spectrum based on Methyl α-phenylseleno isobutylate (MSEPI) as model compound of the ω-chain end of poly(MMA). Further, photopolymerization of poly (MMA) containing phenylseleno group at ω-chain end as a polymeric photoiniferter with MMA effectively afforded a poly (MMA) having higher molecular weight. 相似文献
40.
Transparent hybrid materials have been prepared by incorporating either an alumina or titania alkoxide sol with triethoxysilane end-capped polytetramethylene oxide (PTMO) oligomer. In order to avoid undesirable precipitation after the addition of water, a β-dicarbonyl ligand, ethyl acetoacetate, was used. Triethoxysilane endcapped polytetramethylene oxide with a molecular weight of 2000 (g/mol) was chosen to react with either the alumina or titania sol to demonstrate the features of the reaction scheme. The extent of reaction leading to network formation has been qualitatively followed by infrared spectroscopy. A series of solid films were prepared by varying the molar ratio of either aluminum tri(sec-butoxide) or titanium tetraisopropoxide to ethyl acetoacetate, and the weight fraction of alumina or titania to that of PTMO. The refractive index as well as the general structure-property behavior of these hybrid materials were studied. 相似文献