Ionic liquid modified GC electrode for the direct electrochemistry of chloroperoxidase

Chloropcroxidase （CPO） was immobilized by konjac glucomannan （KGM） on the 1-butyl-3-methyl imidazolium tetrafluoroborate [BMIM][BF4]/Nafion modified glassy carbon eloctrode. The electrochemical behaviors of the immobilized CPO were investigated by cyclic voltammetry. The results showed that CPO was successfully immobilized on the GCE and underwent fast direct electron transfer reactions with the formal potential at -0.3 V vs. SCE. The modified electrode showed a good catalytic activity for elcctrocatalytical reduction of O2 and H2O2.     

Nanocomposite of polymerized ionic liquid and graphene used as modifier for direct electrochemistry of cytochrome c and nitric oxide biosensing

In the present work, nanocomposite of polymerized ionic liquid (PIL), poly (1-vinyl-3-ethyl imidazolium) bromide, modified graphene nanosheet (PIL-Gr) was prepared. The PIL-Gr nanosheet composite was evaluated using scanning electron microscopy, transmission electron microscopy, and Fourier transform infrared spectroscopy. Then, a robust and effective sensing strategy based on the nanocomposite for cytochrome c (Cyt c) immobilization on basal plane graphite (BPG) electrode surface was proposed. Direct electrochemistry and electrocatalysis of immobilized Cyt c were investigated in detail. The cyclic voltammogram results indicated that the PIL-Gr nanocomposite film showed an obvious promotion for the direct electron transfer between Cyt c and the underlying electrode. The immobilized Cyt c exhibited an excellent electrocatalytic activity towards the reduction of nitric oxide (NO). The fabricated biosensor exhibited a fast response and a good electrochemical activity for NO with comparable liner range and low detection limit. The low apparent Michaelis–Menten constant $ (K_{\text{m}}^{\text{app}}) $ indicated the affinity of PIL-Gr and Cyt c. Moreover, the modified electrode displayed a rapid response to NO and possessed good stability and reproducibility. Based on the nanocomposite, a third-generation reagentless biosensor could be constructed for the determination of NO. The present work broadens the applications of graphene and ionic liquid in biosensor field.     

Direct electrochemistry of glucose oxidase based on its direct immobilization on carbon ionic liquid electrode and glucose sensing

Direct electrochemistry of glucose oxidase (GOx) has been achieved by its direct immobilization on carbon ionic liquid electrode (CILE) with a conductive hydrophobic ionic liquid, 1-butyl pyridinium hexafluophosphate ([BuPy][PF₆]) as binder for the first time. A pair of reversible peaks is exhibited on GOx/CILE by cyclic voltammetry. The peak-to-peak potential separation (ΔE_P) of immobilized GOx is 0.056 V in 0.067 M phosphate buffer solution (pH 6.98) with scan rate of 0.1 V/s. The average surface coverage and the apparent Michaelis–Menten constant are 6.69 × 10⁻¹¹ mol·cm⁻² and 2.47 μM. GOx/CILE shows excellent electrocatalytic activity towards glucose determination in the range of 0.1–800 μM with detection limit of 0.03 μM (S/N = 3). The biosensor has been successfully applied to the determination of glucose in human plasma with the average recoveries between 95.0% and 102.5% for three times determination. The direct electrochemistry of GOx on CILE is achieved without the help of any supporting film or any electron mediator. GOx/CILE is inexpensive, stable, repeatable and easy to be fabricated.     

Optical determination of glucose and hydrogen peroxide using a nanocomposite prepared from glucose oxidase and magnetite nanoparticles immobilized on graphene oxide

Fe₃O₄ nanoparticles were deposited on sheets of graphene oxide (GO) by a precipitation method, and glucose oxidase (GOx) was then immobilized on this material to produce a GOx/Fe₃O₄/GO magnetic nanocomposite containing crosslinked enzyme clusters. The 3-component composite functions as a binary enzyme that was employed in a photometric method for the determination of glucose and hydrogen peroxide where the GOx/Fe₃O₄/GO nanoparticles cause the generation of H₂O₂ which, in turn, oxidize the substrate N,N-diethyl-p-phenylenediamine to form a purple product with an absorption maximum at 550 nm. The absorbance at 550 nm can be correlated to the concentration of glucose and/or hydrogen peroxide. Under optimized conditions, the calibration plot is linear in the 0.5 to 600 μM glucose concentration range, and the detection limit is 0.2 μM. The respective plot for H₂O₂ ranges from 0.1 to 10 μM, and the detection limit is 0.04 μM. The method was successfully applied to the determination of glucose in human serum samples. The GOx/Fe₃O₄/GO nanoparticles are reusable.

Direct electrochemistry of glucose oxidase on sulfonated graphene/gold nanoparticle hybrid and its application to glucose biosensing

Sulfonated graphene nanosheet/gold nanoparticle (SGN/Au) hybrid was synthesized by electrostatic self-assembly of anionic SGN and positively charged gold nanoparticles. Due to the well-dispersivity of SGN in aqueous solution and its adequate negative charge, Au nanoparticles were assembled uniformly on graphene surface with high distribution. With the advantages of both graphene and Au nanoparticles, SGN/Au hybrid showed enhanced electrocatalytic activity towards O₂ reduction. Furthermore, it provided a conductive and favorable microenvironment for the glucose oxidase (GOD) immobilization and thus promoted its direct electron transfer at the glassy carbon electrode. Based on the consumption of O₂ caused by glucose at the interface of GOD electrode modified with SGN/Au hybrid, the modified electrode displayed satisfactory analytical performance, including high sensitivity (14.55 μA mM^?1 cm^?2), low detection limit (0.2 mM), an acceptable linear range from 2 to 16 mM, and also the prevention from the interference of some species. These results indicated that the prepared SGN/Au hybrid is a promising candidate material for high-performance glucose biosensor.     

High electrocatalytic activity of non-noble Ni-Co/graphene catalyst for direct ethanol fuel cells

The electrocatalytic oxidation of ethanol is studied on the non-noble catalysts Ni-Co/graphene and Ni/graphene supported on glass carbon electrode (GCE) in alkaline medium. The synthesized materials are characterized by X-ray diffraction, X-ray photoelectron spectroscopy, transmission electron microscopy, and scanning transmission electron microscopy. The elements of Ni-Co/graphene and Ni/graphene catalysts are characterized using energy-dispersive X-ray spectroscopy. The electrocatalytic properties of Ni-Co/graphene and Ni/graphene for ethanol oxidation are investigated by cyclic voltammetry, chronoamperometry, and Tafel plot. Compared with Ni/graphene catalyst, Ni-Co/graphene has the higher electroactivity and better stability for ethanol oxidation. The rate constant (k _s) and charge-transfer coefficient (α) are calculated for the electron exchange reaction of the modified GCE. The results indicate that Co addition could promote the oxidation reaction at the Ni/graphene catalyst. Our study demonstrates that the low-cost electrocatalyst Ni-Co/graphene has a great potential for real direct ethanol fuel cells’ application.     

Study of direct electron transfer and enzyme activity of glucose oxidase on graphene surface

In recent years, graphene has been widely used as a high performance two-dimensional material in the development of biosensors and biofuel cells for facilitating direct electron transfer (DET) of glucose oxidase (GOx). However, almost all of these reports perform experiments in the presence of oxygen (a natural mediator of oxidase) and whether the GOx with DET property retained their catalytic activity in the absence of mediators has not been studied in detail so far. In this paper, we investigated the DET property and enzyme activity of GOx on graphene surface without and with mediators. Experimental results showed that the biosensor had no response to glucose in mediator-free solutions, even though the DET of GOx was observed, indicating that the GOx with DET property lacked enzymatically catalytic activity. However, in the presence of mediators, the biosensor showed sensitive response to glucose, illustrating that the mediated enzymatic oxidation of glucose occurred, which can be attributed to the catalytically active GOx without DET capability. These results suggest that DET property and enzyme catalytic activity cannot occur on the same GOx simultaneously. Therefore, keeping enzyme activity and DET of GOx at the same time is still a major challenge for biosensor and biofuel cell researches.     

Tin disulfide nanoflakes decorated with gold nanoparticles for direct electrochemistry of glucose oxidase and glucose biosensing

Previously, we have prepared nanoflake-like tin disulfide (SnS2) and used for the immobilization of proteins and biosensing. We have now modified an electrode with a composite consisting of nanoflake-like SnS2 decorated with gold nanoparticles (Au-NPs) and have immobilized glucose oxidase (GOx) on its surface in order to study its direct electrochemistry. Scanning electron microscopy, electrochemical impedance spectroscopy, Fourier transform IR spectroscopy and cyclic voltammetry were used to examine the interaction between GOx and the AuNP-SnS2 film. It is shown that the composite film has a larger surface area and offers a microenvironment that facilitates the direct electron transfer between enzyme and electrode surface. The immobilized enzyme retains its bioactivity and undergoes a surface-controlled, reversible 2-proton and 2-electron transfer reaction, with an apparent electron transfer rate constant of 3.87 s ^-1. Compared to the nanoflake-like SnS2-based glucose sensor, the GOx-based biosensor exhibits a lower detection limit (1.0 :M), a better sensitivity (21.8 mA?M ^-1 ?cm ^-2), and a wider linear range (from 0.02 to 1.3 mM). The sensor displays excellent selectivity, good reproducibility, and acceptable stability. It was successfully applied to reagentless sensing of glucose at ?0.43 V.

The direct electrochemistry of glucose oxidase based on the synergic effect of amino acid ionic liquid and carbon nanotubes

Amino acid ionic liquids (AAILs) have attracted much attention due to their special chemical and physical properties, especially their outstanding biocompatibility and truly green aspect. In this work, a novel electrochemical biosensing platform based on AAILs/carbon nanotubes (CNTs) composite was fabricated. AAILs were used as a novel solvent for glucose oxidase (GOD) and the GOD-AAILs/CNTs/GC electrode was conveniently prepared by immersing the carbon nanotubes (CNTs) modified glassy carbon (GC) electrode into AAILs containing GOD. The direct electrochemistry of GOD on the GOD-AAILs/CNTs/GC electrode has been investigated and a pair of reversible peaks was obtained by cyclic voltammetry. The immobilized glucose oxidase could retain bioactivity and catalyze the reduction of dissolved oxygen. Due to the synergic effect of AAILs and CNTs, the GOD-AAILs/CNTs/GC electrode shows excellent electrocatalytic activity towards glucose with a linear range from 0.05 to 0.8 mM and a detection limit of 5.5 μM (S/N = 3). Furthermore, the biosensor exhibits good stability and ability to exclude the interference of commonly coexisting uric and ascorbic acid. Therefore, AAILs/CNTs composite can be a good candidate biocompatible material for the direct electrochemistry of the redox-active enzyme and the construction of third- generation enzyme sensors.     

Direct electrodeposition of a biocomposite consisting of reduced graphene oxide, chitosan and glucose oxidase on a glassy carbon electrode for direct sensing of glucose

We have electrodeposited a composite film consisting of graphene oxide, chitosan and glucose oxidase directly on a glassy carbon electrode (GCE) through electrochemical reduction of a solution of the 3 components under controlled direct electrical potential. The procedure takes only several minutes, and the thickness of the resulting film is uniform and controllable. The GOx has uncompromised bioactivity and exhibits reversible 2-proton and 2-electron transfer in presence of glucose. It therefore can be used amperometric sensing of glucose. The biosensor has a fast response (<3 s), a detection limit of 0.4 μM (which is 50-fold lower compared to the biosensor prepared by drop-casting solutions of the same materials onto an GCE), and a linear response in the 0.4 μM to 2 mM concentration range (which again is much better than that of the biosensor prepared by the drop-casting method). Other features include high reproducibility, long-time storage stability, and satisfactory selectivity. We presume that the direct single-step electrodeposition of this nanocomposite offers a promising approach towards novel types of highly sensitive and stable electrochemical biosensors.

ZnO/Cu nanocomposite: a platform for direct electrochemistry of enzymes and biosensing applications

Unique structured nanomaterials can facilitate the direct electron transfer between redox proteins and the electrodes. Here, in situ directed growth on an electrode of a ZnO/Cu nanocomposite was prepared by a simple corrosion approach, which enables robust mechanical adhesion and electrical contact between the nanostructured ZnO and the electrodes. This is great help to realize the direct electron transfer between the electrode surface and the redox protein. SEM images demonstrate that the morphology of the ZnO/Cu nanocomposite has a large specific surface area, which is favorable to immobilize the biomolecules and construct biosensors. Using glucose oxidase (GOx) as a model, this ZnO/Cu nanocomposite is employed for immobilization of GOx and the construction of the glucose biosensor. Direct electron transfer of GOx is achieved at ZnO/Cu nanocomposite with a high heterogeneous electron transfer rate constant of 0.67 ± 0.06 s(-1). Such ZnO/Cu nanocomposite provides a good matrix for direct electrochemistry of enzymes and mediator-free enzymatic biosensors.     

Glucose biosensor based on immobilization of glucose oxidase in platinum nanoparticles/graphene/chitosan nanocomposite film

The bionanocomposite film consisting of glucose oxidase/Pt/functional graphene sheets/chitosan (GOD/Pt/FGS/chitosan) for glucose sensing is described. With the electrocatalytic synergy of FGS and Pt nanoparticles to hydrogen peroxide, a sensitive biosensor with a detection limit of 0.6 μM glucose was achieved. The biosensor also has good reproducibility, long-term stability and negligible interfering signals from ascorbic acid and uric acid comparing with the response to glucose. The large surface area and good electrical conductivity of graphene suggests that graphene is a potential candidate as a sensor material. The hybrid nanocomposite glucose sensor provides new opportunity for clinical diagnosis and point-of-care applications.     

Electrografting of amino-TEMPO on graphene oxide and electrochemically reduced graphene oxide for electrocatalytic applications

4-Amino-2,2,6,6-tetramethyl-1-piperridine N-oxyl (4-amino-TEMPO), an electroactive nitroxide radical, was attached to the surface of graphene oxide (GO) and electrochemically reduced graphene oxide (ERGO) modified glassy carbon electrode by a simple, rapid and green electrografting method. The electroactive interfaces were analyzed by X-ray photoelectron spectroscopy (XPS) and cyclic voltammetry (CV). The calculated surface coverage for 4-amino-TEMPO is up to 1.55 × 10^− 9 mol·cm^− 2. The modified electroactive interface exhibited excellent electrocatalytic activity towards the electro-oxidation of reduced glutathione (GSH) and hydrogen peroxide (H₂O₂).     

In situ synthesis of a Prussian blue nanoparticles/graphdiyne oxide nanocomposite with high stability and electrocatalytic activity

Herein we report an in situ synthesis of Prussian blue nanoparticles (PB) on graphdiyne oxide (GDYO) which acts as an excellent substrate. The hybrid was then used as an electrode with high electrochemical catalytic activity towards hydrogen peroxide. The PB/GDYO hybrid was prepared by simply adding FeCl₃ to GDYO solution, and then mixing with Fe(CN)₆^3 − at room temperature. The GDYO was able to anchor PB in nanoparticle form and stabilize it in neutral and weakly basic solutions. The hybrid was investigated by transmission electron microscopy, X-ray diffraction, X-ray photoelectron spectroscopy and electrochemical measurements. The PB/GDYO hybrid showed high electrochemical catalytic activity and stability for the detection of hydrogen peroxide.     

Direct electrochemistry and enhanced electrocatalytic activity of hemoglobin entrapped in graphene and ZnO nanosphere composite film

A biocomposite film for sensing hydrogen peroxide (HP) is described that is based on nanospheres made from hemoglobin (Hb), graphene, and zinc oxide. The composition, morphology and size of the film were studied by transmission electron microscopy. UV-vis spectroscopy revealed that the Hb entrapped in the graphene and ZnO nanosphere retains its native structure. A pair of stable and well-defined quasi-reversible redox peaks of Hb was obtained, with a formal potential of ?30 mV at pH 6.5. Hb exhibits excellent long-term bioelectrocatalytic activity towards HP. The apparent heterogeneous electron transfer rate constant is 1.0 s^?1, indicating that the presence of graphene in the composite film facilitates the electron transfer between matrix and the electroactive center of Hb. The sensor responds linearly to HP in the range from 1.8 μM to 2.3 mM, with a detection limit of 0.6 μM (at S/N?=?3). The apparent Michaelis-Menten constant is 1.46 mM. The biosensor displays high sensitivity, good reproducibility, and long-term stability.

Evaluation of the catocene/graphene oxide nanocomposite catalytic activity on ammonium perchlorate thermal decomposition

A novel nanocomposite catalyst for thermal degradation of the ammonium perchlorate (AP) has been synthesized, and its effect on the thermal behavior of AP has been investigated. Preparation of the catalyst was carried out via functionalization of the graphene oxide with phenyl isocyanate and its noncovalent bonding to catocene. The catalytic activity of the catalyst was studied by thermal gravimetric analysis/differential scanning calorimetry at various heating rates. In addition, the effect of the catalyst on the AP thermal decomposition has been investigated by Kissinger and Friedman methods as two model-free methods for calculation of the activation energy parameter. According to the Kissinger method calculations, the E_a of AP decomposition reduced about 151 kJ⋅mol⁻¹ lower than the reported value for pure AP in the presence of the catalyst. Calculation of the E_a value for various reaction conversion rates by the Friedman method also confirmed the Kissinger method results.     

Surface nanocrystallization of glassy carbon electrode: Application in direct electrochemistry of glucose oxidase

The surface nanocrystallization of glassy carbon (GC) electrode was carried out using cyclic voltammetry in anhydrous dimethylformamide containing 0.05 M tetra-n-butylammonium bromine, and carbon nanoparticles with diameter of 10–40 nm were formed on the electrode surface. Comparing with the typical GC electrode, the surface-nanocrystalline GC (SNGC) electrode showed higher electrocatalytic activity for direct electrochemistry of glucose oxidase (GOD) due to higher proportion of edge sites presented on the surface of the SNGC electrode. Because of the surface nanocrystallization of the electrode, a pair of well-defined and quasi-reversible redox peaks of the immobilized GOD was observed for the first time on the GC electrode.     

Ionic liquid-functionalized graphene as modifier for electrochemical and electrocatalytic improvement: comparison of different carbon electrodes

Electrochemical activities of typically electrochemical targets at three kinds of modified carbon electrodes, i.e. carbon ionic liquid electrode (CILE), graphene/carbon paste electrode (CPE), and ionic liquid-functionalized graphene (IL-graphene)/CPE, were compared in detail. The redox processes of the probes at IL-graphene/CPE were faster than those at CILE and graphene/CPE from cyclic voltammetry. An electrochemical method for the simultaneous determination of guanine and adenine was described with detection limits of 6.5 × 10⁻⁸ mol L⁻¹ (guanine) and 3.2 × 10⁻⁸ mol L⁻¹ (adenine). Single A → G mutation of sequence-specific DNA could be discriminated by the IL-graphene/CPE.     

Predominating stable adsorption and direct electrochemistry of glucose oxidase on carbon nanotubes by oxygen-containing groups

Stable adsorption and direct electrochemistry of glucose oxidase (GOx) occurred on nitric acid (HNO3)-treated multi-walled carbon nanotubes (MWNTs) instead of as-received MWNTs, demonstrating the critical roles of oxygen-containing groups in stableadsorption and direct electrochemistry of GOx on carbon nanotubes (CNTs).