全文获取类型
收费全文 | 289篇 |
免费 | 9篇 |
国内免费 | 2篇 |
专业分类
化学 | 263篇 |
力学 | 1篇 |
数学 | 13篇 |
物理学 | 23篇 |
出版年
2021年 | 1篇 |
2019年 | 5篇 |
2017年 | 1篇 |
2016年 | 5篇 |
2015年 | 4篇 |
2014年 | 5篇 |
2013年 | 9篇 |
2012年 | 9篇 |
2011年 | 13篇 |
2010年 | 12篇 |
2009年 | 12篇 |
2008年 | 34篇 |
2007年 | 29篇 |
2006年 | 28篇 |
2005年 | 23篇 |
2004年 | 24篇 |
2003年 | 18篇 |
2002年 | 24篇 |
2001年 | 2篇 |
2000年 | 4篇 |
1999年 | 1篇 |
1998年 | 1篇 |
1997年 | 6篇 |
1996年 | 3篇 |
1995年 | 2篇 |
1994年 | 4篇 |
1992年 | 3篇 |
1991年 | 5篇 |
1989年 | 1篇 |
1986年 | 1篇 |
1985年 | 1篇 |
1984年 | 1篇 |
1982年 | 2篇 |
1981年 | 2篇 |
1980年 | 1篇 |
1978年 | 1篇 |
1977年 | 1篇 |
1968年 | 1篇 |
1960年 | 1篇 |
排序方式: 共有300条查询结果,搜索用时 93 毫秒
71.
A simple and cost-effective laboratory-made liquid junction interface was used for coupling of CE with MS. In this device the capillary column and the spray tip were positioned in the electrode vessel containing appropriate spray liquid. The electrospray potential was applied on the electrode inside the liquid junction. A stable electrospray was produced at nanoliter per minute flow rates generated in the emitter tip without using an external pump. This arrangement provided high durability of the spray tip and independent optimization of the CE separation (use of coated capillaries) and ESI conditions. CE-MS analysis of mixtures of drugs, peptides, tryptic digests of proteins and biological fluids was optimized with respect to the effects of the distance between the separation capillary and electrospray tip and pressure applied on the liquid junction. The sensitivity of the system, in terms of the LOD (base peak monitoring) was below 10 ng/mL for the beta-blocker drugs and below 200 ng/mL for peptide analysis. 相似文献
72.
Open-tubular columns for CEC separations having inner-wall coated with a thin layer of porous monolithic polymer have been studied. A two-step process including (i) UV-initiated polymerization leading to a layer of porous poly(butyl methacrylate-co-ethylene dimethacrylate), and (ii) UV-initiated grafting of ionizable monomers appear to be well suited for the preparation of these columns. The thickness of the porous polymer layer is controlled by the percentage of monomers in the polymerization mixture and/or length of the irradiation time. The layer thickness significantly affects retention, efficiency, and resolution in open-tubular CEC. Under optimized conditions, column efficiencies up to 400,000 plates/m can be achieved. Use of higher temperature and application of pressure enables a significant acceleration of the open-tubular CEC separations. 相似文献
73.
An on-line coupled capillary isotachophoresis--capillary zone electrophoresis (cITP-CZE) method for the determination of domoic acid in shellfish and algae is described. The optimised cITP-CZE electrolyte system was 10 mM HCl + 20 mM beta-alanine (BALA) + 0.05% hydroxyethylcellulose (leading electrolyte), 5 mM caproic acid (terminating electrolyte) and 20 mM caproic acid + 20 mM BALA + 0.1% HPMC (background electrolyte). A clear separation of the domoic acid from the other components of methanolic sample extract was achieved within 25 min. Method characteristics, i.e., linearity (0-200 microg/l), accuracy (recovery 101+/-3%), intra-assay repeatability (2.4%) and detection limit (1.5 microg/l) were determined. Speed of analysis, low laboriousness, high sensitivity and low running cost are the typical attributes of the cITP-CZE method. Developed method was successfully applied to analysis of shellfish samples and food supplements containing algae extract. 相似文献
74.
Photochromic nitrospiropyrans substituted with 2,2'-bipyridine (bpy), [Ru(bpy)3]2+, and [Os(bpy)3]2+ groups were synthesized, and their photophysical, photochemical, and redox properties investigated. Substitution of the spiropyran with the metal complex moiety results in strongly decreased efficiency of the ring-opening process as a result of energy transfer from the excited spiropyran to the metal center. The lowest excited triplet state of the spiropyran in its open merocyanine form is lower in energy than the excited triplet MLCT level of the [Ru(bpy)3]2+ moiety but higher in energy than for [Os(bpy)3]2+, resulting in energy transfer from the excited ruthenium center to the spiropyran but inversely in the osmium case. The open merocyanine form reduces and oxidizes electrochemically more easily than the closed nitrospiropyran. Like photoexcitation, electrochemical activation also causes opening of the spiropyran ring by first reducing the closed form and subsequently reoxidizing the corresponding radical anion in two well-resolved anodic steps. Interestingly, the substitution of the spiropyran with a Ru or Os metal center does not affect the efficiency of this electrochemically induced ring-opening process, different from the photochemical path. 相似文献
75.
Jirka I Plsek J Sutara F Matolín V Cháb V Prince KC 《The journal of physical chemistry. B》2006,110(47):23837-23844
A model catalyst system, palladium on tungsten oxide, has been examined by temperature-programmed desorption and photoemission spectroscopy. The samples were prepared by evaporation of palladium onto an oxidized tungsten foil under ultrahigh vacuum conditions. Mostly three-dimensional (3-D) palladium (Pd) clusters were found to be present on oxidized tungsten (WOx) surfaces at room temperature. Upon annealing to 670 K, the palladium clusters are redispersed and decorated by the WOx surface layer. The nature of the WOx phase on top of the palladium clusters is dependent on the mode of oxidation of the tungsten foil prior to palladium deposition. Mainly W(2+) species decorate palladium deposits on tungsten oxidized at room temperature, while mainly W(4+) species are on top of palladium deposits on the surface oxidized at 1300 K. The appearance of a Pd(n+)-O-W(4+) mixed oxide phase with n < 2 was observed on the oxidized tungsten surface. The substantial reduction (relative to nonannealed samples) of molecular CO coverage induced by annealing is discussed in terms of the changes in chemical composition and morphology of the outermost surface. 相似文献
76.
It is proved that if a Schur superalgebra is not semisimple,then it is neither cellular nor quasi-hereditary (Theorem 2),and it has infinite global dimension (Corollary 18). The algebraS(m|n, r) with m, n 1 is semisimple if and only if p, the characteristicof the ground field, is zero or greater than r, or when m =n = 1 and p does not divide r. 2000 Mathematics Subject Classification17A70 (primary), 20C30 (secondary). 相似文献
77.
Martina Hribova Frantisek Rybnikar Jarmila Vilcakova 《Journal of Macromolecular Science: Physics》2013,52(1):16-25
Microscopical, differential scanning colorimetry (DSC), and X-ray structural investigations of solution crystallized carbon nanotube (CNT) composites with linear polyethylene (LPE), isotactic polypropylene (iPP), polybutene-1 (PB-1), and nylon 6 (PA6) disclosed varying degrees of surface interaction and nucleation effect of CNT in these polymers and formation of oriented shish-kebab overgrowths on the CNT ropes in LPE and PA6. The character of the attraction and orientation forces at the CNT-polymer interface is discussed. 相似文献
78.
79.
Ivan Martincek Dusan Pudis Alexander Satka Ivica Janigova Katarina Csomorova Frantisek Cernobila 《Optik》2008,119(11):523-527
Optical properties of the spinal cuticle taken from the species of Lucilia sericata are studied by the reflectance measurements and their structural properties by scanning electron microscopy. The multilayer structure of the cuticle has been confirmed from the scanning electron micrographs. The temperature sensitivity of the multilayer structure is documented by the modification of optical properties in a heating process. The heating process and the local heating using the focused laser beam causes the local changes of the optical properties what is finally demonstrated by the structural color shift of the reflected spectra. 相似文献
80.
A new chiral monomer derived from cinchona alkaloid, namely O-9-(tert-butylcarbamoyl)-11-[2-(methacryloyloxy)ethylthio]-10,11-dihydroquinine 1, was employed for the preparation of enantioselective monolithic capillary columns by an in situ copolymerization with 2-hydroxyethyl methacrylate 2 (HEMA), ethylene dimethacrylate 3 (EDMA) in the presence of cyclohexanol and 1-dodecanol as porogens (UV or thermal initiation of azobisisobutyronitrile (AIBN) as radical initiator). The porous properties and the electrochromatographic behavior of the new chiral monoliths were comparatively evaluated with previously described analogs obtained from O-9-[2-(methacryloyloxy)ethylcarbamoyl]-10,11-dihydroquinidine 4 as chiral monomer. Despite close structural and physicochemical similarities of the both chiral monomers, the pore distribution profiles of the resulting monoliths were shifted typically towards larger pore diameters with the new monomer 1. Once more, it was confirmed that a low cross-linking (10 wt% related to total monomers) and a pore diameter of about 1 microm in the dry state provides the best electrochromatographic efficiency as a result of lower resistance to mass transfer (smaller C-term contribution to peak broadening) and more homogeneous flow profile (smaller A-term). Most importantly, as expected the new poly(1-co-HEMA-co-EDMA) monoliths showed enhanced enantioselectivities and in addition faster separations as compared to poly(4-co-HEMA-co-EDMA) analogs, which represents a significant improvement. Further, the elution order was reversed owing to the pseudoenantiomeric behavior of quinine- and quinidine-derived monomers. Fluorescence-labeled 9-fluorenylmethoxycarbonyl (FMOC), dansyl (DNS), 7-dimethylaminosulfonyl-1,3,2-benzoxadiazol-4-yl (DBD), carbazole-9-carbonyl (CC) amino acids could be separated with resolution values between 2 and 4 (with efficiencies typically between 100,000 and 200,000 plates/m) and fluorescence detection (variable wavelength fluorescence detector in-line with UV) yielding routinely a gain in detection sensitivities up to two orders of magnitude without specific optimization of the conditions with regards to fluorescence efficiency. 相似文献