Reported here is an efficient recognition of K+ by 15-crown-5 functionalized gold nanoparticles in aqueous matrix containing physiologically important cations, such as Li+, Cs+, NH4+, Mg2+, Ca2+, and excess amount of Na+. Upon exposure to K+, the colloidal solution changes from red to blue, in response to surface plasmon absorption of dispersed and aggregated nanoparticles. The concentration ranges of K+ detected in this study are 0.099-0.48 mM and 7.6 microM-0.14 mM, when concentrations of colloidal gold are 54.9 and 7.1 nM, respectively. Recognition of K+ and formation of the aggregates are proposed via a sandwich complex of 2:1 between 15-crown-5 moiety and K+. Also discussed is the possibility of a preorganized structure of 15-crown-5 at the water-organic interface for the efficient complexation with K+.

One of the critical issues for the realization of molecular electronics is the development of ideal molecule-electrode contacts that render efficient charge transportation and thus attenuate the unwanted voltage drop and power loss. The conductance at the single-molecule level has long been expected to be correlated strongly with the electrode materials. However, other than gold, systematic studies of a homologous series of molecules to extract the headgroup-metal contact conductance (G(n=0)) have not been reported. Carefully examined herein are the conductances of alkanedithiols anchored onto electrode materials of Au and Pt as well as the conductances of alkanediisothiocyanates on Au, Pd, and Pt by utilizing the method of STM-BJ (scanning tunneling microscopy break junction). In comparison with Au substrate, Pd and Pt are group 10 elements with stronger d-orbital characteristics, and larger local density of states near the Fermi level. The model compounds, SCN(CH(2))(n)NCS (n = 4, 6, and 8), are studied because the isothiocyanate (-NCS) headgroup is a versatile ligand for organometallics, an emerging class of molecular wires, and can bind to substrates of noble metals to complete a metal-molecule-metal configuration for external I-V measurements. Also studied include alkanedithiols, one of the most scrutinized systems in the field of single-molecule conductance. The results show that the conductance for single molecules bridged between a pair of Pt electrodes is about 3.5-fold superior to those between Au electrodes. On all electrode materials, observed are two sets of conductance values, with the smaller set being 1 order of magnitude less conductive. These findings are ascribed to the degree of electronic coupling between the headgroup and the electrode.

A thiolated bis(cobalt) cofacial diporphyrin chemisorbed on an edge plane pyrolytic graphite electrode has the electrocatalytic activity of a four-electron (n g 3.6) dioxygen reduction catalyst. When chemisorbed on a gold electrode surface, the same catalyst exhibits the activity of only a two-electron catalyst, producing hydrogen peroxide (n ) 2.1). The edge plane graphite surface thus plays a crucial, but not understood, role in designed dioxygen reduction catalysis. Analysis of X-ray photoelectron spectroscopy and UV-vis results is consistent with the rings of the thiolated porphyrins being coplanar to the Au electrode plane. A structurally modified catalyst exhibits greater coplanarity and a slight increase in activity (n ≈ 2.4). The present results set the stage for a strategy of cochemisorbing functionalities onto the thiolated diporphyrin-coated Au surface, seeking those functionalities which will chemically mimic the graphite surface and elevate the catalytic reactivity to a four-electron dioxygen reduction. Such functionalities could include host-guest cochemisorption of putative carbon surface ligands within the porphyrin electrode cavity. † Present address: Collman, J. P.; Hutchison, J. E.; Lopez, M. A.; Tabard, A.; Guilard, R.; Seok, W. K.; Ibers, J. A.; L'Her, M. J. Am. Chem. Soc. 1992, 114, 9869-9877.(3) (a) Collman, J. P.; Hendricks, N. H.; Leidner, C. R.; Ngameni, E.; L'Her, M. Inorg. Chem. 1988, 27, 387. (b) Collman, J. P.; Wagenknecht, P. S.; Hutchison, J. E.

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