Polypeptide folding-mediated tuning of the optical and structural properties of gold nanoparticle assemblies.

Responsive hybrid nanomaterials with well-defined properties are of significant interest for the development of biosensors with additional applications in tissue engineering and drug delivery. Here, we present a detailed characterization using UV-vis spectroscopy and small angle X-ray scattering of a hybrid material comprised of polypeptide-decorated gold nanoparticles with highly controllable assembly properties. The assembly is triggered by a folding-dependent bridging of the particles mediated by the heteroassociation of immobilized helix-loop-helix polypeptides and a complementary nonlinear polypeptide present in solution. The polypeptides are de novo designed to associate and fold into a heterotrimeric complex comprised of two disulfide-linked four-helix bundles. The particles form structured assemblies with a highly defined interparticle gap (4.8±0.4 nm) that correlates to the size of the folded polypeptides. Transitions in particle aggregation dynamics, mass-fractal dimensions and ordering, as a function of particle size and the concentration of the bridging polypeptide, are observed; these have significant effects on the optical properties of the assemblies. The assembly and ordering of the particles are highly complex processes that are affected by a large number of variables including the number of polypeptides bridging the particles and the particle mobility within the aggregates. A fundamental understanding of these processes is of paramount interest for the development of novel hybrid nanomaterials with tunable structural and optical properties and for the optimization of nanoparticle-based colorimetric biodetection strategies.

Observation of interference effects in coherent diffraction of nanocrystals under X-ray standing-wave illumination.

Coherent X-ray diffraction is a useful technique for understanding the structure of compact objects including those which can be represented as phase objects. X-rays are highly penetrating and have wavelengths very close to atomic spacing. In this work, gold nanocrystals (on a reflecting substrate) were imaged at the Advanced Photon Source and found to produce a novel double diffraction pattern. Simulations were carried out to explain the experimental diffraction pattern in terms of reflection of the incident beam from the substrate to produce a standing wave. The experimental data were then phased to produce a two-dimensional real-space image of the gold. It is expected that the standing-wave illumination may be a useful tool to aid the convergence of the phasing algorithms for nanocrystals.