The development of optically tunable
and intensely scattering materials
is of wide interest in biophotonics and medicine, provided they are
biocompatible. Highly linear, tunable, narrow-gap, and intensely scattering
gold nanobead chains were prepared by a green synthesis scheme, starting
from ultrapure gold nanosphere monomers having a virgin surface. These
Au nanochains exhibit a tunable longitudinal surface plasmon resonance
(SPR) over the range from 590 to 710 nm. To determine the ensemble
statistics of the synthesized nanobead chain lengths and their branching,
transmission electron microscopy (TEM) images were acquired, in batch,
correlated with the nanochain longitudinal SPR maxima (590 to 640
nm). Monte Carlo simulations quantify the selectivity of the chemical
reaction: chain-end gold nanosphere units are about 4 times more reactive
than chain-center units and assemble under a high-inverse-order-dependent
diffusion. Discrete dipole approximation (DDA) computations predict
the experimental extinction spectra and the narrow gap distance of
the chains, as well as the elongated chain’s optical scattering
enhancement, relative to Au nanosphere monomers (approximately 3×
enhancement at equivalent mass). In vitro dark-field
microscopy, cell studies, and biocompatibility tests demonstrate the
nanochains’ (1) intense optical scattering cross sections,
related to the plasmon coupling between the constituent nanospheres,
(2) highly accessible gold surfaces, enabling facile conjugation with
cell targeting ligands, and (3) absence of cell toxicity. The herein
reported scalable, green synthesized, readily conjugatable gold nanobead
chains are thus of great potential utility for serving as a wide range
of biophotonic platforms, such as for enhanced in vitro and in vivo contrast imaging, diagnostics, and
targeted nanotheranostics.