Mark Reeves

Small molecule- and amino acid-induced aggregation of gold nanoparticles.

To understand which organic molecules are capable of binding to gold nanoparticles and/or inducing nanoparticle aggregation, we investigate the interaction of gold nanoparticles with small molecules and amino acids at variable pH. Dynamic Light Scattering (DLS) and ultraviolet-visible (UV-vis) spectra were measured on mixtures of colloidal gold with small molecules to track the progression of the aggregation of gold nanoparticles. We introduce the 522 to 435 nm UV-vis absorbance ratio as a sensitive method for the detection of colloidal gold aggregation, whereby we delineate the ability of thiol, amine, and carboxylic acid functional groups to bind to the surfaces of gold nanoparticles and investigate how combinations of these functional groups affect colloidal stability. We present models for mechanisms of aggregation of colloidal gold, including surface charge reduction and bridging linkers. For all molecules whose addition leads to the aggregation of gold nanoparticles, the aggregation kinetics were accelerated at acidic pH values. Colloidal gold is maintained only in the presence of anionic carboxyl groups, which are neutralized by protonation at lower pH. The overall reduced charge on the stabilizing carboxyl groups accounts for the accelerated aggregation at lower pH values.

Self assembled nanoparticle wires by discontinuous vertical colloidal deposition

We report a simple, one-step method for assembling spherical nanoparticles into wires without the need for lithographic templating. It is effective for a variety of conducting and nonconducting nanoparticles and substrates, and the only material requirement is that the nanoparticles be placed in a colloidal suspension that is wettable on the desired substrate. The shape of the meniscus defines the wire’s geometry, and we report the synthesis and physical properties of wires several millimeters long by a few micrometers wide. As we demonstrate here, the technique is fast and easily controlled, and can be used to make integrated nanoparticle wire arrays.

Surface vertical deposition for gold nanoparticle film

In this rapid communication, we present the surface vertical deposition (SVD) method to synthesize the gold nanoparticle films. Under conditions where the surface of the gold nanoparticle suspension descends slowly by evaporation, the gold nanoparticles in the solid–liquid–gas junction of the suspension aggregate together on the substrate by the force of solid and liquid interface. When the surface properties of the substrate and colloidal nanoparticle suspension define for the SVD, the density of gold nanoparticles in the thin film made by SVD only depends on the descending velocity of the suspension surface and on the concentration of the gold nanoparticle suspension.

Theoretical analysis of vertical colloidal deposition

We have modeled the dynamics of a relatively new deposition technique, vertical colloidal deposition (VCD), for preparing nanoparticle thin films. In this process, the substrate is placed vertically in a nanoparticle suspension and is gradually exposed by evaporation or other slow solvent removal. During the films formation, we observe that the colloidal particles are deposited only at the solid-liquid-gas interface. In contrast with the horizontal geometry, treated elsewhere, where the meniscus is pinned, we observe qualitatively different deposition behaviors. In particular, uniform films rather than rings or lines are produced. Thus, we are led to model a diffusion-driven rather than a convection-driven film growth kinetics, and we are able to predict, consistent with our experimental observations, that the films areal density is inversely proportional to the descent speed of the suspension surface. Additionally, we find that for submonolayer films, the areal density is proportional to the square of the suspension concentration, converting to a linear dependence once monolayer coverage is attained.

Laser desorption/ionization from nanostructured surfaces: nanowires, nanoparticle films and silicon microcolumn arrays

Due to their optical properties and morphology, thin films formed of nanoparticles are potentially new platforms for soft laser desorption/ionization (SLDI) mass spectrometry. Thin films of gold nanoparticles (with 12±1 nm particle size) were prepared by evaporation-driven vertical colloidal deposition and used to analyze a series of directly deposited polypeptide samples. In this new SLDI method, the required laser fluence for ion detection was equal or less than what was needed for matrix-assisted laser desorption/ionization (MALDI) but the resulting spectra were free of matrix interferences. A silicon microcolumn array-based substrate (a.k.a. black silicon) was developed as a new matrix-free laser desorption ionization surface. When low-resistivity silicon wafers were processed with a 22 ps pulse length 3×Z Nd:YAG laser in air, SF6 or water environment, regularly arranged conical spikes emerged. The radii of the spike tips varied with the processing environment, ranging from approximately 500 nm in water, to ~2 μm in SF6 gas and to ~5 μm in air. Peptide mass spectra directly induced by a nitrogen laser showed the formation of protonated ions of angiotensin I and II, substance P, bradykinin fragment 1-7, synthetic peptide, pro14-arg, and insulin from the processed silicon surfaces but not from the unprocessed areas. Threshold fluences for desorption/ionization were similar to those used in MALDI. Although compared to silicon nanowires the threshold laser pulse energy for ionization is significantly (~10u) higher, the ease of production and robustness of microcolumn arrays offer complementary benefits.

Tip preparation for near-field ablation at mid-infrared wavelengths

A fabrication method for high-throughput, fiber-based tips for near-field scanning microscopy (NSOM) in the mid-infrared (λ ~ 3 μm) has been developed. Several fiber materials have been investigated and recipes for wet-chemical etching have been varied to produce tips that are physically robust and are capable of low-loss transmission of high-power pulses of mid-infrared light. Ultimately, wet-chemical etching techniques are used on glass fibers to produce tips capable of focusing mid-infrared light to ablate material from sub-micron-sized regions of organic films. The power throughput of the tips is significantly increased by using a novel material, previously unreported for NSOM applications: germanate fibers. The tips produced are mechanically strong and capable of transmitting high light fluence without sustaining physical damage. Here, the development of these tips and their performance are described.

Near-field ablation threshold of cellular samples in the mid-infrared wavelength region

We report the near-field ablation of biological material with spot sizes as small as 1.5 μm under 3 μm wavelength radiation. The fluence dependence of the ablation of both cellulose acetate coverslips in water and myoblast cell samples in growth media has been studied. We find that for all near-field experiments, the ablation thresholds are very high compared to far-field experiments. A detailed analysis of the length and time scales of the systems provides support for the identification of a plasma-induced mechanism. Thus, applications of sub-wavelength ablation will require robust near-field techniques with capability for high-power density delivery of light.

Cavity resonators of metal-coated dielectric nanorods

Metallic nanoparticles bridge the length scale between atoms and crystals, exhibiting mesoscopic properties unique to their size. Thus, they have generated much interest for their potential applications as chemical or biological sensors and particularly as waveguides for light in nanoscale structures. [Y. W. C. Cao, R. C. Jin, and C. A. Mirkin, Science 297, 1536 (2002); H. J. Lezec et al., Science 297, 820 (2002); S. A. Maier, P. G. Kik, and H. A. Atwater, Appl. Phys. Lett. 81, 1714 (2002); J. M. Oliva and S. K. Gray, Chem. Phys. Lett. 379, 325 (2003)]. One important direction of research into the properties of individual metal nanoparticles involves the controlled variation of their geometry, which can yield new and tunable optical properties that simple spherical configurations do not possess. [T. S. Ahmadi, Z. L. Wang, T. C. Green, A. Henglein, and M. A. Ei-Sayed, Science 272, 1924 (1996)]. A prime example of this is the core-shell nanostructure that has a central material surrounded by differing cladding layer.

Fiberoptic nanobiosensor: A quantitative calibration method

A fiber optic nanobiosensor, with sensitivity comparable to commercial plasmonic sensors, a highly reduced sensing area, and the possibility of in-situ use is presented.

PAME: plasmonic assay modeling environment

Plasmonic assays are an important class of optical sensors that measure biomolecular interactions in real-time without the need for labeling agents, making them especially well-suited for clinical applications. Through the incorporation of nanoparticles and fiberoptics, these sensing systems have been successfully miniaturized and show great promise for in-situ probing and implantable devices, yet it remains challenging to derive meaningful, quantitative information from plasmonic responses. This is in part due to a lack of dedicated modeling tools, and therefore we introduce PAME, an open-source Python application for modeling plasmonic systems of bulk and nanoparticle-embedded metallic films. PAME combines aspects of thin-film solvers, nanomaterials and fiber-optics into an intuitive graphical interface. Some of PAME’s features include a simulation mode, a database of hundreds of materials, and an object-oriented framework for designing complex nanomaterials, such as a gold nanoparticles encased in a protein shell. An overview of PAME’s theory and design is presented, followed by example simulations of a fiberoptic refractometer, as well as protein binding to a multiplexed sensor composed of a mixed layer of gold and silver colloids. These results provide new insights into observed responses in reflectance biosensors.