Wei-Chen Wu

Large-Scale Synthesis of Gold Nanorods through Continuous Secondary Growth

Gold nanorods (GNRs) exhibit a tunable longitudinal surface plasmon resonance (LSPR) that depends on the GNR aspect ratio (AR). Independently controlling the AR and size of GNRs remains challenging but is important because the scattering intensity strongly depends on the GNR size. Here, we report a secondary (seeded) growth procedure, wherein continuous addition of ascorbic acid (AA) to a stirring solution of GNRs, stabilized by cetyltrimethylammonium bromide (CTAB) and synthesized by a common GNR growth procedure, deposits the remaining (~70%) of the Au precursor onto the GNRs. The growth phase of GNR synthesis is often performed without stirring, since stirring has been believed to reduce the yield of rod-shaped nanoparticles, but we report that stirring coupled with continuous addition of AA during secondary growth allows improved control over the AR and size of GNRs. After a common primary GNR growth procedure, the LSPR of GNRs is ~820 nm, which can be tuned between ~700-880 nm during secondary growth by adjusting the rate of AA addition or adding benzyldimethylhexadecylammonium chloride hydrate (BDAC). This approach for secondary growth can also be used with primary GNRs of different ARs to achieve different LSPRs and can likely be extended to nanoparticles of different shapes and other metals.

Large-Scale Silica Overcoating of Gold Nanorods with Tunable Shell Thicknesses

Gold nanorods (GNRs) overcoated with SiO2 are of interest for enhancing the shape stability of GNRs during photothermal heating, for further functionalization with silanes, and for biomedical applications. While methods have recently been developed for synthesizing GNRs on a large scale, SiO2 overcoating of GNRs is still conducted on a small reaction scale. Here, we report a method for large-scale synthesis of SiO2-overcoated GNRs (SiO2-GNRs), which gives ∼190 mg of SiO2-GNRs. SiO2 is deposited onto and encapsulates the cetyltrimethylammonium bromide (CTAB) coatings that stabilize GNRs by adding tetraethoxysilane (TEOS) via syringe pump. Control over the CTAB concentration is critically important for obtaining uniform overcoatings. Optical absorbance spectra of SiO2-GNRs closely resemble those of uncoated GNRs, which indicates overcoating of single rather than multiple GNRs and confirms that they remain well dispersed. By adjusting the reaction conditions, shells as thick as ∼20 nm can be obtained. For thin shells (<10 nm), addition of poly(ethylene glycol) silane (PEG-silane) at different times during the overcoating reaction allows facile control over the shell thickness, giving shells as thin as ∼2 nm. The bulky PEG chain terminates further cross-linking and deposition of SiO2.

Probing biological nanotopology via diffusion of weakly constrained plasmonic nanorods with optical coherence tomography

Significance Many diseases are characterized by nanostructural changes in connective fibers and soluble proteins, which can indicate or drive disease progression. Noninvasive methods sensitive to nanotopological changes in 3D tissue models can elucidate biophysical changes associated with disease progression. Nanoparticles probe their environment via their diffusion, which is impacted by the size and connectivity of pores into which they freely diffuse. Here, we show that optical coherence tomography provides depth-resolved imaging of gold nanorods (GNRs) to infer local biological nanotopology. We demonstrate the broad potential of this method by sensing changes in diffusion of GNRs in 3D models of mammary ECM and pulmonary mucus. Biological materials exhibit complex nanotopology, i.e., a composite liquid and solid phase structure that is heterogeneous on the nanoscale. The diffusion of nanoparticles in nanotopological environments can elucidate biophysical changes associated with pathogenesis and disease progression. However, there is a lack of methods that characterize nanoprobe diffusion and translate easily to in vivo studies. Here, we demonstrate a method based on optical coherence tomography (OCT) to depth-resolve diffusion of plasmon-resonant gold nanorods (GNRs) that are weakly constrained by the biological tissue. By using GNRs that are on the size scale of the polymeric mesh, their Brownian motion is minimally hindered by intermittent collisions with local macromolecules. OCT depth-resolves the particle-averaged translational diffusion coefficient (DT) of GNRs within each coherence volume, which is separable from the nonequilibrium motile activities of cells based on the unique polarized light-scattering properties of GNRs. We show how this enables minimally invasive imaging and monitoring of nanotopological changes in a variety of biological models, including extracellular matrix (ECM) remodeling as relevant to carcinogenesis, and dehydration of pulmonary mucus as relevant to cystic fibrosis. In 3D ECM models, DT of GNRs decreases with both increasing collagen concentration and cell density. Similarly, DT of GNRs is sensitive to human bronchial-epithelial mucus concentration over a physiologically relevant range. This novel method comprises a broad-based platform for studying heterogeneous nanotopology, as distinct from bulk viscoelasticity, in biological milieu.

Aerosynthesis: Growth of Vertically-Aligned Carbon Nanofibres with Air DC Plasma

Vertically-aligned carbon nanofibres (VACNFs) have been synthesized in a mixture of acetone and air using catalytic DC plasma-enhanced chemical vapour deposition. Typically, ammonia or hydrogen is used as an etchant gas in the mixture to remove carbon that otherwise passivates the catalyst surface and impedes growth. Our demonstration of the use of air as the etchant gas opens up the possibility that ion etching could be sufficient to maintain the catalytic activity state during synthesis. It also demonstrates a path toward growing VACNFs in the open atmosphere.