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note
-
Similar parameters give a good fit to near-UV absorption spectra of GSH → arsenite titrations (Supporting Information), but the fit is poor at larger excess of GSH, which might be due to spectral contributions from an increasing amount of the GSH thiolate anion.
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29
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17444399517
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note
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2:3 value corresponds to a clear minimum in the sum of squares residuals in the Specfit analysis of this titration data.
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30
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17444425518
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note
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Rapid continuous stirring of the ITC cell led to equilibration of these samples between injections, as indicated by the return to baseline and the absence of baseline drift over the course of As(III) → GSH titrations.
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31
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17444391477
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note
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The GSH → arsenite ITC data eventually return to a smaller heat of dilution at higher molar ratios, but there is some discrepancy with the fit, presumably because of the large deviation from ideal solution behavior at high titrant (solute) concentrations.
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32
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17444409126
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note
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When K is small, there is a larger uncertainty in the corresponding value of ΔH, which is particularly true for the intermediate 1:2 species.
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33
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0021137469
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17444390290
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note
-
The DHLA carboxylate is separated by four additional methylenes from the thiols and is not expected to effect dithiolate coordination to As(III).
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0000969945
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