Electrochemical impedance spectroscopy (EIS) is used to compare the apparent electron transfer rate constant (k(app)) for a series of alkanethiol and of carbohydrate-terminated alkanethiol self-assembled monolayers (SAMs) on both flat gold and on nanoporous gold (np-Au). Using the surface area for np-Au determined by oxide stripping, the values of k(app) for the alkanethiol modified np-Au are initially over two orders of magnitude smaller than the values found on flat Au. This result provides evidence that the diffusing redox probe Fe(CN)(6)(3-/4-) only accesses a fraction of the np-Au surface after alkanethiol modification suggesting very limited wetting of the internal pores due to the hydrophobic nature of these surfaces. In contrast, for np-Au modified by carbohydrate-terminated (mannose or galactose) alkanethiols the values of k(app) are about 10-40 fold smaller than on flat gold, suggesting more extensive access of the diffusing redox probe within the pores and better but still incomplete wetting, a result also found for modification of np-Au with mercaptododecanoic acid. A short chain PEG thiol derivative is found to result in a comparison of k(app) values that suggests nearly complete wetting of the internal pores for this highly hydrophilic derivative. These results are of significance for the potential.applications of SAM modified np-Au in electrochemical sensors, especially for those based on carbohydrate-protein recognition, or those of np-Au modified by SAMs with polar terminal groups. (C) 2016 Elsevier B.V. All rights reserved.