Hanjun Cheng

Graphene as a Spacer to Layer-by-Layer Assemble Electrochemically Functionalized Nanostructures for Molecular Bioelectronic Devices

This study demonstrates the capability of graphene as a spacer to form electrochemically functionalized multilayered nanostructures onto electrodes in a controllable manner through layer-by-layer (LBL) chemistry. Methylene green (MG) and positively charged methylimidazolium-functionalized multiwalled carbon nanotubes (MWNTs) were used as examples of electroactive species and electrochemically useful components for the assembly, respectively. By using graphene as the spacer, the multilayered nanostructures of graphene/MG and graphene/MWNT could be readily formed onto electrodes with the LBL method on the basis of the electrostatic and/or π-π interaction(s) between graphene and the electrochemically useful components. Scanning electron microscopy (SEM), ultraviolet-visible spectroscopy (UV-vis), and cyclic voltammetry (CV) were used to characterize the assembly processes, and the results revealed that nanostructure assembly was uniform and effective with graphene as the spacer. Electrochemical studies demonstrate that the assembled nanostructures possess excellent electrochemical properties and electrocatalytic activity toward the oxidation of NADH and could thus be used as electronic transducers for bioelectronic devices. This potential was further demonstrated by using an alcohol dehydrogenase-based electrochemical biosensor and glucose dehydrogenase-based glucose/O(2) biofuel cell as typical examples. This study offers a simple route to the controllable formation of graphene-based electrochemically functionalized nanostructures that can be used for the development of molecular bioelectronic devices such as biosensors and biofuel cells.

Hybridization of bioelectrochemically functional infinite coordination polymer nanoparticles with carbon nanotubes for highly sensitive and selective in vivo electrochemical monitoring.

This study demonstrates the formation of a three-dimensional conducting framework through hybridization of bioelectrochemically active infinite coordination polymer (ICP) nanoparticles with single-walled carbon nanotubes (SWNTs) for highly sensitive and selective in vivo electrochemical monitoring with combination with in vivo microdialysis. The bioelectrochemically active ICP nanoparticles are synthesized through the self-assembly process of NAD(+) and Tb(3+), in which all biosensing elements including an electrocatalyst (i.e., methylene green, MG), cofactor (i.e., β-nicotinamide adenine dinucleotide, NAD(+)), and enzyme (i.e., glucose dehydrogenase, GDH) are adaptively encapsulated. The ICP/SWNT-based biosensors are simply prepared by drop-coating the as-formed ICP/SWNT nanocomposite onto a glassy carbon substrate. Electrochemical studies demonstrate that the simply prepared ICP/SWNT-based biosensors exhibit excellent biosensing properties with a higher sensitivity and stability than the ICP-based biosensors prepared only with ICP nanoparticles (i.e., without hybridization of SWNTs). By using a GDH-based electrochemical biosensor as an example, we demonstrate a technically simple yet effective online electroanalytical platform for continuously monitoring glucose in the brain of guinea pigs with the ICP/SWNT-based biosensor as an online detector in a continuous-flow system combined with in vivo microdialysis. Under the experimental conditions employed here, the dynamic linear range for glucose with the ICP/SWNT-biosensor is from 50 to 1000 μM. Moreover, in vivo selectivity investigations with the biosensors prepared by the GDH-free ICPs reveal that ICP/SWNT-based biosensors are very selective for the measurement of glucose in the cerebral system. The basal level of glucose in the microdialysates from the striatum of guinea pigs is determined to be 0.31 ± 0.03 mM (n = 3). The study offers a simple route to the preparation of electrochemical biosensors, which is envisaged to be particularly useful for probing the chemical events involved in some physiological and pathological processes.

Rational Design and One-Step Formation of Multifunctional Gel Transducer for Simple Fabrication of Integrated Electrochemical Biosensors

This study demonstrates a new strategy to simplify the biosensor fabrication and thus minimize the biosensor-to-biosensor deviation through rational design and one-step formation of a multifunctional gel electronic transducer integrating all elements necessitated for efficiently transducing the biorecognition events to signal readout, by using glucose dehydrogenase (GDH) based electrochemical biosensor as an example. To meet the requirements for preparing integrated biosensors and retaining electronic and ionic conductivities for electronically transducing process, ionic liquids (ILs) with enzyme cofactor (i.e., oxidized form of nicotinamide adenine dinucleotide) as the anion were synthesized and used to form a bucky gel with single-walled carbon nanotubes, in which methylene green electrocatalyst was stably encapsulated for the oxidation of nicotinamide adenine dinucleotide. With such kind of rationally designed and one-step-formed multifunctional gel as the electronic transducer, the GDH-based electrochemical biosensors were simply fabricated by polishing the electrodes onto the gel followed by enzyme immobilization. This capability greatly simplifies the biosensor fabrication, prolongs the stability of the biosensors, and, more remarkably, minimizes the biosensor-to-biosensor deviation. The relative standard deviations obtained both with one electrode for the repeated measurements of glucose and with the different electrodes prepared with the same method for the concurrent measurements of glucose with the same concentration were 3.30% (n = 7) and 4.70% (n = 6), respectively. These excellent properties of the multifunctional gel-based biosensors substantially enable them to well-satisfy the pressing need of rapid measurements, for example, environmental monitoring, food analysis, and clinical diagnoses.

Ionic liquid-assisted preparation of laccase-based biocathodes with improved biocompatibility.

Laccase enzyme has been widely used as the catalyst of the biocathodes in enzymatic biofuel cells (BFCs); the poor biocompatibility of this enzyme (e.g., poor catalytic activity in neutral media and low tolerance against chloride ion) and the lack of selectivity for oxygen reduction at the laccase-based biocathode against ascorbic acid, unfortunately, offer a great limitation to future biological applications of laccase-based BFCs. This study demonstrates a facial yet effective solution to these limitations with the assistance of hydrophobic room temperature ionic liquid, 1-butyl-3-methylimidazolium hexafluorophosphate (Bmim(+)PF(6)(-)). With the Bmim(+)PF(6)(-) overcoating, the laccase-based biocathodes possess a good bioelectrocatalytic activity toward O(2) reduction in neutral media and a high tolerance against Cl(-). Moreover, the Bmim(+)PF(6)(-) overcoating applied to the laccase-based biocathodes also well suppresses the oxidation of ascorbic acid (AA) at the biocathodes and thereby avoids the AA-induced decrease in the power output of the laccase-based BFCs. The mechanisms underlying the excellent properties of the Bmim(+)PF(6)(-) overcoating are proposed based on the intrinsic features of ionic liquid Bmim(+)PF(6)(-). To demonstrate the applications of the BFCs with the as-prepared biocathodes in biologically relevant systems, an AA/O(2) BFC is assembled with single-walled carbon nanotubes (SWNTs) as electrode materials both for accelerating AA oxidation at the bioanode and for promoting direct electron transfer of laccase at the biocathode. With the presence of 0.50 mM AA in 0.10 M quiescent phosphate buffer (pH 7.2), the assembled BFC has an open circuit voltage of 0.73 V and a maximum power output of 24 μW cm(-2) at 0.40 V under ambient air and room temperature. This study essentially offers a new strategy for the development of enzymatic BFCs with a high biocompatibility.

Potential-controllable green synthesis and deposition of metal nanoparticles with electrochemical method

A controllable and environmentally friendly electrochemical method for task specific synthesis and deposition of metal nanoparticles was first demonstrated by simply adjusting the potentials for the reduction of metal precursors in ionic liquids.

Galvanic Redox Potentiometry for Self-Driven in Vivo Measurement of Neurochemical Dynamics at Open-Circuit Potential

Understanding the real-time correlation between chemical patterns and neural processes is critical for deciphering brain function. Voltammetry has enabled this task but with a number of challenges for current-based electrolysis in vivo. Herein, we report galvanic redox potentiometry (GRP) potentially as a universal strategy for in vivo monitoring of neurochemicals, with ascorbic acid (AA) as a typical example. The GRP sensor is constructed on a self-driven galvanic cell configuration, where AA is spontaneously oxidized at the indicating single-walled carbon nanotube-modified carbon fiber electrode (SWNT-CFE), while oxygen reduced at the laccase-modified reference CFE (Lac-CFE). At thermodynamic equilibrium, open-circuit potential (OCP) can be a linear indicator of the concentration of AA. The resulting sensor shows a high selectivity to AA dynamics in the presence of coexisting electroactive neurochemicals, which is mainly determined by the driving force for the cell reaction, as suggested by principal investigation. Sensing sensitivity of this OCP-based GRP method is not affected by nonspecific protein adsorption and electrode fouling. Moreover, a micropipette compartment of the reference electrode is designed to suppress mass crossover and prevent disturbance to oxygen reduction through confinement effect. The in vivo application of the GRP sensor is illustrated by measuring the basal level of cortical AA in live rat brain (230 ± 40 μM) and its dynamics during ischemia/reperfusion. The GRP concept is demonstrated as a prominent method for in vivo, real-time, quantitative analysis of brain neurochemistry.