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51.
Poly[2-(perfluorooctyl)ethyl acrylate-co-poly(ethylene glycol) methacrylate], P(POA-co-PEGm) was prepared as a new surfactant for scCO2. The random copolymer was obtained by the radical polymerization of 2-(perfluorooctyl)ethyl acrylate (POA) and poly(ethylene
glycol) methacrylate (PEGm) in DMF. The molar ratio of the POA and PEGm units in the copolymer was POA/PEGm = 0.972/0.028
by 1H NMR. The molecular weight and molecular weight distribution were estimated by size exclusion chromatography to be Mn = 133,000
and Mw/Mn = 8.25, respectively. It was suggested that the copolymer formed micellar aggregates with the cores of the PEGm
chains in scCO2, based on the analyses of the copolymer in hexafluorobenzene by 1H NMR and dynamic light scattering. The copolymer was soluble in scCO2 and had a cloud point at a much higher pressure than the critical pressure. It was found that the copolymer solubilized CO2-insoluble proteins such as bovine serum albumin and subtilisin Carlsberg in scCO2. The solubility of the copolymer was not influenced by the presence of the proteins; however, the solubility decreased in
the presence of a small amount of water along with the protein. The activity of the subtilisin slightly decreased when only
placed in scCO2, whereas a marked decrease in the activity was observed for the subtilisin in the presence of the copolymer in scCO2. The subtilisin activity decreased as the CO2 pressure increased. 相似文献
52.
Tokutaro Ogata Misae Doe Aya Matsubara Eri Torii Chiaki Nishiura Arisa Nishiuchi Yusuke Kobayashi Tetsutaro Kimachi 《Tetrahedron》2014
The oxidative intramolecular cyclization of 3-hydroxyalkyl-1,2,4-trimethoxynaphthalenes was investigated. A series of 1,2-naphthoquinone fused cyclic ethers were synthesized directly from 3-hydroxyalkyl-1,2,4-trimethoxynaphthalenes by exposure to diammonium cerium (IV) nitrate. To understand the reaction mechanism, the intramolecular cyclization of 3-hydroxyalkyl-naphthoquinones that were formed as reaction intermediates was also examined. The results suggested that the reaction proceeds by a stepwise oxidation–cyclization mechanism. Using this methodology, five-step synthesis of rhinacanthone was achieved with high yield. 相似文献
53.
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55.
Eri Yoshida 《Colloid and polymer science》2010,288(18):1745-1749
The photoradical polymerization of methyl methacrylate (MMA) was performed at room temperature using (2RS,2’RS)-azobis(4-methoxy-2,4-dimethylvaleronitrile)
as the initiator and 4-methoxy-2,2,6,6-tetramethylpiperidine-1-oxyl (MTEMPO) as the mediator in the presence of (η6-benzene)(η5-cyclopentadienyl)FeII hexafluorophosphate (BzCpFeII). The bulk polymerization provided narrower molecular weight distributions (Mw/Mn = 1.4 − 1.5) than the solution polymerization
in acetonitrile, although BzCpFeII was insoluble in MMA. The polymerization rate was retarded by an increase in the amount of BzCpFeII. BzCpFeII, which had no ability to control the molecular weight by itself, could control it through the interaction with MTEMPO. The
interaction of BzCpFeII and MTEMPO was attributed to the electron transfer involving the MTEMPO–aminoxy anion redox system and the iron redox system.
The polymerization was confirmed to occur in accordance with a living mechanism because linear correlations were obtained
for both the plots of the first order time–conversion and the conversion–molecular weight. 相似文献
56.
Eri Yoshida 《Colloid and polymer science》2010,288(12-13):1321-1325
The self-assembly of poly(allylamine hydrochloride) (PAH) through an electrostatic interaction with sodium dodecyl sulfate (SDS) was explored. PAH itself showed no self-assembly in water. A light scattering study demonstrated that PAH formed monodispersed spherical aggregates in water in the presence of SDS. The hydrodynamic diameter of the aggregates was estimated to be ca. 170 nm based on the cumulant analysis. The scattering intensity and UV absorbance at 258 nm based on the aggregation increased with an increase in the molar ratio of SDS to the allylamine hydrochloride unit (SDS/AH), indicating an increase in the number of aggregates. On the other hand, the hydrodynamic diameter of aggregates was constant, i.e., independent of the SDS/AH ratio. The constant size of the aggregates in spite of the increase in the number of aggregates suggests the formation of the micellar aggregates by the intramolecular association through an electrostatic interaction. 相似文献
57.
Eri Yoshida 《Colloid and polymer science》2010,288(1):73-78
The photoradical polymerization of vinyl acetate was performed using 4-methoxy-2,2,6,6-tetramethylpiperidine-1-oxyl (MTEMPO) as the mediator in the presence of bis(alkylphenyl)iodonium hexafluorophosphate (BAI). The MTEMPO/BAI system using 2,2’-azobis(isobutyronitrile) or 2,2’-azobis(4-methoxy-2,4-dimethylvaleronitrile) as the initiator did not succeed in controlling the molecular weight and produced polymers that showed a bimodal gel permeation chromatography with the broad molecular weight distribution. On the other hand, the polymerization using 1-(cyano-1-methylethoxy)-4-methoxy-2,2,6,6-tetramethylpiperidine and BAI proceeded by the living mechanism based on linear increases in the first order time–conversion and conversion–molecular weight plots. The molecular weight distribution also increased with the increasing conversion due to cloudiness of the solution as the polymerization proceeded. It was found that the polymerization had a photolatency because the propagation stopped by interruption of the irradiation and was restarted by further irradiation. 相似文献
58.
Aqueous chromatography system using pH- and temperature-responsive stationary phase with ion-exchange groups 总被引:1,自引:0,他引:1
Ayano E Nambu K Sakamoto C Kanazawa H Kikuchi A Okano T 《Journal of chromatography. A》2006,1119(1-2):58-65
We report on the development of a novel analytical HPLC technique of nonsteroidal anti-inflammatory drugs (NSAIDs), such as ibuprofen, ketoprofen and naproxen, with an isocratic aqueous mobile phase. In this study, we designed a new pH- and temperature-responsive copolymer of N-isopropylacrylamide (NIPAAm), butyl methacrylate (BMA) and N,N-dimethylaminopropylacrylamide (DMAPAAm). The copolymer was modified with cross-linked poly(NIPAAm-co-BMA-co-DMAPAAm) (IBD) hydrogel on to aminopropyl silica beads, and the products were evaluated as HPLC packing materials for an ion-exchange- and temperature-responsive chromatography. The property of the surface of the stationary phase was altered from hydrophilic to hydrophobic, and from charged to non-charged by changes in the temperature and pH. In addition, it is possible that ion-exchange groups can appear or be hidden on the polymer chain surface by temperature changes. The interactions of NSAIDs with this stationary phase were controlled by the temperature and the pH with a constant aqueous mobile phase. PH- and temperature-responsive chromatography is expected to be useful for the separation of pharmaceuticals and biomolecules. 相似文献
59.
Extensive research has been carried out on functional polymers which are currently playing important roles in various fields such as medicine and engineering. Such functional polymers which respond to various kinds of stimuli are termed 'intelligent materials'. Poly(N-isopropylacrylamide) (PNIPAAm), a temperature-responsive polymer, was utilized as a chromatography column matrix modifier for a novel chromatographic approach in which only aqueous media are used as a mobile phase. The ability of the developed temperature-responsive chromatography system to separate solutes without using an organic solvent is advantageous from the point of view of maintaining the structure and activity of bioactive compounds. Recently, we designed and synthesized a new pH- and temperature-responsive copolymer as a representative of such environment-responsive polymers and grafted it onto aminopropyl silica beads. The products were evaluated as HPLC packing materials for separation systems based on a new concept, according to which the properties of the stationary phase surface are altered by external stimuli such as pH and temperature. This chromatography system utilizing the PNIPAAm copolymer is very useful for the separation of bioactive substances, such as proteins and peptides, because separation in the aqueous mobile phase is controlled solely by changing the temperature. This analytical system reduces organic waste because no organic solvent is used to separate the solutes and can therefore be classified as environmentally friendly. Future medical and pharmaceutical applications are expected. 相似文献
60.
Tsuda M Yasuda T Fukushi E Kawabata J Sekiguchi M Fromont J Kobayashi J 《Organic letters》2006,8(19):4235-4238
Diffusion-ordered NMR spectroscopy (DOSY) is a versatile and powerful NMR technique and a noninvasive analytical method for mixture analysis that does not require prior physical separation of the analytes. In our search for new metabolites from natural resources, DOSY was applied for constituent analysis of crude bromopyrrole fractions separated from an Okinawan marine sponge Agelas sp. so that two new bromopyrrole alkaloids, agesamides A (1) and B (2), have been isolated. The structures and relative stereochemistry of 1 and 2 were elucidated from spectroscopic data. 相似文献