Electrochemically Functionalized Seamless Three-Dimensional Graphene-Carbon Nanotube Hybrid for Direct Electron Transfer of Glucose Oxidase and Bioelectrocatalysis.

Three-dimensional seamless chemical vapor deposition (CVD) grown graphene-carbon nanotubes (G-CNT) hybrid film has been studied for its potential in achieving direct electron transfer (DET) of glucose oxidase (GOx) and its bioelectrocatalytic activity in glucose detection. A two-step CVD method was employed for the synthesis of seamless G-CNT hybrid film where CNTs are grown on already grown graphene film on copper foil using iron as a catalyst. Physical characterization using SEM and TEM show uniform dense coverage of multiwall carbon nanotubes (MWCNT) grown directly on graphene with seamless contacts. The G-CNT hybrid film was electrochemically modified to introduce oxygenated functional groups for DET favorable immobilization of GOx. Pristine and electrochemically functionalized G-CNT film was characterized by electrochemical impedance spectroscopy (EIS), cyclic voltammetry, X-ray photoelectron-spectroscopy, and Raman spectroscopy. The DET between GOx and electrochemically oxidized G-CNT electrode was studied using cyclic voltammetry which showed a pair of well-defined and quasi-reversible redox peaks with a formal potential of -459 mV at pH 7 corresponding to the redox site of GOx. The constructed electrode detected glucose concentration over the clinically relevant range of 2-8 mM with the highest sensitivity of 19.31 µA/mM/cm(2) compared to reported composite hybrid electrodes of graphene oxide and CNTs. Electrochemically functionalized CVD grown seamless G-CNT structure used in this work has potential to be used for development of artificial mediatorless redox enzyme based biosensors and biofuel cells.

Highly Flexible Transistor Threads for All-Thread Based Integrated Circuits and Multiplexed Diagnostics.

Physically intimate, real-time monitoring of human biomarkers is becoming increasingly important to modern medicine and patient wellness. Such monitoring is possible due to advances in soft and flexible materials, devices and bioelectronics systems. Compared to other flexible platforms, multifilament textile fibers or threads offer superior flexibility, material diversity, and simple ambient processing to realize a wide range of flexible devices such as sensors, electronics, and microfluidics. In this paper, we realize unique flexible transistors on threads and interconnect them to realize logic gates and small-scale integrated circuits. Compared to prior textile-based transistors, the proposed thread-based transistors (TBTs) are realized with a readily shaped, colloidally dispersed gel consisting of silica nanoparticles and 1-ethyl-3-methylimidazolium bis(trifluoromethylsulfonyl)imide (EMI TFSI) ionic liquid for all-around electrolyte gating of a carbon nanotube (CNT) semiconducting network assembled on the thread. We interconnect TBTs with thread-based electrochemical sensors (TBEs) to realize an all-thread based multiplexed diagnostic device. All-thread based platforms are thin, highly flexible and conformal, allowing them to be worn directly on the skin without any polymeric substrate, or sutured transdermally using a needle.

Graphene nanogap electrodes in electrical biosensing.

Graphene nanogap electrodes are reported here for the first time in an electrical biosensor for the detection of biomolecular interactions. Streptavidin-biotin was chosen as a model system for evaluating the sensor's performance. High-affinity interactions of streptavidin-gold nanoparticles (strep-AuNPs) to the biotin-functionalized nanogap localizes AuNPs, thereby bridging the gap and resulting in changes in device conductance. Biosensing performance was optimized by varying the gap size, AuNP diameter, and streptavidin coverage on AuNPs. The sensitivity and limit of detection (LOD) of streptavidin detection with the optimized parameters were determined to be 0.3 µA/nM and 0.25 pM, respectively. The proposed platform suggests high potential as a portable point-of-use biosensor for the detection of other affinity-based biomolecular interactions, such as antigen-antibody, nucleic acid, or chemo-selective interactions.

Electrochemical properties of seamless three-dimensional carbon nanotubes-grown graphene modified with horseradish peroxidase.

Horseradish peroxidase (HRP) was immobilized through sodium dodecyl sulfate (SDS) on the surface of a seamless three-dimensional hybrid of carbon nanotubes grown at the graphene surface (HRP-SDS/CNTs/G) and its electrochemical properties were investigated. Compared with graphene alone electrode modified with HRP via SDS (HRP-SDS/G electrode), the surface coverage of electroactive HRP at the CNTs/G electrode surface was approximately 2-fold greater because of CNTs grown at the graphene surface. Based on the increase in the surface coverage of electroactive HRP, the sensitivity to H2O2 at the HRP-SDS/CNTs/G electrode was higher than that at the HRP-SDS/G electrode. The kinetics of the direct electron transfer from the CNTs/G electrode to compound I and II of modified HRP was also analyzed.

Bioelectrochemistry of heme peptide at seamless three-dimensional carbon nanotubes/graphene hybrid films for highly sensitive electrochemical biosensing.

A seamless three-dimensional hybrid film consisting of carbon nanotubes grown at the graphene surface (CNTs/G) is a promising material for the application to highly sensitive enzyme-based electrochemical biosensors. The CNTs/G film was used as a conductive nanoscaffold for enzymes. The heme peptide (HP) was immobilized on the surface of the CNTs/G film for amperometric sensing of H2O2. Compared with flat graphene electrodes modified with HP, the catalytic current for H2O2 reduction at the HP-modified CNTs/G electrode increased due to the increase in the surface coverage of HP. In addition, microvoids in the CNTs/G film contributed to diffusion of H2O2 to modified HP, resulting in the enhancement of the catalytic cathodic currents. The kinetics of the direct electron transfer from the CNTs/G electrode to compound I and II of modified HP was also analyzed.

Graphene hybrids: synthesis strategies and applications in sensors and sensitized solar cells.

Graphene exhibits unique 2-D structural, chemical, and electronic properties that lead to its many potential applications. In order to expand the scope of its usage, graphene hybrids which combine the synergetic properties of graphene along with metals/metal oxides and other nanostructured materials have been synthesized and are a widely emerging field of research. This review presents an overview of the recent progress made in the field of graphene hybrid architectures with a focus on the synthesis of graphene-carbon nanotube (G-CNT), graphene-semiconductor nanomaterial (G-SNM), and graphene-metal nanomaterial (G-MNM) hybrids. It attempts to identify the bottlenecks involved and outlines future directions for development and comprehensively summarizes their applications in the field of sensing and sensitized solar cells.