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111.
Brewer Christopher M. Bujalski Duane R. Parent Virginia E. Su Kai Zank Gregg A. 《Journal of Sol-Gel Science and Technology》1999,14(1):49-68
We have undertaken a systematic study of the oxidation chemistry for a range of SiOC ceramics derived from silsesquioxane polymeric precursors. This study examines the oxidation for 500 hours at 600, 800, 1000 and 1200°C for four SiOC powders. The material changes upon oxidation were characterized qualitatively by color change and optical microscopy and quantitatively by weight and composition change. In this study we employ a very easy method that uses the weight change upon oxidation and a carbon analysis after oxidation to arrive at the composition of the oxidized SiOC. Combined these qualitative and quantitative techniques have shown that on oxidation at 800 and 600°C the SiOC composition is more rapidly changed to that of silica than oxidation over the same time frame at 1000 or 1200°C. The data indicates that this difference is due to the relative rates of oxidation of the excess carbon versus the Si—C bonds in the SiOC. At lower temperatures initially the carbon oxidation predominates which leads to higher porosity throughout the material and an increase in the surface area with eventually complete oxidation to silica. At higher temperatures the Si—C bond oxidation rate is comparable to the rate of oxidation of carbon. This allows a silica-like surface to build up on the SiOC, which slows all subsequent reactions due to the necessity to diffuse O2 in and COx out of the bulk. Under these oxidation conditions materials that originally contain high amounts of excess carbon are more quickly oxidized to silica than those that contain minimal amounts of excess carbon, as confirmed by elemental analysis and optical microscopy. Regardless of the time or temperature of the oxidation conditions no materials were found to be completely stable to oxidation. SiOC materials with low levels of excess carbon showed the best resistance to change upon oxidation. 相似文献
112.
Mehlstäubl M Kottas GS Colella S De Cola L 《Dalton transactions (Cambridge, England : 2003)》2008,(18):2385-2388
A tetrametallic iridium-ytterbium complex has been synthesised that shows sensitized near-infrared emission (lambda(max) = 976 nm) upon excitation of the iridium unit in the visible region (400 nm) due to efficient energy transfer from the iridium units to the Yb(III) ion. The iridium phosphorescence is quenched nearly quantitatively while the ytterbium ion emits brightly in the NIR. 相似文献
113.
Dhanpat Rai Mikazu Yui Dean A. Moore Gregg J. Lumetta Kevin M. Rosso Yuanxian Xia Andrew R. Felmy Frances N. Skomurski 《Journal of solution chemistry》2008,37(12):1725-1746
No thermodynamic data for Th complexes with aqueous Si are available. To obtain such data, extensive studies on ThO2(am) solubility were carried out as functions of: (1) a wide range of aqueous silica concentrations (0.0004 to 0.14 mol⋅L−1) at fixed pH values of about 10, 11, 12, and 13; and (2) and variable pH (ranging from 10 to 13.3) at fixed aqueous Si concentrations
of about 0.006 mol⋅L−1 or 0.018 mol⋅L−1. The samples were equilibrated over long periods (ranging up to 487 days), and the data showed that steady-state concentrations
were reached in < 29 days. X-ray diffraction, FTIR, and Raman analyses of the equilibrated solid phases showed that the Th
solids were amorphous ThO2(am) containing some adsorbed Si. The solubility of ThO2(am) at pH values ranging from 10 to 13.3 at fixed 0.018 mol⋅L−1 aqueous Si concentrations decreases rapidly with an increase in pH, and increases dramatically with an increase in Si concentrations
beyond about 0.003 mol⋅L−1 at fixed pH values > 10. The data were interpreted using both the Pitzer and SIT models, and required only the inclusion
of one mixed-hydroxy-silica complex of Th [Th(OH)3(H3SiO4)32−]. Both models provided similar complexation constant values for the formation of this species. Density functional theory
calculations predict complexes of this stoichiometry, having six-fold coordination of the Th cation, to be structurally stable.
Predictions based on the fitted value of log 10
K
0=−18.5±0.7 for the ThO2(am) solubility reaction involving Th(OH)3(H3SiO4)32−[ThO2(am)+3H4SiO4+H2O↔Th(OH)3(H3SiO4)32−+2H+], along with the thermodynamic data for aqueous Si species reported in the literature, agreed closely with the extensive
experimental data and showed that under alkaline conditions aqueous Si makes very strong complexes with Th. 相似文献
114.
Alex R. Jurgens Kenneth Green Edward R. Ruso Mellard N. Jennings David M. Blum Gregg B. Feigelson 《合成通讯》2013,43(8):1171-1177
An improved scalable procedure for preparation of an α-ketoester acyl anion synthon is described. 相似文献
115.
Kathryn M. Chepiga Changming Qin Joshua S. Alford Spandan Chennamadhavuni Timothy M. Gregg Jeremy P. Olson Huw M.L. Davies 《Tetrahedron》2013,69(27-28):5765-5771
Catalytic enantioselective methods for the generation of cyclopropanes have been of long standing pharmaceutical interest. Chiral dirhodium(II) catalysts prove to be an effective means for the generation of diverse cyclopropane libraries. Rh2(R-DOSP)4 is generally the most effective catalyst for asymmetric intermolecular cyclopropanation of methyl aryldiazoacetates with styrene. Rh2(S-PTAD)4 provides high levels of enantioinduction with ortho-substituted aryldiazoacetates. The less-established Rh2(R-BNP)4 plays a complementary role to Rh2(R-DOSP)4 and Rh2(S-PTAD)4 in catalyzing highly enantioselective cyclopropanation of 3-methoxy substituted aryldiazoacetates. Substitution on the styrene has only moderate influence on the asymmetric induction of the cyclopropanation. 相似文献
116.
Qin Zhao Gregg M. Schieffer Matthew W. Soyk Timothy J. Anderson R. S. Houk Ethan R. Badman 《Journal of the American Society for Mass Spectrometry》2010,21(7):1208-1217
Positive ions from cytochrome c are studied in a 3-D ion trap/ion mobility (IM)/quadrupole-time-of-flight (TOF) instrument with three independent ion sources. The IM separation allows measurement of the cross section of the ions. Ion/ion reactions in the 3-D ion trap that remove protons cause the cytochrome c ions to refold gently without other degradation of protein structure, i.e., fragmentation or loss of heme group or metal ion. The conformation(s) of the product ions generated by ion/ion reactions in a given charge state are similar regardless of whether the cytochrome c ions are originally in +8 or +9 charge states. In the lower charge states (+1 to +5) cytochrome c ions made by the ion/ion reaction yield a single IM peak with cross section of ~1110 to 1180 Å2, even if the original +8 ion started with multiple conformations. The conformation expands slightly when the charge state is reduced from +5 to +1. For product ions in the +6 to +8 charge states, ions created from higher charge states (+9 to +16) by ion/ion reaction produce more compact conformation(s) in somewhat higher abundances compared with those produced directly by the electrospray ionization (ESI) source. For ions in intermediate charge states that have a variety of resolvable conformers, the voltage used to inject the ions into the drift tube, and the voltage and duration of the pulse that extracts ions from the ion trap, can affect the observed abundances of various conformers. 相似文献
117.
118.
Garilyn M Jentarra Shannon L Olfers Stephen G Rice Nishit Srivastava Gregg E Homanics Mary Blue SakkuBai Naidu Vinodh Narayanan 《BMC neuroscience》2010,11(1):19
Background
Rett syndrome (RTT), a common cause of mental retardation in girls, is associated with mutations in the MECP2 gene. Most human cases of MECP2 mutation in girls result in classical or variant forms of RTT. When these same mutations occur in males, they often present as severe neonatal encephalopathy. However, some MECP2 mutations can also lead to diseases characterized as mental retardation syndromes, particularly in boys. One of these mutations, A140V, is a common, recurring missense mutation accounting for about 0.6% of all MeCP2 mutations and ranking 21st by frequency. It has been described in familial X-linked mental retardation (XLMR), PPM- X syndrome (Parkinsonism, Pyramidal signs, Macroorchidism, X-linked mental retardation) and in other neuropsychiatric syndromes. Interestingly, this mutation has been reported to preserve the methyl-CpG binding function of the MeCP2 protein while compromising its ability to bind to the mental retardation associated protein ATRX. 相似文献119.
Gregg F. Keaney 《Tetrahedron letters》2005,46(23):4031-4034
Rhodium perfluorobutyramide (Rh2(pfm)4) has been shown to catalyze the conversion of olefins to trichloroethoxysulfonyl, nosyl, and tosyl aziridines. Advantages of this aziridination procedure include the microwave-assisted preparation of the catalyst and the practical use of the alkene substrate as the limiting reagent. 相似文献