Ps. Woolley et al., SURFACE-ENHANCED RESONANCE RAMAN-SPECTRA OF WATER-INSOLUBLE TETRAPHENYLPORPHYRIN AND CHLOROPHYLL-A ON SILVER HYDROSOLS WITH A DIOXANE MOLECULAR SPACER, Chemical physics letters, 258(3-4), 1996, pp. 501-506
A surface-enhanced resonance Raman spectroscopic (SERRS) study of tetr
aphenylporphyrin (TPP) on a silver hydrosol, obtained by mixing a diox
ane solution of the water-insoluble TPP with the hydrosol, indicates t
hat there is no metallation of the porphyrin. By contrast, water-solub
le porphyrins such as tetra-N-methylpyridylporphyrin (TMPyP) have been
shown to undergo metallation, We suggest that the TPP is encapsulated
within a dioxane envelope which is co-adsorbed to the surface of the
silver hydrosol and functions as a molecular spacer. This spacer does
not eliminate the analytical advantages afforded by SERRS, but does pr
event significant perturbation from the native conformation, as is dem
onstrated by results obtained using chlorophyll a.