Ja. Baldwin et al., SURFACE-ENHANCED RAMAN-SCATTERING OF MERCAPTOPYRIDINES AND PYRAZINAMIDE INCORPORATED IN SILVER COLLOID ADSORBATE FILMS, Langmuir, 13(14), 1997, pp. 3744-3751
Pyrazinamide (pza) and 2-mercaptopyridine (2-MPy) are shown to form Ag
colloid-adsorbate films at the interface between an aqueous Ag colloi
d and a solution of an adsorbate in dichloromethane. By contrast, unde
r the same conditions, 4-mercaptopyridine (4-MPy) forms Ag organosol a
ggregates by the interface transfer of adsorbate-covered Ag colloidal
particles from the aqueous phase to the organic phase, This result con
firms that formation of Ag colloid-adsorbate films is an adsorbate spe
cific process. Transmission electron and optical microscopy and surfac
e plasmon adsorption measurements are used to characterize the morphol
ogy of the deposited Ag colloid-adsorbate structures while SERS spectr
a of the incorporated adsorbates probe their internal structure. Furth
ermore, we demonstrate that, for a particular adsorbate, the process o
f Ag colloid-adsorbate film formation, the morphology of the deposited
films, and the SERS spectra are substantially influenced by the Ag co
ntent of the parent colloid (Ag-pza and Ag-4-MPy films) and/or by the
concentration of the adsorbate in the organic phase (Ag-2-MPy films).
We propose that the observed differences in the rates of formation of
the films, their morphology, and the orientation of the adsorbate with
respect to the Ag surface are related to differences in the actual su
rface coverage of Ag colloidal particles by adsorbate molecules.