Theoretical and Experimental Studies of Molecular Interactions between Engineered Graphene and Phosphate Ions for Graphene-Based Phosphate Sensing.

Fundamental understanding of the interactions of nanoscale materials with molecules of interest is essential for the development of electronic devices, such as sensors. In particular, structures and molecular interaction properties of engineered graphenes are still largely unexplored, despite these materials' great potential to be used as molecular sensors. As an example of end user application, the detection of phosphorus in the form of phosphate in a soil environment is important for soil fertility and plant growth. However, due to the lack of an affordable technology, it is currently hard to measure the amount of phosphate directly in the soil; therefore, suitable sensor technologies need to be developed for phosphate sensors. In this work, pristine graphene and several modified graphene materials (oxygenated graphene, graphene with vacancies, and curved graphene) were studied as candidates for phosphate sensor materials using density functional theory (DFT) calculations. Our calculations showed that both pristine graphene and functionalized graphene were able to adsorb phosphate species strongly. In addition, these graphene nanomaterials showed selectivity of adsorption of phosphate with respect to nitrate, with stronger adsorption energies for phosphate. Furthermore, our calculations showed significant changes in electrical conductivities of pristine graphene and functionalized graphenes after phosphate species adsorption, in particular, on graphene with oxygen (hydroxyl and epoxide) functional groups. Experimental measurements of electrical resistivity of graphene before and after adsorption of dihydrogen phosphate showed an increase in resistivity upon adsorption of phosphate, consistent with the theoretical predictions. Our results recommend graphene and functionalized graphene-based nanomaterials as good candidates for the development of phosphate sensors.

Chemically Exfoliated Titanium Carbide MXene for Highly Sensitive Electrochemical Sensors for Detection of 4-Nitrophenols in Drinking Water.

Soil and water contamination by numerous pollutants has been increasingly posing threats to food, water, agriculture, and human health. Using novel nanoscale materials to develop rapid electrochemical sensors is very promising due to the discovery of a number of new two-dimensional (2D) electronic materials. Of particular importance is 2D transition-metal carbide MXene that has been shown to possess transformative properties pertaining to its physical, chemical, and environmental characteristics, leading to their potential sensor applications. Designing electrochemical sensors using MXene has the potential to pave the way for monitoring environmental pollutants. Here, a stacked layer of chemically exfoliated MXene (Ti3C2T x ) was demonstrated as an electrochemical sensor for detection of 4-nitrophenol (4-NP) with high sensitivity and a low limit of detection. Successful selective exfoliation of the MAX (Ti3AlC2) phase of the material by chemical etching without oxidation is shown to be the key to achieving higher sensitivity and a lower detection limit. In the optimal conditions, the proposed MXene sensor electrodes were capable of detecting 4-NP in a broad concentration range from 500 nM to 100 µM with a good linear sensing range (regression fit, R = 0.995). The higher sensitivity and notable limit of detection reached about 16.35 µA µM-1 cm-2 and 42 nM/L, respectively, with good reproducibility and repeatability. The real-time application of the proposed MXene sensor electrodes was confirmed by testing in tap water samples with excellent recoveries of 95-99%.

CIP2A immunosensor comprised of vertically-aligned carbon nanotube interdigitated electrodes towards point-of-care oral cancer screening.

Vertically aligned carbon nanotube array (VANTA) coatings have recently garnered significant attention due in part to their unique material properties including light absorption, chemical inertness, and electrical conductivity. Herein we report the first use of VANTAs grown via chemical vapor deposition in a 2D interdigitated electrode (IDE) footprint with a high height-to-width aspect ratio (3:1 or 75:25 µm). The VANTA-IDEs were functionalized with an antibody (Ab) specific to the human cancerous inhibitor PP2A (CIP2A)-an oncoprotein that is associated with a variety of malignancies such as oral, breast, and multiple myeloma cancers. The resultant label-free immunosensor was capable of detecting CIP2A across a wide linear sensing range (1-100 pg/mL) with a detection limit of 0.24 pg/mL within saliva supernatant-a range that is more sensitive than the corresponding CIP2A enzyme linked immunosorbent assay (ELISA). These results help pave the way for rapid cancer screening tests at the point-of-care (POC) such as for the early-stage diagnosis of oral cancer at a dentist's office.

Advances in Controlling Differentiation of Adult Stem Cells for Peripheral Nerve Regeneration.

Adult stems cells, possessing the ability to grow, migrate, proliferate, and transdifferentiate into various specific phenotypes, constitute a great asset for peripheral nerve regeneration. Adult stem cells' ability to undergo transdifferentiation is sensitive to various cell-to-cell interactions and external stimuli involving interactions with physical, mechanical, and chemical cues within their microenvironment. Various studies have employed different techniques for transdifferentiating adult stem cells from distinct sources into specific lineages (e.g., glial cells and neurons). These techniques include chemical and/or electrical induction as well as cell-to-cell interactions via co-culture along with the use of various 3D conduit/scaffold designs. Such scaffolds consist of unique materials that possess controllable physical/mechanical properties mimicking cells' natural extracellular matrix. However, current limitations regarding non-scalable transdifferentiation protocols, fate commitment of transdifferentiated stem cells, and conduit/scaffold design have required new strategies for effective stem cells transdifferentiation and implantation. In this progress report, a comprehensive review of recent advances in the transdifferentiation of adult stem cells via different approaches along with multifunctional conduit/scaffolds designs is presented for peripheral nerve regeneration. Potential cellular mechanisms and signaling pathways associated with differentiation are also included. The discussion with current challenges in the field and an outlook toward future research directions is concluded.

Real-Space Imaging of the Tailored Plasmons in Twisted Bilayer Graphene.

We report a systematic plasmonic study of twisted bilayer graphene (TBLG)-two graphene layers stacked with a twist angle. Through real-space nanoimaging of TBLG single crystals with a wide distribution of twist angles, we find that TBLG supports confined infrared plasmons that are sensitively dependent on the twist angle. At small twist angles, TBLG has a plasmon wavelength comparable to that of single-layer graphene. At larger twist angles, the plasmon wavelength of TBLG increases significantly with apparently lower damping. Further analysis and modeling indicate that the observed twist-angle dependence of TBLG plasmons in the Dirac linear regime is mainly due to the Fermi-velocity renormalization, a direct consequence of interlayer electronic coupling. Our work unveils the tailored plasmonic characteristics of TBLG and deepens our understanding of the intriguing nano-optical physics in novel van der Waals coupled two-dimensional materials.

Superhydrophobic inkjet printed flexible graphene circuits via direct-pulsed laser writing.

Solution-phase printing of exfoliated graphene flakes is emerging as a low-cost means to create flexible electronics for numerous applications. The electrical conductivity and electrochemical reactivity of printed graphene has been shown to improve with post-print processing methods such as thermal, photonic, and laser annealing. However, to date no reports have shown the manipulation of surface wettability via post-print processing of printed graphene. Herein, we demonstrate how the energy density of a direct-pulsed laser writing (DPLW) technique can be varied to tune the hydrophobicity and electrical conductivity of the inkjet-printed graphene (IPG). Experimental results demonstrate that the DPLW process can convert the IPG surface from one that is initially hydrophilic (contact angle ∼47.7°) and electrically resistive (sheet resistance ∼21 MΩ â–¡-1) to one that is superhydrophobic (CA ∼157.2°) and electrically conductive (sheet resistance ∼1.1 kΩ â–¡-1). Molecular dynamic (MD) simulations reveal that both the nanoscale graphene flake orientation and surface chemistry of the IPG after DPLW processing induce these changes in surface wettability. Moreover, DPLW can be performed with IPG printed on thermally and chemically sensitive substrates such as flexible paper and polymers. Hence, the developed, flexible IPG electrodes treated with DPLW could be useful for a wide range of applications such as self-cleaning, wearable, or washable electronics.

Rapid and Label-Free Detection of Interferon Gamma via an Electrochemical Aptasensor Comprising a Ternary Surface Monolayer on a Gold Interdigitated Electrode Array.

A label-free electrochemical impedance spectroscopy (EIS) aptasensor for rapid detection (<35 min) of interferon-gamma (IFN-γ) was fabricated by immobilizing a RNA aptamer capture probe (ACP), selective to IFN-γ, on a gold interdigitated electrode array (Au IDE). The ACP was modified with a thiol group at the 5' terminal end and subsequently co-immobilized with 1,6-hexanedithiol (HDT) and 6-mercapto-1-hexanolphosphate (MCH) to the gold surface through thiol-gold interactions. This ACP/HDT-MCH ternary surface monolayer facilitates efficient hybridization with IFN-γ and displays high resistance to nonspecific adsorption of nontarget proteins [i.e., fetal bovine serum (FBS) and bovine serum albumin (BSA)]. The Au IDE functionalized with ACP/HDT-MCH was able to measure IFN-γ in actual FBS solution with a linear sensing range from 22.22 pM to 0.11 nM (1-5 ng/mL) and a detection limit of 11.56 pM. The ability to rapidly sense IFN-γ within this sensing range makes the developed electrochemical platform conducive toward in-field disease detection of a variety of diseases including paratuberculosis (i.e., Johne's Disease). Furthermore, experimental results were numerically validated with an equivalent circuit model that elucidated the effects of the sensing process and the influence of the immobilized ternary monolayer on signal output. This is the first time that ternary surface monolayers have been used to selectively capture/detect IFN-γ on Au IDEs.

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.

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.

3D nanostructured inkjet printed graphene via UV-pulsed laser irradiation enables paper-based electronics and electrochemical devices.

Emerging research on printed and flexible graphene-based electronics is beginning to show tremendous promise for a wide variety of fields including wearable sensors and thin film transistors. However, post-print annealing/reduction processes that are necessary to increase the electrical conductivity of the printed graphene degrade sensitive substrates (e.g., paper) and are whole substrate processes that are unable to selectively anneal/reduce only the printed graphene-leaving sensitive device components exposed to damaging heat or chemicals. Herein a pulsed laser process is introduced that can selectively irradiate inkjet printed reduced graphene oxide (RGO) and subsequently improve the electrical conductivity (Rsheet∼0.7 kΩ□(-1)) of printed graphene above previously published reports. Furthermore, the laser process is capable of developing 3D petal-like graphene nanostructures from 2D planar printed graphene. These visible morphological changes display favorable electrochemical sensing characteristics-ferricyanide cyclic voltammetry with a redox peak separation (ΔEp) ≈ 0.7 V as well as hydrogen peroxide (H2O2) amperometry with a sensitivity of 3.32 µA mM(-1) and a response time of <5 s. Thus this work paves the way for not only paper-based electronics with graphene circuits, it enables the creation of low-cost and disposable graphene-based electrochemical electrodes for myriad applications including sensors, biosensors, fuel cells, and theranostic devices.