Portable Microelectrochemical Sensors for Rapid and Sensitive Determination of Hesperidin in Citrus reticulate 'Chachi' Peel.

Portable and low-cost analytical devices are essential for rapid detection of bioactive substrates in agricultural products. This study presents the first highly integrated microelectrochemical sensor based on pencil graphite for rapid and sensitive detection of hesperidin in Citrus reticulate 'Chachi' peel. The surface morphology and characterization as well as the electrochemical property of pencil graphite was investigated and discussed. A high electrocatalytic efficiency of hesperidin has been found at used pencil graphite-based microelectrodes. Kinetic analysis was carried out to further understand the electrochemical process of hesperidin at a pencil graphite microelectrode. Consequently, a portable and highly-integrated microelectrochemical sensor exhibits a sensitivity of 0.7251 µA cm-2 µM-1 and a detection limit as low as 25 nM (S/N = 3), and high selectivity was fabricated. Proposed microelectrochemical sensors were applied to electrochemically determinate the hesperidin content in the extract of Citrus reticulata "chachi" peel. As a result, the concentration of hesperidin in the actual real sample detected electrochemically with the proposed portable and low-cost microelectrochemical sensors is highly consistent to that obtained with a common chromatographic method, thus indicating the good reliability and that it can be used in practical applications.

In Situ Forming Epidermal Bioelectronics for Daily Monitoring and Comprehensive Exercise.

Conventional epidermal bioelectronics usually do not conform well with natural skin surfaces and are susceptible to motion artifact interference, due to incompatible dimensions, insufficient adhesion, imperfect compliance, and usually require complex manufacturing and high costs. We propose in situ forming hydrogel electrodes or electronics (ISF-HEs) that can establish highly conformal interfaces on curved biological surfaces without auxiliary adhesions. The ISF-HEs also have favorable flexibility and soft compliance comparable to human skin (≈0.02 kPa-1), which can stably maintain synchronous movements with deformed skins. Thus, the as-prepared ISF-HEs can accurately monitor large and tiny human motions with short response time (≈180 ms), good biocompatibility, and excellent performance. The as-obtained nongapped hydrogel electrode-skin interfaces achieve ultralow interfacial impedance (≈50 KΩ), nearly an order of magnitude lower than commercial Ag|AgCl electrodes as well as other reported dry and wet electrodes, regardless of the intrinsic micro-obstacles (wrinkles, hair) and skin deformation interference. Therefore, the ISF-HEs can collect high-quality electrocardiography and surface electromyography (sEMG) signals, with high signal-to-noise ratio (SNR ≈ 32.04 dB), reduced signal crosstalk, and minimized motion artifact interference. Simultaneously monitoring human motions and sEMG signals have also been implemented for the general exercise status assessment, such as the shooting competition in the Olympics. The as-prepared ISF-HEs can be considered as supplements/substitutes of conventional electrodes in percutaneously noninvasive monitoring of multifunctional physiological signals for health and exercise status.

Comparative investigation of bioflavonoid electrocatalysis in 1D, 2D, and 3D carbon nanomaterials for simultaneous detection of naringin and hesperidin in fruits.

Electrocatalysis of bioflavonoids in carbon nanomaterials plays an important role in electrochemical sensors for the detection of their content in fruits. In this study, three types of carbon nanomaterials with 1D, 2D, and 3D structures, namely carbon nanotubes (CNTs), graphene oxide (GO), and Ketjen black (KB), were modified onto glassy carbon electrodes for the electrocatalysis of hesperidin and naringin, which are two important bioflavonoids in fruits. As a result, the CNT-modified electrodes showed the highest electrocatalytic activity for both hesperidin and naringin compared to GO and KB. The morphology and surface chemistry of the carbon nanomaterials were characterized. The structural defects and carbon status of carbon nanomaterials are proposed to be the most important factors affecting the electrocatalysis of hesperidin and naringin. Finally, a CNT-based electrochemical sensor was fabricated to simultaneously detect hesperidin and naringin. Real sample tests on the fruit extract of Citrus grandis "Tomentosa" show that the proposed electrochemical sensors with high recovery thus could be employed in practical applications.

Tackling the Challenges of Enzymatic (Bio)Fuel Cells.

The ever-increasing demands for clean and sustainable energy sources combined with rapid advances in biointegrated portable or implantable electronic devices have stimulated intensive research activities in enzymatic (bio)fuel cells (EFCs). The use of renewable biocatalysts, the utilization of abundant green, safe, and high energy density fuels, together with the capability of working at modest and biocompatible conditions make EFCs promising as next generation alternative power sources. However, the main challenges (low energy density, relatively low power density, poor operational stability, and limited voltage output) hinder future applications of EFCs. This review aims at exploring the underlying mechanism of EFCs and providing possible practical strategies, methodologies and insights to tackle these issues. First, this review summarizes approaches in achieving high energy densities in EFCs, particularly, employing enzyme cascades for the deep/complete oxidation of fuels. Second, strategies for increasing power densities in EFCs, including increasing enzyme activities, facilitating electron transfers, employing nanomaterials, and designing more efficient enzyme-electrode interfaces, are described. The potential of EFCs/(super)capacitor combination is discussed. Third, the review evaluates a range of strategies for improving the stability of EFCs, including the use of different enzyme immobilization approaches, tuning enzyme properties, designing protective matrixes, and using microbial surface displaying enzymes. Fourth, approaches for the improvement of the cell voltage of EFCs are highlighted. Finally, future developments and a prospective on EFCs are envisioned.

Carbon-nanotube-caged microbial electrodes for bioelectrocatalysis.

A method to stably immobilize microbes on electrodes was developed. Resting cells of Methylobacterium extorquens AM1(MeAM1) were caged within multiwalled carbon nanotubes (MWNTs)by adding the cells to a water dispersion of MWNTs then allowing the resulting mixture to dry on electrodes. The MeAM1-MWCNTs electrode thus obtained displayed excellent activities in the bidirectional bioelectrocatalysis due to formate dehydrogenase(s) in the resting cells; formate oxidation and carbon dioxide reduction proceeded at steady-state catalytic current densities of 0.6 ±â€¯0.1 and -0.8 ±â€¯0.1 mA cm-2, respectively, using methyl viologen as mediator under very mild conditions (pH 7.0, atmospheric pressure, and 37 °C). In addition, the catalytic signal was stable for more than one week under continuous operation.

Electrochemical Biosensor for Polycyclic Organic Compounds Screening Based on a Methylene Blue-incorporated DNA Polyion Complex Modified Electrode.

A reagent-less electrochemical DNA biosensor for rapid non-electroactive polycyclic organic compounds (POCs) screening and detection was proposed. In this method, methylene blue (MB) was incorporated into DNA/chitosan polyion complex membrane and then modified onto a glassy carbon electrode (GCE). The electrochemical analysis for the prepared DNA-MB/chitosan/GCE showed that the modified electrode exhibited high electrochemical activity and stability. The addition of tetracycline hydrochloride (TC), a model analyte of non-electroactive POCs, resulted in an obvious peak current decrease in DNA-MB/chitosan/GCE, and this electrochemical response was affected by the DNA type and MB/DNA ratio in the modified electrodes. Ultraviolet-visible (UV-Vis) absorption spectroscopy was utilized to furthermore investigate the interaction between TC and DNA-MB/chitosan/GCE. As a result, a competitive interaction and displacement effect between TC and the intercalated MB was proposed. In our condition, the prepared DNA-MB/chitosan/GCE showed high sensitivity to POCs and had almost no response to common interferences. Besides, the good stability and reproducibility of the prepared electrode made it suitable for practical use.

Direct Electron Transfer-type Bioelectrocatalysis of Peroxidase at Mesoporous Carbon Electrodes and Its Application for Glucose Determination Based on Bienzyme System.

Non-catalytic direct electron transfer (DET) signal of Compound I of horseradish peroxidase (POD) was first detected at 0.7 V on POD/carbon nanotube mixture-modified electrodes. Excellent performance of DET-type bioelectrocatalysis was achieved with POD immobilized with glutaraldehyde on Ketjen Black (KB)-modified electrodes for H2O2 reduction with an onset potential of 0.65 V (vs. Ag | AgCl | sat. KCl) without any electrode surface modification. The POD-immobilized KB electrode was found to be suitable for detecting H2O2 with a low detection limit (0.1 µM at S/N = 3) at -0.1 V. By co-immobilizing glucose oxidase (GOD) and POD on the KB-modified electrode, a bienzyme electrode was constructed to couple the oxidase reaction of GOD with the DET-type bioelectrocatalytic reduction of H2O2 by POD. The amperometric detection of glucose was performed with a high sensitivity (0.33 ± 0.01 µA cm-2 µM-1) and a low detection limit (2 µM at S/N = 3).

Factors affecting the interaction between carbon nanotubes and redox enzymes in direct electron transfer-type bioelectrocatalysis.

The effects of three types of water-soluble carbon nanotubes (CNTs) of different lengths on the direct electron transfer (DET)-type bioelectrocatalysis of redox enzymes were investigated. Bilirubin oxidase (BOD), copper efflux oxidase (CueO), and a membrane-bound NiFe hydrogenase (H2ase) were used as model redox enzymes for four-electron dioxygen (O2) reduction (in the case of BOD and CueO) and two-electron dihydrogen (H2) oxidation (in the case of H2ase). As a result, diffusion-controlled O2 reduction in an O2-saturated neutral buffer was realized by BOD on CNTs of a length of 1µm, but the catalytic current densities decreased as the length of CNTs increased. However, almost opposite trends were obtained when CueO and H2ase were utilized as the biocatalysts. Factors of the CNTs and the enzymes affecting the characteristics of the DET-type bioelectrocatalysis of the three enzymes were discussed. Finally, the electrostatic interaction between an enzyme (especially the portion near the redox active center) and CNTs is proposed as one of the most important factors governing the performance of DET-type bioelectrocatalysis.