Allison A. Cargill

Increasing the activity of immobilized enzymes with nanoparticle conjugation

The efficiency and selectivity of enzymatic catalysis is useful to a plethora of industrial and manufacturing processes. Many of these processes require the immobilization of enzymes onto surfaces, which has traditionally reduced enzyme activity. However, recent research has shown that the integration of nanoparticles into enzyme carrier schemes has maintained or even enhanced immobilized enzyme performance. The nanoparticle size and surface chemistry as well as the orientation and density of immobilized enzymes all contribute to the enhanced performance of enzyme-nanoparticle conjugates. These improvements are noted in specific nanoparticles including those comprising carbon (e.g., graphene and carbon nanotubes), metal/metal oxides and polymeric nanomaterials, as well as semiconductor nanocrystals or quantum dots.

Electrical Differentiation of Mesenchymal Stem Cells into Schwann-Cell-Like Phenotypes Using Inkjet-Printed Graphene Circuits

Graphene-based materials (GBMs) have displayed tremendous promise for use as neurointerfacial substrates as they enable favorable adhesion, growth, proliferation, spreading, and migration of immobilized cells. This study reports the first case of the differentiation of mesenchymal stem cells (MSCs) into Schwann cell (SC)-like phenotypes through the application of electrical stimuli from a graphene-based electrode. Electrical differentiation of MSCs into SC-like phenotypes is carried out on a flexible, inkjet-printed graphene interdigitated electrode (IDE) circuit that is made highly conductive (sheet resistance < 1 kΩ/sq) via a postprint pulse-laser annealing process. MSCs immobilized on the graphene printed IDEs and electrically stimulated/treated (etMSCs) display significant enhanced cellular differentiation and paracrine activity above conventional chemical treatment strategies [≈85% of the etMSCs differentiated into SC-like phenotypes with ≈80 ng mL-1 of nerve growth factor (NGF) secretion vs. 75% and ≈55 ng mL-1 for chemically treated MSCs (ctMSCs)]. These results help pave the way for in vivo peripheral nerve regeneration where the flexible graphene electrodes could conform to the injury site and provide intimate electrical simulation for nerve cell regrowth.

Biosensing with Förster Resonance Energy Transfer Coupling between Fluorophores and Nanocarbon Allotropes

Nanocarbon allotropes (NCAs), including zero-dimensional carbon dots (CDs), one-dimensional carbon nanotubes (CNTs) and two-dimensional graphene, exhibit exceptional material properties, such as unique electrical/thermal conductivity, biocompatibility and high quenching efficiency, that make them well suited for both electrical/electrochemical and optical sensors/biosensors alike. In particular, these material properties have been exploited to significantly enhance the transduction of biorecognition events in fluorescence-based biosensing involving Förster resonant energy transfer (FRET). This review analyzes current advances in sensors and biosensors that utilize graphene, CNTs or CDs as the platform in optical sensors and biosensors. Widely utilized synthesis/fabrication techniques, intrinsic material properties and current research examples of such nanocarbon, FRET-based sensors/biosensors are illustrated. The future outlook and challenges for the research field are also detailed.

Enabling Inkjet Printed Graphene for Ion Selective Electrodes with Postprint Thermal Annealing

Inkjet printed graphene (IPG) has recently shown tremendous promise in reducing the cost and complexity of graphene circuit fabrication. Herein we demonstrate, for the first time, the fabrication of an ion selective electrode (ISE) with IPG. A thermal annealing process in a nitrogen ambient environment converts the IPG into a highly conductive electrode (sheet resistance changes from 52.8 ± 7.4 MΩ/□ for unannealed graphene to 172.7 ± 33.3 Ω/□ for graphene annealed at 950 °C). Raman spectroscopy and field emission scanning electron microscopy (FESEM) analysis reveals that the printed graphene flakes begin to smooth at an annealing temperature of 500 °C and then become more porous and more electrically conductive when annealed at temperatures of 650 °C and above. The resultant thermally annealed, IPG electrodes are converted into potassium ISEs via functionalization with a poly(vinyl chloride) (PVC) membrane and valinomycin ionophore. The developed potassium ISE displays a wide linear sensing range (0.01-100 mM), a low detection limit (7 μM), minimal drift (8.6 × 10-6 V/s), and a negligible interference during electrochemical potassium sensing against the backdrop of interfering ions [i.e., sodium (Na), magnesium (Mg), and calcium (Ca)] and artificial eccrine perspiration. Thus, the IPG ISE shows potential for potassium detection in a wide variety of human fluids including plasma, serum, and sweat.

Integration of biochemical sensors into wearable biomaterial platforms

With rapidly inflating healthcare costs, a limited supply of physicians and an alarming surge in lifestyle diseases, radical changes must be made to improve preventative medicine and ensure a sustainable healthcare system. A compelling solution is to equip the population with wearable health monitors to continuously record representative and actionable physiological data. Herein, we present a preliminary design and evaluation of a biochemical sensor node enabled by a substrate comprised of a nanocellulose thin-film that conforms to the skin and carries a printed sensor element. The nanocellulose layer ensures conformal and biocompatible contact with the skin, while a printed layer provides a high surface-area electrode. While the recognition/transduction element can be exchanged for many different sensing motifs, we utilize the general structure of an electrochemical glucose sensor.

Hybrid Metallic Nanoparticles: Enhanced Bioanalysis and Biosensing via Carbon Nanotubes, Graphene, and Organic Conjugation

Composite materials, incorporating noble metal and metal oxide nanoparticles, have attracted much interest as active substrates for biosensor electronics. These nanoparticles provide a viable microenvironment for biomolecule immobilization by retaining their biological activity with desired orientation and for facilitating transduction of the biorecognition event. Herein, we discuss various methods for fabrication of metal and metal oxide nanoparticle composite materials and their applications in different electrochemical biosensors. The materials are organized by the corresponding component with the nanoparticles, i.e. carbon-based composites, polymers, and DNA. The performance of hybrids is compared and examples of biosensing apparatus are discussed. In all cases, the engineering of morphology, particle size, effective surface area, functionality, adsorption capability, and electron-transfer properties directly impact the resultant biosensing capabilities. Ultimately, these attractive features of metal and metal-oxide hybrid materials are expected to find applications in the next generation of smart biosensors.

Effect of platinum nanoparticle deposition parameters on hydrogen peroxide transduction for applications in wearable electrochemical glucose biosensors

Enhanced interest in wearable biosensor technology over the past decade is directly related to the increasing prevalence of diabetes and the associated requirement of daily blood glucose monitoring. In this work we investigate the platinum-carbon transduction element used in traditional first-generation glucose biosensors which rely on the concentration of hydrogen peroxide produced by the glucose–glucose oxidase binding scheme. We electrodeposit platinum nanoparticles on a commercially-available screen printed carbon electrode by stepping an applied current between 0 and 7.12 mA/cm2 for a varying number of cycles. Next, we examine the trends in deposition and the effect that the number of deposition cycles has on the sensitivity of electrochemical glucose sensing. Results from this work indicate that applying platinum nanoparticles to screen printed carbon via electrodeposition from a metal salt solution improves overall biosensor sensitivity. This work also pinpoints the amount of platinum (i.e., number of deposition cycles) that maximizes biosensor sensitivity in an effort to minimize the use of the precious metals, viz., platinum, in electrode fabrication. In summary, this work quantifies the relationship between platinum electrodeposition and sensor performance, which is crucial in designing and producing cost-effective sensors.