PubMed · 1180228
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1975. Analytical guide: manganese.. https://doi.org/10.1080/0002889758507322
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Water oxidation at photosystem II Mn-cluster is mediated by the redox-active tyrosine Y(Z). We calculated the redox potential (E(m)) of Y(Z) and its symmetrical counterpart Y(D), by solving the linearized Poisson-Boltzmann equation. The calculated E(m)(Y( )/Y(-)) were +926 mV/+694 mV for Y(Z)/Y(D) with the Mn-cluster in S2 state. Together with the asymmetric position of the Mn-cluster relative to Y(Z/D), differences in H-bond network between Y(Z) (Y(Z)/D1-His(190)/D1-Asn(298)) and Y(D) (Y(D)/D2-His(189)/D2-Arg(294)/CP47-Glu(364)) are crucial for E(m)(Y(Z/D)). When D1-His(190) is protonated, corresponding to a thermally activated state, the calculated E(m)(Y(Z)) was +1216 mV, which is as high as the E(m) for P(D1/D2). We observed deprotonation at CP43-Arg(357) upon S-state transition, which may suggest its involvement in the proton exit pathway. E(m)(Y(D)) was affected by formation of P(D2)(+) (but not P(D1)(+)) and sensitive to the protonation state of D2-Arg(180). This points to an electrostatic link between Y(D) and P(D2).
In this work, methodologies to determine manganese (Mn) in urine and whole blood by electrothermal atomic absorption spectrometry were developed. The use of Ru, Rh, and Zr as permanent modifiers, Pd as a modifier in solution, and the condition without modifier were investigated for the direct determination of Mn in urine and whole blood samples. The best results for Mn in urine and in whole blood were obtained without modifier use. The analytical characteristic, such as accuracy, precision and limit of detection of the proposed methodology were adequate.
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