Plasmonic-polymer nanocomposites
can serve as a multifunctional
platform for a wide range of applications such as biochemical sensing
and photothermal treatments, where they synergistically benefit from
the extraordinary optical properties of plasmonic nanoparticles (NPs)
and biocompatible characteristics of biopolymers. The field translation
of plasmonic-polymer nanocomposites requires design rules for scalable
and reproducible fabrication with tunable and predictable optical
properties and achieving the best performance. The optical properties
of NPs and the optimal analytical performance of nanocomposites could
be affected by many fabrication parameters, but a fundamental understanding
of such parameters is still minimal. Herein, we systematically investigated
the NP distribution and their optical properties in gold nanostar
(GNS)-polymer nanocomposites as a function of GNS concentration, polymer
identity, and the method of GNS incorporation into a polymer matrix.
We performed a comprehensive analysis of the single-particle scattering
spectra of GNS incorporated into agarose gel and chitosan hydrogels
via embedding and surface deposition, using dark-field spectroscopy.
While relative GNS concentration affects the GNS scattering property
distribution in both polymer matrices, chemical interactions between
a polymer matrix and GNS is the key determinant of the GNS stability
and homogenous distribution in nanocomposites. When GNS are embedded
in a polymer matrix and there are stronger chemical interactions between
GNS and a polymer, significantly less aggregation and a more homogenous
distribution of GNS, which leads to a larger percentage of GNS optical
property preservation, were observed at all the concentrations. In
a proof-of-concept surface-enhanced Raman spectroscopy (SERS) study,
we observed that the SERS detection efficiency is dictated by the
analyte accessibility of GNS, which is governed by the polymer matrix
porosity, polymer-GNS interactions, and other polymer physical characteristics.
This work presents the interplay between key fabrication parameters
and foundational design parameters for more predictable and reliable
fabrication of plasmonic-polymer nanocomposites as an optical platform.