論文

Efficient detection of sodium nitrite in human urine could be used to diagnose urinary tract infections rapidly. Here, we demonstrate a fast and novel method for the selective detection of sodium nitrite in different human urine samples using electrolysis with a bare boron-doped diamond electrode. The measurement is performed without adding any other species, such as enzymes, and uses a simple electrochemical approach with an oxidation step followed by reduction. In the present study, we pay attention to the reduction potential range for the measurement, which is substantially different from many previous literature reports that focus on the oxidation reaction. The determination of added sodium nitrite based on cyclic voltammetry or differential pulse voltammetry is employed for two pooled urine samples and three individual urine matrices. From this, the linear response ranges for sodium nitrite detection are 0.5-10 mg/L (7.2-140 μmol/L) and 10-400 mg/L (140-5800 μmol/L). The results from these urine samples convert well to the calibration curve, with a limit of detection established as 0.82 mg/L (R2 = 0.9914), which is clinically relevant.

The hydroxyapatite-lanthanum strontium cobalt ferrite (HA-LSCF) composite showed a good response on a screen-printed carbon electrode (SPCE) electrochemical aptasensor to detect SARS-CoV-2. SPCE/HA-LSCF with a thiolated aptamer has a strong affinity for the SARS-CoV-2 spike RBD protein. This occurs due to the binding of -SH to the HA-positive region. In the presence of LSCF, which is conductive, an increase in electron transfer from the redox system [Fe(CN)6]3−/4− occurs. The interaction of the aptamer with the RBD protein can be observed based on the decrease in the electron transfer process. As a result, the developed biosensor is highly sensitive to the SARS-CoV-2 spike RBD protein with a linear range of 0.125 to 2.0 ng mL−1, a detection limit of 0.012 ng mL−1, and a quantification limit of 0.040 ng mL−1. The analytical application of the aptasensor demonstrates its feasibility in the analysis of saliva or swab samples.

Boron-doped diamond (BDD) was modified with copper and gold particles by using an electrodeposition technique to improve its catalytic effect on CO2 reduction in a flow system. The system was optimized based on the production of formic acid by the electroreduction process. At the optimum applied potential of −1.0 V (vs. Ag/AgCl) and flow rate of 50 mL min−1, the copper-gold-modified BDD produced formic acid at the highest rate of 4.88 mol m−2 s−1 and a concentration of 15.93 ppm, while acetic acid was produced with a rate of 0.11 mol m−2 s−1 and a concentration of 0.47 ppm. An advantage of the flow system using the modified BDD was that it was found to accelerate the production rate of acetic acid as well as to decrease the reduction potential of CO2. Furthermore, better stability of the metal particles was observed when using mixed copper-gold modification on the BDD surface than single modification by either metal. The results indicated that a flow system is suitable to be employed for electroreduction of CO2 using the bimetal-modified BDD electrodes, especially with copper and gold as the modifying particles.

Electrogenerated chemiluminescence (ECL) refers to the phenomenon of light emission from molecular species which is triggered by an electrochemical reaction. Therefore, like most electrochemical systems, the electrode material plays a pivotal role and much effort has been made in order to find the best material for ECL, in terms of light signal intensity and long-term stability, especially after the development of ECL for analytical applications. In this article, we will introduce and highlight the distinctive features of boron-doped diamond (BDD) as an electrode material for ECL which has complementary properties compared to the most common metals (e.g., Au or Pt) and carbon materials (e.g., glassy carbon, carbon nanotubes and graphene). Boron-doped diamond electrodes emerged as novel electrodes, gaining more and more interest from the electrochemical community for their peculiar characteristics such as a wide solvent window, low capacitance, resistance to fouling and mechanical robustness. Furthermore, compared to metal electrodes, BDD does not form an oxide layer in aqueous solutions, and the sp3 carbon hybridization gives BDD the ability to enable peculiar electrochemical reactions that are not possible on sp2 carbon materials. Electrogenerated chemiluminescence investigations with boron-doped diamond electrodes have been reported for common ECL systems (luminophores and co-reactants), and special ECL that is only possible on BDD which includes the in situ electrochemical generation of the co-reactant.

The rising concentration of carbon dioxide (CO2) as one of the greenhouse gases in the atmosphere is a major source of worry. Electrochemical reduction of CO2 is one of many ways to convert CO2 gas into usable compounds. An electrochemical technique was applied in this study to reduce CO2 using a boron-doped diamond (BDD) working electrode modified with MXene (Ti3C2Tx) material to improve electrode performance. MXene concentrations of 0.5 mg/mL (MXene-BDD 0.5), 1.0 mg/mL (MXene-BDD 1.0), and 2.0 mg/mL (MXene-BDD 2.0) were drop-casted onto the BDD surface. MXene was effectively deposited on top of the BDD surface, with Ti weight loads of 0.12%, 4.06%, and 7.14% on MXene-BDD 0.5, MXene-BDD 1.0, and MXene-BDD 2.0, respectively. The modified working electrode was employed for CO2 electroreduction with optimal CO2 gas aeration. The existence of the MXene substance in BDD reduced the electroreduction overpotential of CO2. For the final result, we found that the MXene-BDD 2.0 electrode effectively generated the most formic acid product with a maximum reduction potential as low as −1.3 V (vs. Ag/AgCl).

Polycrystalline phosphorus-doped diamond was fabricated by the quartz-tube-type microwave plasma-assisted chemical vapor deposition method. Significantly, red phosphorus was used as a source of phosphorous, instead of PH3. Phosphorus-doped diamond electrodes with hydrogen-terminated and oxygen-terminated surfaces were investigated for the redox reactions of K3[Fe(CN)6] and [Ru(NH3)6]Cl3. The carrier concentration was estimated as 2.1-5.3 × 1018 cm−3 from electrochemical impedance measurements. Polycrystalline phosphorus-doped diamond shows great promise as chemical electrode materials.

Three-dimensional (3D) architected electrode materials are expected to exhibit advantageous properties such as enlarged surface area, increased mass transfer, enhanced adsorption and more active sites exposed. In this paper, boron-doped diamond (BDD) electrodes on 3D printed patterned silicon carbide (SiC) scaffolds have been fabricated using chemical vapor deposition (CVD). The stabilization of the plasma sphere by using clamshell type CVD reactor, introducing the outer protecting plate, the optimization of CVD parameters, and the design of 3D-SiC scaffolds improved the sp3/sp2 ratio, uniformity and growth rate of BDD. 3D-BDD electrodes exhibit enough electrical conductivity for electrochemical applications. The preliminary test for electrochemical carbon dioxide reduction (CO2R) has showed the potential advantages of this type of 3D structured BDD electrodes.

On-site monitoring of plasma drug concentrations is required for effective therapies. Recently developed handy biosensors are not yet popular owing to insufficient evaluation of accuracy on clinical samples and the necessity of complicated costly fabrication processes. Here, we approached these bottlenecks via a strategy involving engineeringly unmodified boron-doped diamond (BDD), a sustainable electrochemical material. A sensing system based on a ∼1 cm2 BDD chip, when analysing rat plasma spiked with a molecular-targeting anticancer drug, pazopanib, detected clinically relevant concentrations. The response was stable in 60 sequential measurements on the same chip. In a clinical study, data obtained with a BDD chip were consistent with liquid chromatography–mass spectrometry results. Finally, the portable system with a palm-sized sensor containing the chip analysed ∼40 μL of whole blood from dosed rats within ∼10 min. This approach with the ‘reusable’ sensor may improve point-of-monitoring systems and personalised medicine while reducing medical costs.

An acrylamide biosensor was developed by utilizing purine bases, i.e. guanine and adenine, through computational and electrochemical approaches. The molecular docking simulation proved that interaction of double-stranded DNA with the purine bases has the lowest Gibbs binding free energy compared to other biomolecules with a ΔGbinding of -4.2759 kcal/mol. Meanwhile, cyclic voltammetry of both guanine and adenine in 0.1M phosphate buffer solution at pH 7.4 using a boron-doped diamond electrode showed an irreversible oxidation peak in the potential range of 0 to +1.8V (vs. Ag/AgCl), confirming that the oxidation reaction was irreversible. The current of these peaks decreased linearly with the concentration of acrylamide due to the adduct formation between the purine bases and acrylamide. The formation of acrylamide adducts between acrylamide and purine bases was confirmed by the shift of the peak wavelength of the UV spectrum from 260 to 257 nm. The use of guanine for acrylamide sensing showed a linear calibration curve in the concentration range of 0.20-1.00 μM (R2 = 0.99) with a limit of detection and limit of quantification attained at 0.11 and 0.36 μM, respectively. In the case of adenine, a linear calibration curve was observed in the concentration range of 0.14-1.00 μM (R2 = 0.99) with a limit of detection and limit of quantification of 0.10 and 0.34 μM, respectively. The developed method was successfully performed for the acrylamide determination in coffee samples and was validated by HPLC.

The study of Ofloxacin (OFL) electrochemical sensor on the surface of zinc modified boron-doped diamond (Zn-BDD) electrode is reported. OFL has been known as one of the fluoroquinolone antibiotics which is used in treating infectious diseases and also in animal agriculture. Despite its effectiveness, long-term consumption could promote antimicrobial resistance. Therefore, a sensitive and selective detection method is important. Meanwhile, BDD has been known for its low background current and high stability, in which, it is necessary for sensor application. Besides, Zn nanoparticles have been widely used for sensor applications due to their low toxicity and low cost. In this work, Zn-BDD electrode was prepared through electrodeposition. The S/B value and sensitivity for OFL analysis were 9.5 and 0.42 respectively on Zn-BDD, in which, it is higher compared to the use of a bare BDD electrode. The analysis in milk was possible with the recovery of 83.05% and 101.20% for BDD and Zn-BDD electrodes respectively. It is suggested that Zn-BDD electrode could be applied for OFL analysis for further real application.

In the mechanistic investigations of electrochemical CO2 reduction reaction (eCO2RR), the undercoordinated site and oxidized metals are generally considered the most likely sources of catalytic sites. However, in the eCO2RR on boron-doped diamond (BDD) electrodes, metal centers are not available, and undercoordinated sites from boron doping did not demonstrated a favorable effect on the catalytic activity. By means of electrochemical activation, we found that when the surface of BDD electrodes is in a stable reduced state, the catalytic activity of eCO2RR for CO production is optimal. The Faradaic efficiency for CO production was increased up to 64 %, and the corresponding production rate reached 23 μmol cm−2 h−1, which was more than three times of the non-activated BDD set as comparison. This work demonstrates that the catalytic activity for eCO2RR can also originate from a reduced surface of BDD electrode.

We report on the coupling of photoelectrochemical water oxidation and electrochemical CO2 reduction to formic acid for a photoelectrochemical system capable of light and electrochemical energy conversion to chemical energy. Titanium oxide nanotubes (TiO2 NT) and boron-doped diamond (BDD) electrodes were used as a photoanode and a cathode, respectively. From CO2 electrochemical reduction at BDD, formic acid was obtained with a faradaic efficiency of about 86% and the system provided an overall energy conversion efficiency of 5.5%. From previous CO2 reduction at a dark electrolyzer based on a BDD cathode, the cell voltage was reduced from 2.7 V to 1.4 V with 52% saving of the electrical energy input. This resulted in an increase from 50% to nearly 80% of electrical-to-chemical energy conversion efficiency.

Spin manipulation of transition-metal catalysts has great potential in mimicking enzyme electronic structures to improve activity and/or selectivity. However, it remains a great challenge to manipulate room-temperature spin state of catalytic centers. Herein, we report a mechanical exfoliation strategy to in situ induce partial spin crossover from high-spin (s=5/2) to low-spin (s=1/2) of the ferric center. Due to spin transition of catalytic center, mixed-spin catalyst exhibits a high CO yield of 19.7 mmol g−1 with selectivity of 91.6 %, much superior to that of high-spin bulk counterpart (50 % selectivity). Density functional theory calculations reveal that low-spin 3d-orbital electronic configuration performs a key function in promoting CO2 adsorption and reducing activation barrier. Hence, the spin manipulation highlights a new insight into designing highly efficient biomimetic catalysts via optimizing spin state.

ConspectusBoron-doped diamond (BDD) electrodes have emerged as next-generation electrode materials for various applications in electrochemistry such as electrochemical sensors, electrochemical organic synthesis, CO2 reduction, ozone water generation, electrochemiluminescence, etc. An optimal BDD electrode design is necessary to realize these applications. The electrochemical properties of BDD electrodes are determined by important parameters such as (1) surface termination, (2) surface orientation, and (3) boron doping level.In this Account, we discuss how these parameters contribute to the function of BDD electrodes. First, control of the surface termination (hydrogen/oxygen) is described. The electrochemical conditions such as the solution pH and the application potential were studied precisely. It was confirmed that an acidic solution and the application of negative potential accelerate hydrogenation, and the mechanism behind this is discussed. For oxygenation, we directly observed changes in surface functional groups by in situ attenuated total reflection infrared spectroscopy and electrochemical X-ray photoelectron spectroscopy measurements.Next, the difference in surface orientation was examined. We prepared homoepitaxial single-crystal diamond electrodes comprising (100) and (111) facets with similar boron concentrations and resistivities and evaluated their electrochemical properties. Experimental results and theoretical calculations revealed that (100)-oriented single-crystal BDD has a wider space charge layer than (111)-oriented BDD, resulting in a slower response. Furthermore, isolated single-crystal microparticles of BDD with exposed (100) and (111) crystal facets were grown, and we studied the electrochemical properties of the respective facets by combination with hopping-mode scanning electrochemical cell microscopy.We also systematically investigated how the boron concentration and sp2 species affect the electrochemical properties. The results showed that the appropriate composition (boron and sp2 species level) is dependent on the application. The transmission electron microscopy images and electron energy loss spectra of highly boron-doped BDD are shown, and the relationship between the composition and electrochemical properties is discussed. Finally, we investigated in detail the effect of the sp2 component on low-doped BDD. Surprisingly, although the sp2 component is usually expected to induce a narrowing of the potential window and an increase in the charging current, low-doped BDD showed the opposite trend depending on the degree of sp2 carbon.The results and discussion presented in this Account will hopefully promote a better understanding of the fundamentals of BDD electrodes and be useful for the optimal development of electrodes for future applications.

While it is well recognized that mass transfer is an important factor in electrochemical reactions, the influence of mass transfer, especially of the convection on the electrochemical CO2 reduction has not been investigated. In this study, we focused on the influence of convection in a flow cell system using a boron-doped diamond electrode. The results clearly showed that convection improved the product selectivity and electrode potentials in CO2 reduction. It suggested that convection controls CO2 mass transfer in a flow cell system and influences the reactivity of electrochemical CO2 reduction.

The detection of molecular hydrogen in water using platinum modified boron doped diamond (Pt-BDD) was presented. A clear peak of hydrogen desorption was observed around −0.1 V in 0.1 M KCl solution. With a simple electrochemical pretreatment, the signal at Pt-BDD electrode was found to be higher and more stable compared to those using bare Pt electrode. The performance of the sensor was compared with gas chromatography method. The result shows a similar trend with either same or different concentration of H2. Lastly, the measurement was successfully conducted in the tap water even without addition of electrolyte. These result shows that Pt-BDD could be promoted as a good electrode candidate for sensing dissolved H2 in the water-based solution.

A straightforward electro-conversion of cumene into acetophenone has been reported using boron-doped diamond (BDD) electrodes. This particular conversion is driven by the addition reaction of a cathodically generated hydroperoxide anion to an anodically generated cumyl cation, where the BDD's wide potential window enables the direct anodic oxidation of cumene into the cumyl cation. Since electricity is directly employed as the oxidizing and reducing reagents, the present protocol is easy to use, suitable for scale-up, and inherently safe.

Urine is one of the most used biological fluids for screening drug delivery and the resultant metabolites. In sports, the use of diuretics such as triamterene is considered a violation of anti-doping rules and is stipulated to be present at less than 79 nM in urine by the World Anti-Doping Agency (WADA). It is therefore important to develop effective rapid and low-cost tests for this diuretic. Here we apply electrochemical analysis using boron-doped diamond (BDD) electrodes, which have superior properties such as low background current, a wide potential window, and high resistance to deactivation. Since real urine samples show clear oxidation current peaks in the potential range more positive than 0.5 V (vs. Ag/AgCl) due to the presence of bio-components such as protein, uric acid, and ascorbic acid, to detect triamterene effectively, the electrochemical protocol was optimized towards a potential range where the other components have limited effect. Our results show that reduced triamterene exhibits an oxidation peak at 0.1 V (vs. Ag/AgCl) in 0.1 M phosphate buffer (PB) and at 0.2 V (vs. Ag/AgCl) in pooled human urine. The peak current value increased according to the triamterene concentration. The limit of detection (LOD) was 3.15 nM in the PB and 7.80 nM in pooled human urine. Finally, triamterene detection was attempted in individual urine samples. Triamterene was electrochemically detectable in individual urine samples, excluding urine samples containing an excess amount of ascorbic acid. The limit of detection (LOD) in individual urine samples was determined to be 20.8 nM.

Levofloxacin (LEV) was known as one of the fluoroquinolone antibiotics that widely used as an antibacterial agent. Monitoring of LEV is important due to its negative side effect on humans. The determination of LEV was studied for the first time on nickel modified on a boron-doped diamond (NiBDD) electrode using the square wave voltammetry (SWV) method to improve the catalytic and sensitivity of the sensor. The response was linear in the range of 30–100 mM LEV. LEV sensor on NiBDD was found to be selective in the presence of urea, glucose, and ascorbic acid interferences. Good reproducibility with % a relative standard deviation of 1.45% (n = 10) was achieved. Therefore, the NiBDD electrode could be potentially applied for the real detection method of LEV.

Electrogenerated chemiluminescence (ECL) of luminol at a boron-doped diamond electrode has been used for hypochlorite determination. The presence of H2O2 induces the generation of the ECL signals of luminol. In contrast, the presence of hypochlorite oxidizes luminol directly to decrease the ECL signals of luminol. Accordingly, a decrease of the ECL signals of luminol in the presence of H2O2 was used as the signal response for hypochlorite detection. A linear decrease of ECL signals with the NaClO concentration in the range from 0 to 20 μM was observed with a sensitivity of 18.56 a.u. μM−1 cm−2. An estimated detection limit of 0.88 μM was achieved, which is around one order lower than the detection limit obtained using the normal electrochemical method with the same electrode. The system also provides a good selectivity towards Cu2+ and Na+. A reproducibility of 3.40%RSD was noted for 15 repetitive measurements. The analytical performance was found to be favourable in comparison to those of other typical electrochemical and electrochemiluminescence methods, indicating that it is applicable for real sample detection.