Emulsion Assembly of Graphene Oxide/Polymer Composite Membranes.

Graphene oxide/polymer composite water filtration membranes were developed via coalescence of graphene oxide (GO) stabilized Pickering emulsions around a porosity-generating polymer. Triptycene poly(ether ether sulfone)-CH2NH2:HCl polymer interacts with the GO at the water-oil interface, resulting in stable Pickering emulsions. When they are deposited and dried on polytetrafluoroethylene substrate, the emulsions fuse to form a continuous GO/polymer composite membrane. X-ray diffraction and scanning electron microscopy demonstrate that the intersheet spacing and thickness of the membranes increased with increasing polymer concentration, confirming the polymer as the spacer between the GO sheets. The water filtration capability of the composite membranes was tested by removing Rose Bengal from water, mimicking separations of weak black liquor waste. The composite membrane achieved 65% rejection and 2500 g m-2 h-1 bar-1. With high polymer and GO loading, composite membranes give superior rejection and permeance performance when compared with a GO membrane. This methodology for fabrication membranes via GO/polymer Pickering emulsions produces membranes with a homogeneous morphology and robust chemical separation strength.

Wireless Tags with Hybrid Nanomaterials for Volatile Amine Detection.

Quality control in the production and processing of raw meat is currently one of the biggest concerns for food industry and would benefit from portable and wireless sensors capable of detecting the onset of spoilage. Raw meat is a natural source of biogenic and volatile amines as byproducts of decarboxylation reactions, and the levels of these compounds can be utilized as quality control parameters. We report herein a hybrid chemiresistor sensor based on inorganic nanofibers of SiO2:ZnO (an n-type material) and single-walled carbon nanotubes functionalized with 3,5-dinitrophenyls (a p-type material) with dosimetric sensitivity ∼40 times higher for amines than for other volatile organic compounds, which also provides excellent selectivity. The hybrid nanomaterial-based chemiresistor sensory material was used to convert radio-frequency identification tags into chemically actuated resonant devices, which constitute wireless sensors that can be potentially employed in packaging to report on the quality of meat. Specifically, the as-developed wireless tags report on cumulative amine exposure inside the meat package, showing a decrease in radio-frequency signals to the point wherein the sensor ceased to be smartphone-readable. These hybrid material-modified wireless tags offer a path to scalable, affordable, portable, and wireless chemical sensor technology for food quality monitoring without the need to open the packaging.

Reconfigurable Pickering Emulsions with Functionalized Carbon Nanotubes.

Pickering emulsions (PEs) achieve interfacial stabilization by colloidal particle surfactants and are commonly used in food, cosmetics, and pharmaceuticals. Carbon nanotubes (CNTs) have recently been used as stabilizing materials to create dynamic single emulsions. In this study, we used the formation of Meisenheimer complexes on functionalized CNTs to fabricate complex biphasic emulsions containing hydrocarbons (HCs) and fluorocarbons (FCs). The reversible nature of Meisenheimer complex formation allows for further functionalization at the droplet-water interface. The strong affinity of fluorofluorescent perylene bisimide (F-PBI) to the CNTs was used to enhance the assembly of CNTs on the FC-water interface. The combination of different concentrations of the functionalized CNTs and the pelene additive enables predictable complex emulsion morphologies. Reversible morphology reconfiguration was explored with the addition of molecular surfactants. Our results show that the interfacial properties of functionalized CNTs have considerable utility in the fabrication of complex dynamic emulsions.

Polymer Nanocomposite Microactuators for On-Demand Chemical Release via High-Frequency Magnetic Field Excitation.

On-demand delivery of substances has been demonstrated for various applications in the fields of chemistry and biomedical engineering. Single-pulse release profile has been shown previously for micro/nanoparticles in different form factors. However, to obtain a sustained release, a pulsatile release profile is needed. Here, we demonstrate such a release profile from polymer magnetic nanocomposite microspheres loaded with chemicals. By exciting the microactuators with AC magnetic fields, we could achieve up to 61% cumulative release over a five-day period. One of the main advantages of using a magnetic stimulus is that the properties of the environment (e.g., transparency, density, and depth) in which the particles are located do not affect the performance. The operating magnitude of the magnetic field used in this work is safe and does not interact with any nonmetallic materials. The proposed approach can potentially be used in microchemistry, drug delivery, lab-on-chip, and microrobots for drug delivery.

Roll-to-Roll Gravure Printed Electrochemical Sensors for Wearable and Medical Devices.

As recent developments in noninvasive biosensors spearhead the thrust toward personalized health and fitness monitoring, there is a need for high throughput, cost-effective fabrication of flexible sensing components. Toward this goal, we present roll-to-roll (R2R) gravure printed electrodes that are robust under a range of electrochemical sensing applications. We use inks and electrode morphologies designed for electrochemical and mechanical stability, achieving devices with uniform redox kinetics printed on 150 m flexible substrate rolls. We show that these electrodes can be functionalized into consistently high performing sensors for detecting ions, metabolites, heavy metals, and other small molecules in noninvasively accessed biofluids, including sensors for real-time, in situ perspiration monitoring during exercise. This development of robust and versatile R2R gravure printed electrodes represents a key translational step in enabling large-scale, low-cost fabrication of disposable wearable sensors for personalized health monitoring applications.

Cation-Dependent Light-Induced Halide Demixing in Hybrid Organic-Inorganic Perovskites.

Mixed cation metal halide perovskites with increased power conversion efficiency, negligible hysteresis, and improved long-term stability under illumination, moisture, and thermal stressing have emerged as promising compounds for photovoltaic and optoelectronic applications. Here, we shed light on photoinduced halide demixing using in situ photoluminescence spectroscopy and in situ synchrotron X-ray diffraction (XRD) to directly compare the evolution of composition and phase changes in CH(NH2)2CsPb-halide (FACsPb-) and CH3NH3Pb-halide (MAPb-) perovskites upon illumination, thereby providing insights into why FACs-perovskites are less prone to halide demixing than MA-perovskites. We find that halide demixing occurs in both materials. However, the I-rich domains formed during demixing accumulate strain in FACsPb-perovskites but readily relax in MA-perovskites. The accumulated strain energy is expected to act as a stabilizing force against halide demixing and may explain the higher Br composition threshold for demixing to occur in FACsPb-halides. In addition, we find that while halide demixing leads to a quenching of the high-energy photoluminescence emission from MA-perovskites, the emission is enhanced from FACs-perovskites. This behavior points to a reduction of nonradiative recombination centers in FACs-perovskites arising from the demixing process and buildup of strain. FACsPb-halide perovskites exhibit excellent intrinsic material properties with photoluminescence quantum yields that are comparable to MA-perovskites. Because improved stability is achieved without sacrificing electronic properties, these compositions are better candidates for photovoltaic applications, especially as wide bandgap absorbers in tandem cells.

Methylxanthine Drug Monitoring with Wearable Sweat Sensors.

Drug monitoring plays crucial roles in doping control and precision medicine. It helps physicians tailor drug dosage for optimal benefits, track patients' compliance to prescriptions, and understand the complex pharmacokinetics of drugs. Conventional drug tests rely on invasive blood draws. While urine and sweat are attractive alternative biofluids, the state-of-the-art methods require separate sample collection and processing steps and fail to provide real-time information. Here, a wearable platform equipped with an electrochemical differential pulse voltammetry sensing module for drug monitoring is presented. A methylxanthine drug, caffeine, is selected to demonstrate the platform's functionalities. Sweat caffeine levels are monitored under various conditions, such as drug doses and measurement time after drug intake. Elevated sweat caffeine levels upon increasing dosage and confirmable caffeine physiological trends are observed. This work leverages a wearable sweat sensing platform toward noninvasive and continuous point-of-care drug monitoring and management.