Surface-enhanced
Raman scattering (SERS) is a surface sensitive
technique that reveals information regarding molecular adsorption
driving forces at nanoparticles surfaces. While the plasmonic properties
of SERS substrates provide the largest signal enhancements, chemical
enhancement mechanisms are more sensitive to molecular adsorption
and intermolecular interactions. Herein, gold coated silver nanoparticles
that are stabilized inside microporous silica membranes are used for
monitoring short-range chemical enhancement effects. First, the silica
membrane provides plasmonic stability while also facilitating kinetic
measurements so that impacts of molecular protonation, molecule–molecule
interactions, molecule–silica interactions, and molecule–Au
interactions can be identified. To do this, the vibrational frequencies
of 4-mercaptobenzoic acid (4-MBA) are monitored as a function of time
and pH. Applying Fick’s second law to time-dependent responses
reveals that molecular flux decreases with increasing pH. SERS spectra
suggest that the kinetics of this phenomenon depend on the protonation
state of 4-MBA and, hence, the energy required for the molecules to
pass through the negatively charged silica membrane. Namely, repulsive
electrostatic interactions between deprotonated molecules (R-COO–) and the silica shell increase the energy required
for transport, which subsequently decreases the flux of molecules
through the silica shell and subsequent adsorption to the metal surface.
As pH approaches neutral conditions, the fraction of deprotonated
4-MBA increases. These molecules, which have a higher electron density
in the aromatic rings versus protonated ones, favor selective chemical
enhancement of the asymmetric versus symmetric C–C stretching
modes. In addition, increasing intermolecular interactions between
adsorbed molecules promote electron delocalization from aromatic rings
to the carboxylate groups of 4-MBA. This response causes the pK
a of the carboxylate to gradually increase from
4.8 (in solution) to 7.7 (on nanoparticle surfaces). Consequently,
SERS signals for this molecule can be understood with respect to molecular
protonation state, flux, and intermolecular interactions using these
electromagnetically stable plasmonic nanostructures.