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  • 1995-1999  (1)
  • 1985-1989  (2)
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  • 1
    Electronic Resource
    Electronic Resource
    College Park, Md. : American Institute of Physics (AIP)
    The Journal of Chemical Physics 86 (1987), S. 4843-4855 
    ISSN: 1089-7690
    Source: AIP Digital Archive
    Topics: Physics , Chemistry and Pharmacology
    Notes: The radical ion ⋅SO−3 was studied by in situ pulsed radiolysis of aqueous alkaline sodium sulfite solutions in a pulsed EPR spectrometer. Initial radical concentrations on the order of 5×10−4 M were generated, and detailed measurements of the decay of ⋅SO−3 magnetization were performed on the microsecond time scale. It was found that the second order decay of both longitudinal and transverse magnetization lags behind the second order decay of radical population when the reaction rate approaches the relaxation rates 1/T1,2. The observations may be explained in terms of the spin-pairing requirements for formation of a singlet reaction product. The spin pairing gives rise to a "passive'' form of radical pair mechanism (RPM) chemically induced dynamic electron polarization (CIDEP) which has previously gone unrecognized. RPM polarization therefore occurs in ⋅SO−3 encounters despite the lack of hyperfine dependent singlet–triplet mixing between radical reencounters, which is necessary for the accepted RPM mechanism. The implications of these observations for the interpretation of time-resolved EPR experiments are discussed.
    Type of Medium: Electronic Resource
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  • 2
    Electronic Resource
    Electronic Resource
    College Park, Md. : American Institute of Physics (AIP)
    The Journal of Chemical Physics 83 (1985), S. 2686-2707 
    ISSN: 1089-7690
    Source: AIP Digital Archive
    Topics: Physics , Chemistry and Pharmacology
    Notes: A dynamic polarization recovery method for measurement of electron spin T1 relaxation times in free radicals in liquids is described, which is valid even in the presence of chemically induced dynamic electron polarization (CIDEP) and fast chemical decay of the radicals. The method is based on pulsed microwave perturbation and detection of transient magnetization following radical creation in a short pulse. Analysis of the experimental approach and a theoretical description of the method is presented together with a detailed discussion of the advantages and the limitations of the technique. Electron T1 measurements are presented for 14 short-lived free radicals generated in aqueous solution. The magnitudes of the observed relaxation times, which range from 0.1 to 4 μs, are discussed within the framework of current theories of relaxation for small radicals in liquids. It is tentatively concluded that the spin rotation mechanism is responsible for the very short T1's in this series of radicals.
    Type of Medium: Electronic Resource
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  • 3
    ISSN: 1432-136X
    Keywords: Anoxia ; ATP ; Phosphodiester ; Lactic acidosis ; Turtle, Chrysemys
    Source: Springer Online Journal Archives 1860-2000
    Topics: Biology , Medicine
    Notes: Abstract Selected tissues (skeletal muscle, heart ventrical, and liver), sampled from turtles (Chrysemys picta bellii) at 3°C either under normoxic conditions or after 12 weeks of anoxic submergence were quantiaatively analysed for intracellular pH and phosphorus metabolites using 31P-NMR. Plasma was tested for osmolality and for the concentrations of lactate, calcium, and magnesium to confirm anoxic stress. We hypothesized that, in the anoxic animals, tissue ATP levels would be maintained and that the increased osmolality of the body fluids of anoxic turtles would be accounted for by a corresponding increase in the concentrations of phosphodiesters. The responses observed differed among the three tissues. In muscle, ATP was unchanged by anoxia but phosphocreatine was reduced by 80%; in heart, both ATP and phosphocreatine fell by 35–40%. The reduction in phosphocreatine in heart tissue at 3°C was similar to that observed in isolated, perfused working hearts from turtles maintained at 20°C but no decrease in ATP occurred in the latter tissues. In liver, although analyses of several specimens were confounded by line-broadening, neither ATP nor phosphocreatine was detectable in anoxic samples. Phosphosdiesters were detected in amounts sufficient to account for 30% of normoxic cell osmotic concentration in heart and 11% and 12% in liver and muscle, respectively. The phosphodiester levels did not change in anoxia. Heart ventricular phosphodiester levels in turtles at 3°C were significantly higher than those determined for whole hearts from turtles at 20°C. 1H, 13C and 31P NMR analyses of perchloric acid extracts of heart and skeletal muscle from 20°C turtles con firmed that the major phosphodiester observed by NMR in these tissues is serine ethanolamine phosphate. We conclude that the three types of tissues studied differ substantially in their ability to maintain levels of ATP during anoxia, and that liver may continue to function despite NMR-undetectable levels of this metabolite. In addition, we conclude that phosphodiesters do not serve as regulated osmolytes during anoxia, and that the functional significance of their high concentrations in turtle tissues remains uncertain.
    Type of Medium: Electronic Resource
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