Michael P. Cecchini

Self-assembled nanoparticle arrays for multiphase trace analyte detection

Nanoplasmonic structures designed for trace analyte detection using surface-enhanced Raman spectroscopy typically require sophisticated nanofabrication techniques. An alternative to fabricating such substrates is to rely on self-assembly of nanoparticles into close-packed arrays at liquid/liquid or liquid/air interfaces. The density of the arrays can be controlled by modifying the nanoparticle functionality, pH of the solution and salt concentration. Importantly, these arrays are robust, self-healing, reproducible and extremely easy to handle. Here, we report on the use of such platforms formed by Au nanoparticles for the detection of multi-analytes from the aqueous, organic or air phases. The interfacial area of the Au array in our system is ≈25 mm(2) and can be made smaller, making this platform ideal for small-volume samples, low concentrations and trace analytes. Importantly, the ease of assembly and rapid detection make this platform ideal for in-the-field sample testing of toxins, explosives, narcotics or other hazardous chemicals.

Ultrafast Surface Enhanced Resonance Raman Scattering Detection in Droplet-Based Microfluidic Systems

The development of ultrafast Raman-based detection is one of the most interesting challenges underpinning the application of droplet-based microfluidics. Herein, we describe the use of surface-enhanced resonance Raman spectroscopy (SERRS) with submillisecond time resolution as a powerful detection tool in microdroplet reactors. Individual droplets containing silver nanoparticle aggregates functionalized with Raman reporters are interrogated and characterized by full spectra acquisitions with high spatial resolution in real time. Whereas previous works coupling SERRS with droplet-based microfluidics acquire a single spectrum over single or multiple droplets, we build upon these results by increasing our temporal resolution by 2 orders of magnitude. This allows us to interrogate multiple points within one individual droplet. The SERRS signals emitted from the aggregates are utilized to access the influence of flow rate on droplet size and throughput. Accordingly, our approach allows for high-throughput analysis that facilitates the study of other biological assays or molecular interactions.

Rapid Ultrasensitive Single Particle Surface-Enhanced Raman Spectroscopy Using Metallic Nanopores

Nanopore sensors embedded within thin dielectric membranes have been gaining significant interest due to their single molecule sensitivity and compatibility of detecting a large range of analytes, from DNA and proteins, to small molecules and particles. Building on this concept we utilize a metallic Au solid-state membrane to translocate and rapidly detect single Au nanoparticles (NPs) functionalized with 589 dye molecules using surface-enhanced resonance Raman spectroscopy (SERRS). We show that, due to the plasmonic coupling between the Au metallic nanopore surface and the NP, signal intensities are enhanced when probing analyte molecules bound to the NP surface. Although not single molecule, this nanopore sensing scheme benefits from the ability of SERRS to provide rich vibrational information on the analyte, improving on current nanopore-based electrical and optical detection techniques. We show that the full vibrational spectrum of the analyte can be detected with ultrahigh spectral sensitivity and a rapid temporal resolution of 880 μs.

Precise attoliter temperature control of nanopore sensors using a nanoplasmonic bullseye.

Targeted temperature control in nanopores is greatly important in further understanding biological molecules. Such control would extend the range of examinable molecules and facilitate advanced analysis, including the characterization of temperature-dependent molecule conformations. The work presented within details well-defined plasmonic gold bullseye and silicon nitride nanopore membranes. The bullseye nanoantennae are designed and optimized using simulations and theoretical calculations for interaction with 632.8 nm laser light. Laser heating was monitored experimentally through nanopore conductance measurements. The precise heating of nanopores is demonstrated while minimizing the accumulation of heat in the surrounding membrane material.

Self-Assembly and Applications of Ultraconcentrated Nanoparticle Solutions

We demonstrate a highly efficient method for concentrating, purifying and separating gold nanoparticles. The method relies on localized density gradients that can be formed at an aqueous | organic phase interface. We show that this method is able to concentrate aqueous gold nanoparticles to the point where confinement leads to variable interparticle separations. Furthermore, the physical properties of the resulting solution are drastically altered when compared to water. For example, densities higher than 4.5 g/cm(3) could be generated without nanoparticle aggregation. As far as we are aware, this is one of the highest reported densities of an aqueous solution at room temperature. Finally, the compositions of the solutions generated are highly dependent on parameters such as particle size and background analyte making this technique highly advantageous for the separation of multimodal NP populations and chemical purification, with 99.5% and >99.9% efficiency, respectively.

Flow-Based Autocorrelation Studies for the Detection and Investigation of Single-Particle Surface-Enhanced Resonance Raman Spectroscopic Events

We report on the characterization and detection of single metallic nanoparticles using a combination of correlation spectroscopy and surface-enhanced resonance Raman spectroscopy (SERRS). Minimizing the number of independent characterization steps is critical to efficiently perform such an analysis. In this article, we improve upon conventional diffusion-limited approaches by implementing a flow-based system with high temporal resolution detection. The benefits of flow over diffusion measurements allow for a higher throughput of detected events resulting in shorter analysis times. The nanoparticles are sized using their rotational diffusion time calculated with a modified autocorrelation function. Experiments are performed using Au nanoparticles labeled with the reporter molecule malachite green isothiocyanate on a custom-built Raman spectrometer.