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71.
Ghiladi RA Chufan EE del Río D Solomon EI Krebs C Huynh BH Huang HW Moënne-Loccoz P Kaderli S Honecker M Zuberbühler AD Marzilli L Cotter RJ Karlin KD 《Inorganic chemistry》2007,46(10):3889-3902
In the further development and understanding of heme-copper O2-reduction chemistry inspired by the active-site chemistry in cytochrome c oxidase, we describe a dioxygen adduct, [(F8TPP)FeIII-(O22-)-CuII(TMPA)](ClO4) (3), formed by addition of O2 to a 1:1 mixture of the porphyrinate-iron(II) complex (F8TPP)FeII (1a) {F8TPP = tetrakis(2,6-difluorophenyl)porphyrinate dianion} and the copper(I) complex [(TMPA)CuI(MeCN)](ClO4) (1b) {TMPA = tris(2-pyridylmethyl)amine}. Complex 3 forms in preference to heme-only or copper-only binuclear products, is remarkably stable {t1/2 (RT; MeCN) approximately 20 min; lambda max = 412 (Soret), 558 nm; EPR silent}, and is formulated as a peroxo complex on the basis of manometry {1a/1b/O2 = 1:1:1}, MALDI-TOF mass spectrometry {16O2, m/z 1239 [(3 + MeCN)+]; 18O2, m/z 1243}, and resonance Raman spectroscopy {nu(O-O) = 808 cm-1; Delta16O2/18O2 = 46 cm-1; Delta16O2/16/18O2 = 23 cm-1}. Consistent with a mu-eta2:eta1 bridging peroxide ligand, two metal-O stretching frequencies are observed {nu(Fe-O) = 533 cm-1, nu(Fe-O-Cu) = 511 cm-1}, and supporting normal coordinate analysis is presented. 2H and 19F NMR spectroscopies reveal that 3 is high-spin {also muB = 5.1 +/- 0.2, Evans method} with downfield-shifted pyrrole and upfield-shifted TMPA resonances, similar to the pattern observed for the structurally characterized mu-oxo complex [(F8TPP)FeIII-O-CuII(TMPA)]+ (4) (known S = 2 system, antiferromagnetically coupled high-spin FeIII and CuII). M?ssbauer spectroscopy exhibits a sharp quadrupole doublet (zero field; delta = 0.57 mm/s, |DeltaEQ| = 1.14 mm/s) for 3, with isomer shift and magnetic field dependence data indicative of a peroxide ligand and S = 2 formulation. Both UV-visible-monitored stopped-flow kinetics and M?ssbauer spectroscopic studies reveal the formation of heme-only superoxide complex (S)(F8TPP)FeIII-(O2-) (2a) (S = solvent molecule) prior to 3. Thermal decomposition of mu-peroxo complex 3 yields mu-oxo complex 4 with concomitant release of approximately 0.5 mol O2 per mol 3. Characterization of the reaction 1a/1b + O2 --> 2 --> 3 --> 4, presented here, advances our understanding and provides new insights to heme/Cu dioxygen-binding and reduction. 相似文献
72.
The design and performance of a new time-of-flight mass spectrometer is reported. The instrument combines the advantages of a pulsed drawout TOF analyzer with a liquid secondary ion source. Differences from commercially available pulsed TOF analyzers (Wiley/McLaren type) are discussed with regard to operation with ion desorption from a liquid matrix. 相似文献
73.
74.
Jeffery B. Press Victor T. Bandurco Elizabeth M. Wong Zoltan G. Hajos Ramesh M. Kanojia Robert A. Mallory Edward G. Deegan James J. Mcnally Jerry R. Roberts Mary Lou Cotter David W. Graden John R. Lloyd 《Journal of heterocyclic chemistry》1986,23(6):1821-1828
Synthesis of 5,6-dimethoxyquinazolin-2(1H)-one derivatives was the subject of investigations leading to the preparation of title compounds 11, 13, 14 and 26 . Target quinazolines 1 were synthesized in three ways; the route starting from o-vanillin via the intermediacy of 6-amino-2,3-dimethoxyacetophenone ( 19 ) was used for most of the preparative work. The unexpected formation of an acid-labile dimer of 13 was discovered and solid state 13C nmr was used for structural assignment. The 5-methoxy substituent in these systems shows anomalous spectral characteristics and, in one case, was cleaved in acid media to 22 . 相似文献
75.
Stimulated electronic Raman scattering in Ba vapour is used to efficiently convert the output of a XeCl excimer laser (308 nm) to the blue region (475 nm). Photon conversion efficiencies of up to 20% and output energies in the blue greater than 5 mJ are obtained. The multi-line structure of the XeCl laser emission is reproduced in the generated Stokes spectrum. 相似文献
76.
It is shown that for generation of infrared radiation by stimulated Raman scattering, the diffraction spread of the Stokes wave can have a significant effect on the threshold. Compared with an analysis in which gain focussing is neglected, the threshold powers may be much higher with a corresponding reduction in tuning range. The design of a Raman oscillator is considerably influenced by these diffraction effects, and also it is found that the Stokes wave is subject to frequency-pulling which is dependent on the pump power. 相似文献
77.
Moyer SC Cotter RJ Woods AS 《Journal of the American Society for Mass Spectrometry》2002,13(3):274-283
An investigation of phosphate loss from phosphopeptide ions was conducted, using both atmospheric pressure matrix-assisted laser desorption/ionization (AP MALDI) and electrospray ionization (ESI) coupled to an ion trap mass spectrometer (ITMS). These experiments were carried out on a number of phosphorylated peptides in order to investigate gas phase dephosphorylation patterns associated with phosphoserine, phosphothreonine, and phosphotyrosine residues. In particular, we explored the fragmentation patterns of phosphotyrosine containing peptides, which experience a loss of 98 Da under collision induced dissociation (CID) conditions in the ITMS. The loss of 98 Da is unexpected for phosphotyrosine, given the structure of its side chain. The fragmentation of phosphoserine and phosphothreonine containing peptides was also investigated. While phosphoserine and phosphothreonine residues undergo a loss of 98 Da under CID conditions regardless of peptide amino acid composition, phosphate loss from phosphotyrosine residues seems to be dependent on the presence of arginine or lysine residues in the peptide sequence. 相似文献
78.
79.
D. M. Thomas J. M. Cotter D. Holford 《Journal of Radioanalytical and Nuclear Chemistry》1992,161(2):313-323
An effort to define and characterize the environmental effects that control the release and mobility of radon in the environment is presented. The results of our preliminary field experiments on the long-term study of our radon activity measurements are reported. 相似文献
80.
Low pressure SF6 with its isotopes in natural abundance was irradiated by a pulsed CO2 laser operated on theP20 line (10.6 μm band). Dissociation yields of32SF6 and34SF6 were measured separately. If the radiation is focussed into the cell, the dissociation yield is proportional to the 3/2 power
of the laser energy, as was derived under general conditions and confirmed experimentally. The reaction probabilityP(Φ), the fraction of molecules dissociated by an energy flux Φ, was measured using parallel light. For both isotopes,P(Φ) saturates at high energy flux close toP=1. At a lower flux (2 J cm−2), the dissociation probability of32SF6 displays a threshold, whereas the dissociation probability of34SF6 is a very steep function of Φ over the whole range of fluxes.P(Φ) at the higher energy flux was measured in a cavity absorption cell, in which up to 80% of the molecules were dissociated
by a single pulse. Below 0.2 mbar SF6 the dissociation yields for both isotopes are pressure independent. Above 2 mbar the isotopic selectivity is completely lost.
Addition of hydrogen always decreases the dissociation yields. 相似文献