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However, if the pH were lower and/or the time scale of diffusion shorter, a one-electron process might have to be considered instead, because the oxidation may stop at the level of the first cation radical intermediate since this has no time to deprotonate to yield the easily oxidizable phenoxy radical whose oxidation gives rise to the second electron exchange.
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In the present case, adrenaline is a monocation and is presumably replaced by protons and other monovalent cations present in the extracellular medium. However, one must take into account that (although the exact structure of the polyelectrolyte complex is still unknown) the adrenaline cation is prone to form several strong hydrogen bonds to the carboxylate and other groups of the peptidic backbone, while the monovalent ions should only counterbalance the carboxylate charge and therefore give rise to dipole - dipole repulsion between the protonated or ion-paired carboxylate groups. Instead, exchange of the adrenaline cation by polycharged cations is expected to contract the matrix. This has indeed been reported for trivalent ions: for example, the lanthanum trication induces a measurable contraction of the matrix. See: M. J. Curran, M. S. Brodwick, J. Gen. Physiol. 1991, 98, 771.
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-1 depending on the extracellular medium composition), and that ii) the released flux correlates with the granule swelling. Nevertheless, neither of these facts disagrees with diffusion-controlled swelling and diffusion-controlled release as we advocate. Moreover, if the diffusivity of serotonin can be determined in their experiments, it means that diffusion of serotonin is the rate-determining step.
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45
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0039025588
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exp, albeit of lesser magnitude than in Figure 5b. Inspection of the ca. 600 spikes that have been treated show that ca. two thirds of the amperometric traces that do not show an obvious foot component (viz., ≃ 70-80% of the events) present this characteristic feature of a foot release merged with the rising part of the spike release. Since this indicates that the foot release occurred for ≃0.5-1 ms for these events, this validates a posteriori our evaluation of an average of ca. 2 ms duration for a foot release under our conditions.
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46
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0040209560
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note
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2+ under our conditions) to the pore entrance, so that in the vesicle matrix, exchange of the adrenaline cation should occur mainly by monovalent ions [note that Eq. (1) indicates that two protons are produced in the artificial synaptic gap per adrenaline cation detected]. Since the alteration energy per exchanged site in the matrix is expected to be larger when the exchange involves monovalent ions rather than divalent ones (see refs. [12b, 13]), the fact that we observe shorter foot releases than in patch-clamp experiments is perfectly consistent with our considerations on the transition between foot and spike release.
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