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0343492565
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note
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We acknowledge that the adsorbate concentrations employed by Xu et al. 38 and by Yamada and Uosaki 40,41 were substantially lower than those employed in the present study. These differences in concentration might invalidate the adsorption model and corresponding analysis presented here. Future studies will explore concentration effects and will attempt to characterize any observable physisorbed intermediates.
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43
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0342622270
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note
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Recently, Jung et al. 5 proposed that the rates of chemisorption of thiols and disulfides differ due to the different manner in which they displace solvent from the surface. The authors proposed that while thiols require only one site for chemisorption, disulfides simultaneously require two sites for chemisorption. Since, however, the dithiol 1 and the disulfide 3 both simultaneously require two adsorption sites and the rate of adsorption of 1 appears substantially faster than that of 3, our data fail to support their proposal.
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45
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0343928293
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note
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It seems plausible that a similar but less pronounced effect might rationalize the reportedly slower rate of adsorption onto gold for normal dialkyl disulfides compared to that for normal alkanethiols. 8,20,32
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