Brian D. Piorek

Free-surface microfluidic control of surface-enhanced Raman spectroscopy for the optimized detection of airborne molecules

We present a microfluidic technique for sensitive, real-time, optimized detection of airborne water-soluble molecules by surface-enhanced Raman spectroscopy (SERS). The method is based on a free-surface fluidic device in which a pressure-driven liquid microchannel flow is constrained by surface tension. A colloidal suspension of silver nanoparticles flowing through the microchannel that is open to the atmosphere absorbs gas-phase 4-aminobenzenethiol (4-ABT) from the surrounding environment. As surface ions adsorbed on the colloid nanoparticles are substituted by 4-ABT, the colloid aggregates, forming SERS “hot spots” whose concentrations vary predictably along the microchannel flow. 4-ABT confined in these hot spots produces SERS spectra of very great intensity. An aggregation model is used to account quantitatively for the extent of colloid aggregation as determined from the variation of the SERS intensity measured as a function of the streamwise position along the microchannel, which also corresponds to nanoparticle exposure time. This allows us to monitor simultaneously the nanoparticle aggregation process and to determine the location at which the SERS signal is optimized.

Photoreduction at a distance: facile, nonlocal photoreduction of Ag ions in solution by plasmon-mediated photoemitted electrons.

Surface-immobilized, densely packed gold nanoparticles in contact with aqueous silver ions and exposed to red light rapidly photoreduce silver ions in solution producing radially symmetric metal deposits with diameters many times larger than the diameter of the illuminating laser beam. The average particle sizes in the deposit increase with radial distance from the center of the deposit. This reduction-at-a-distance effect arises from surface-plasmon-mediated photoemission, with the photoemitted electrons conducting along percolating silver pathways, reducing silver ions along these conducting channels and especially at their periphery, thereby propagating the effect of the illuminating laser outward.

Nanoscale velocity–drag force relationship in thin liquid layers measured by atomic force microscopy

The relationship between velocity and drag force acting on a nanoprobe has been measured with an atomic force microscope (AFM). A special nanoprobe “whisker” was partially submerged in thin layers of glycerol–water mixtures and moved by using the AFM in scanning mode. The viscous drag force-caused torsion of the cantilever probe was recorded as a function of scanning speed and submersion depth. A linear drag force–velocity function was determined for cylindrical bodies with diameters of the order of 50nm. The experimental results were supported by calculations for the torsional force exerted on an AFM probe dragged through a viscous medium. The viscosity was calculated for each experiment assuming no slip conditions and was in agreement with the macroscopically determined values. With some refinements, this offers a possible means of determining viscosity in thin liquid layers.

Nanoscale resolution microchannel flow velocimetry by atomic force microscopy

The velocity of a microchannel flow was determined by atomic force microscopy (AFM) using a 50nm wide “whisker,” which was partially submerged and scanned transverse to the flow while drag was recorded. A peaked, near parabolic, flow velocity profile was found. Particle image velocity (PIV) measurements using 70nm diameter quantum-dot-coated polystyrene spheres confirmed the shape of the AFM-measured velocity profile. AFM-based nanometer resolution velocimetry confirms that the drag-velocity relationship for the whisker remains consistent over a wide range of shear values and appears to successfully resolve submicron scale flows, which are beyond the limits of conventional PIV measurements.

Discrete Free-Surface Millifluidics for Rapid Capture and Analysis of Airborne Molecules Using Surface-Enhanced Raman Spectroscopy

A lithography-free, low-cost, free-surface millifluidic device is reported using discrete liquid interfaces for capturing and detecting gas-phase analyte molecules at low partial pressures out of a gas flow of time-varying composition. The architecture, based on segmented flow, consists of alternating regions of liquid and gas wherein the liquid regions contain surface-enhanced Raman spectroscopy (SERS)-active silver nanoparticles, while the gas regions contain trace quantities of vapor-phase analyte, thereby controlling and optimizing transport and mixing of the gas-phase analyte with the liquid phase. Once absorbed in the liquid phase, the entrained analyte molecules induce aggregation of the aqueous silver nanoparticles. The resulting aggregates consisting of nanoparticles and adsorbed analyte molecules produce intense SERS spectra that reliably identify the absorbed analyte in real time. The approach can be used to determine the time-variable trace chemical composition of a gas stream with applications in, for example, environmental monitoring and online industrial process monitoring, or as a SERS-based detector following gas chromatographic separation. The operation of the system is demonstrated using 4-aminobenzenethiol vapor at 750 ppb, and the detection response time is <2 min.

A Titanium Based Flat Heat Pipe

1. ABSTRACT We are developing innovative heat pipes based on Nano-Structured Titania (NST) with a potential for high heat carrying capacity and high thermal conductivity. These heat pipes have a flat geometry as opposed to a cylindrical geometry found in conventional heat pipes. The flatness will enable a good contact with microprocessor chips and thus reduce the thermal contact resistance. We refer to it as a Thermal Ground Plane (TGP) because of its flat and thin geometry. It will provide the ability to cool the future generations of power intensive microprocessor chips and circuit boards in an efficient way. It also brings the potential to function in high temperature (>150 0 C) fields because of its high yield strength and compatibility (1). The TGP is fabricated with Titanium. It adopts the recently developed high aspect ratio Ti processing techniques (2) and laser packaging techniques. The three main components of the TGP are 1) a fine wick structure based on arrays of high aspect ratio Ti pillars and hair like structures of Nano-Structured Titania (NST), 2) A shallow Ti cavity welded onto the wick structure and 3) the working fluid, water, sealed between the cavity and the wick. The heat carrying capacity and the thermal conductivity of a heat pipe are generally determined by the speed of capillary flow of the working fluid through its wick. The TGP wick has the potential to generate high flow rates and to meet the growing challenges faced by electronics cooling community. The TGP wick structure, developed by etching high aspect ratio pillars in a titanium substrate and growing nano scale hairs on the surface of the pillars, is super hydrophilic and capable of wicking water at velocities ~ 10 -2 m/s over distances of several centimeters. The thermal conductivity of the current TGP device was measured to be 350 W/m K k = ⋅ . The completed TGP device has the potential of attaining a higher conductivity by improving the wicking material and of carrying higher power density. Washburn equation (3) for dynamics of capillary flow has been employed to explain the results of our experiments. The experiment shows a good agreement with Washburn equation.

Dielectrophoretic Nanoparticle Aggregation for On-Demand Surface Enhanced Raman Spectroscopy Analysis

Rapid chemical identification of drugs of abuse in biological fluids such as saliva is of growing interest in healthcare and law enforcement. Accordingly, a label-free detection platform that accepts biological fluid samples is of great practical value. We report a microfluidics-based dielectrophoresis-induced surface enhanced Raman spectroscopy (SERS) device, which is capable of detecting physiologically relevant concentrations of methamphetamine in saliva in under 2 min. In this device, iodide-modified silver nanoparticles are trapped and released on-demand using electrodes integrated in a microfluidic channel. Principal component analysis (PCA) is used to reliably distinguish methamphetamine-positive samples from the negative control samples. Passivation of the electrodes and flow channels minimizes microchannel fouling by nanoparticles, which allows the device to be cleared and reused multiple times.