Droplet-based microfluidic platforms have the potential to provide superior control over mixing as compared to traditional batch reactions. Ionic liquids have advantageous properties for metal nanoparticle synthesis as a result of their low interfacial tension and complexing ability; however, droplet formation of ionic liquids within microfluidic channels in a two-phase system has not yet been attained because of their complex interfacial properties and high viscosities. Here, breakup of an imidazolium-based ionic liquid into droplets in a simple two-phase system has for the first time been achieved and characterized by using a microchannel modified with a thin film fluoropolymer. This microfluidic/ionic liquid droplet system was used to produce small, spherical gold (4.28 ± 0.84 nm) and silver (3.73 ± 0.77 nm) nanoparticles.

In this work, we demonstrate the two-photon fluorescence of covellite-phase copper sulfide nanodisks and investigate the role of the surface plasmon resonance on emission. Using selenium doping, we blue-shift the plasmon resonance toward the two-photon absorption edge. We observed a 3-fold enhancement of emission in these samples and report two-photon action cross sections that are an order of magnitude greater than conventional fluorophores. These nanomaterials offer a novel “all-in-one” platform for engineering plasmon–exciton coupling in the absence of a physical or chemical interface.

This work demonstrates the use of single-layer graphene as a template for the formation of subnanometer plasmonic gaps using a scalable fabrication process called "nanoskiving." These gaps are formed between parallel gold nanowires in a process that first produces three-layer thin films with the architecture gold/single-layer graphene/gold, and then sections the composite films with an ultramicrotome. The structures produced can be treated as two gold nanowires separated along their entire lengths by an atomically thin graphene nanoribbon. Oxygen plasma etches the sandwiched graphene to a finite depth; this action produces a subnanometer gap near the top surface of the junction between the wires that is capable of supporting highly confined optical fields. The confinement of light is confirmed by surface-enhanced Raman spectroscopy measurements, which indicate that the enhancement of the electric field arises from the junction between the gold nanowires. These experiments demonstrate nanoskiving as a unique and easy-to-implement fabrication technique that is capable of forming subnanometer plasmonic gaps between parallel metallic nanostructures over long, macroscopic distances. These structures could be valuable for fundamental investigations as well as applications in plasmonics and molecular electronics.

This article describes the design of piezoresistive thin-film sensors based on single-layer graphene decorated with metallic nanoislands. The defining characteristic of these composite thin films is that they can be engineered to exhibit a temperature coefficient of resistance (TCR) that is close to zero. A mechanical sensor with this property is stable against temperature fluctuations of the type encountered during operations in the real world, for example, in a wearable sensor. The metallic nanoislands are grown on graphene through thermal deposition of metals (gold or palladium) at a low nominal thickness. Metallic films exhibit an increase in resistance with temperature (positive TCR), whereas graphene exhibits a decrease in resistance with temperature (negative TCR). By varying the amount of deposition, the morphology of the nanoislands can be tuned such that the TCRs of a metal and graphene cancel out. The quantitative analysis of scanning electron microscope images reveals the importance of the surface coverage of the metal (as opposed to the total mass of the metal deposited). The stability of the sensor to temperature fluctuations that might be encountered in the outdoors is demonstrated by subjecting a wearable pulse sensor to simulated solar irradiation.

There is a need to monitor patients with cancer of the head and neck postradiation therapy, as diminished swallowing activity can result in disuse atrophy and fibrosis of the swallowing muscles. This paper describes a flexible strain sensor comprising palladium nanoislands on single-layer graphene. These piezoresistive sensors were tested on 14 disease-free head and neck cancer patients with various levels of swallowing function: from nondysphagic to severely dysphagic. The patch-like devices detected differences in (1) the consistencies of food boluses when swallowed and (2) dysphagic and nondysphagic swallows. When surface electromyography (sEMG) is obtained simultaneously with strain data, it is also possible to differentiate swallowing vs nonswallowing events. The plots of resistance vs time are correlated to specific events recorded by video X-ray fluoroscopy. Finally, we developed a machine-learning algorithm to automate the identification of bolus type being swallowed by a healthy subject (86.4%. accuracy). The algorithm was also able to discriminate between swallows of the same bolus from either the healthy subject or a dysphagic patient (94.7% accuracy). Taken together, these results may lead to noninvasive and home-based systems for monitoring of swallowing function and improved quality of life.

The interior surfaces of pre-assembled poly(dimethylsiloxane) (PDMS) microfluidic devices were modified with a cross-linked fluoropolymer barrier coating that significantly increased the chemical compatibility of the devices.

The theories to describe the rate at which electrochemical reactions proceed, to date, do not consider explicitly the dimensionality or the discreteness and occupancy of the energy levels of the electrodes. We show experimentally that such quantum mechanical aspects are important for dimensionally confined nanostructured materials and yield unusual variation of the kinetic rate constants with applied voltage in single-layer graphene. The observed divergence from conventional electrokinetics was ascribed to the linear energy dispersion as well as a nonzero density of states at the Dirac point in the graphene. The obtained results justify the use of density of states-based rate constants and considerably add to Marcus-Hush-Chidsey kinetics.

Thin-film optical strain sensors have the ability to map small deformations with spatial and temporal resolution and do not require electrical interrogation. This paper describes the use of graphene decorated with metallic nanoislands for sensing of tensile deformations of less than 0.04% with a resolution of less than 0.002%. The nanoisland-graphene composite films contain gaps between the nanoislands, which when functionalized with benzenethiolate behave as hot spots for surface-enhanced Raman scattering (SERS). Mechanical strain increases the sizes of the gaps; this increase attenuates the electric field, and thus attenuates the SERS signal. This compounded, SERS-enhanced “piezoplasmonic” effect can be quantified using a plasmonic gauge factor, and is among the most sensitive mechanical sensors of any type. Since the graphene-nanoisland films are both conductive and optically active, they permit simultaneous electrical stimulation of myoblast cells and optical detection of the strains produced by the cellular contractions.