Electrochemical Detection of Hydrogen Peroxide by Inhibiting the p-Benzenediboronic Acid-Triggered Assembly of Citrate-Capped Au/Ag Nanoparticles on Electrode Surface.
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ABSTRACT: Metal nanoparticles (NPs) possess unique physicochemical attributes for creating effective recognition and transduction processes in chem/bio-sensing. In this work, we suggested that citrate-capped Au/Ag NPs could be used as the reporters for the design of hydrogen peroxide (H₂O₂) sensors with a simple manipulation principle and an easy detection procedure. Specifically, p-benzenediboronic acid (BDBA) induced the aggregation of citrate-capped Au NPs through the cross-linking reaction between citrate and boronic acid of BDBA in solution. By modifying the electrode with a boronic acid derivative, the BDBA-induced assembly of Au NPs was achieved on the electrode surface. This led to a significant decrease in the electron transfer resistance due to the unique conductive ability of Au NPs. However, when the boronate group on the electrode surface was oxidized into its phenol format, the assembly of Au NPs on the electrode surface was not achieved. As a result, a higher electron transfer resistance was observed. The process could be monitored by electrochemical impedance technique. Furthermore, when Ag NPs were used instead of Au NPs in this design, the H₂O₂ concentration could be determined by measuring the linear-sweep voltammetry (LSV) current through the solid-state Ag/AgCl reaction of Ag NPs. The results indicated that NP-based colorimetric assays could be developed into more sensitive electrochemical analysis.
Project description:Hydrogen peroxide (H2O2) is an important molecule in biological and environmental systems. In living systems, H2O2 plays essential functions in physical signaling pathways, cell growth, differentiation, and proliferation. Plasmonic nanostructures have attracted significant research attention in the fields of catalysis, imaging, and sensing applications because of their unique properties. Owing to the difference in the reduction potential, silver nanostructures have been proposed for the detection of H2O2. In this work, we demonstrate the Au@Ag nanocubes for the label- and enzyme-free detection of H2O2. Seed-mediated synthesis method was employed to realize the Au@Ag nanocubes with high uniformity. The Au@Ag nanocubes were demonstrated to exhibit the ability to monitor the H2O2 at concentration levels lower than 200 µM with r2 = 0.904 of the calibration curve and the limit of detection (LOD) of 1.11 µM. In the relatively narrow range of the H2O2 at concentration levels lower than 40 µM, the LOD was calculated to be 0.60 µM with r2 = 0.941 of the calibration curve of the H2O2 sensor. This facile fabrication strategy of the Au@Ag nanocubes would provide inspiring insights for the label- and enzyme-free detection of H2O2.
Project description:The detection of hydrogen peroxide and the control of its concentration are important tasks in the biological and chemical sciences. In this paper, we developed a simple and quantitative method for the non-enzymatic detection of H2O2 based on the selective etching of Au@Ag nanorods with embedded Raman active molecules. The transfer of electrons between silver atoms and hydrogen peroxide enhances the oxidation reaction, and the Ag shell around the Au nanorod gradually dissolves. This leads to a change in the color of the nanoparticle colloid, a shift in LSPR, and a decrease in the SERS response from molecules embedded between the Au core and Ag shell. In our study, we compared the sensitivity of these readouts for nanoparticles with different Ag shell morphology. We found that triangle core-shell nanoparticles exhibited the highest sensitivity, with a detection limit of 10-4 M, and the SERS detection range of 1 × 10-4 to 2 × 10-2 M. In addition, a colorimetric strategy was applied to fabricate a simple indicator paper sensor for fast detection of hydrogen peroxide in liquids. In this case, the concentration of hydrogen peroxide was qualitatively determined by the change in the color of the nanoparticles deposited on the nitrocellulose membrane.
Project description:Effective and facile electrochemical oxidation of chemical fuels is pivotal for fuel cell applications. Herein, we report the electrocatalytic oxidation of hydrazine on a citrate-capped Au-TiO2-modified glassy carbon electrode, which follows two different oxidation paths. These two pathways of hydrazine oxidation are ascribed to occur on Au and the activated TiO2 surface of the Au-TiO2 hybrid electrocatalyst. This activation was achieved through molecular capping of the Au-TiO2 surface by citrate, which leads to favorable hydrazine oxidation with a lower Tafel slope compared to that of the clean surface of the respective materials, that is, Au and TiO2.
Project description:Due to the strong oxidizing properties of H2O2, excessive discharge of H2O2 will cause great harm to the environment. Moreover, H2O2 is also an energetic material used as fuel, with specific attention given to its safety. Therefore, it is of great importance to explore and prepare good sensitive materials for the detection of H2O2 with a low detection limit and high selectivity. In this work, a kind of hydrogen peroxide electrochemical sensor has been fabricated. That is, polypyrrole (PPy) has been electropolymerized on the glass carbon electrode (GCE), and then Ag and Cu nanoparticles are modified together on the surface of polypyrrole by electrodeposition. SEM analysis shows that Cu and Ag nanoparticles are uniformly deposited on the surface of PPy. Electrochemical characterization results display that the sensor has a good response to H2O2 with two linear intervals. The first linear range is 0.1-1 mM (R2 = 0.9978, S = 265.06 μA/ (mM × cm2)), and the detection limit is 0.027 μM (S/N = 3). The second linear range is 1-35 mM (R2 = 0.9969, 445.78 μA/ (mM × cm2)), corresponding to 0.063 μM of detection limit (S/N = 3). The sensor reveals good reproducibility (σ = 2.104), repeatability (σ = 2.027), anti-interference, and stability. The recoveries of the electrode are 99.84-103.00% (for 0.1-1 mM of linear range) and 98.65-104.80% (for 1-35 mM linear range). Furthermore, the costs of the hydrogen peroxide electrochemical sensor proposed in this work are reduced largely by using non-precious metals without degradation of the sensing performance of H2O2. This study provides a facile way to develop nanocomposite electrochemical sensors.
Project description:While seeded growth of quasi-spherical colloidal Au nanoparticles (NPs) has been extensively explored in the literature, the growth of surface supported arrays of such particles has received less attention. The latter scenario offers some significant challenges, including the attainment of sufficient particle-substrate adhesion, growth-selectivity, and uniform mass-transport. To this end, a reaction system consisting of HAuCl4, citrate, and H2O2 is here investigated for the growth of supported arrays of 10 nm Au seeds, derived via block copolymer (BCP) lithography. The effects of the reagent concentrations on the properties of the resultant NPs are evaluated. It is found that inclusion of citrate in the growth medium causes substantial particle desorption from Si surfaces. However, the presence of citrate also yields NPs with more uniformly circular top-view cross sections ("quasi-circular"), motivating the exploration of particle immobilization methods. We demonstrate that atomic layer deposition (ALD) of a single cycle of HfO2 (∼1 Å), after the seed particle formation, promotes adhesion sufficiently to enable the use of citrate without the added oxide noticeably affecting the shape of the resultant NPs. The presented ALD-based approach differs from the conventional sequence of depositing the adhesion layer prior to the seed particle formation and may have advantages in various processing schemes, such as when surface grafting of brush layers is required in the BCP lithography process. A proof-of-concept is provided for the growth of large-area arrays of supported "quasi-circular" Au NPs, in a rapid one-step process at room temperature.
Project description:Hybrid silver (Ag)-gold (Au) nanoparticles (NPs) with different sizes and compositions were synthesized. Ag/Au alloy and Ag@Au core-shell type NPs were prepared from Ag and Au with various ratios using the COCO gemini surfactant, 1,6-bis (N,N-hexadecyldimethylammonium) adipate (COCOGS), 16-6-16 as a stabilizer. The formation of the Ag/Au alloy and Ag@Au core-shell was confirmed by UV-visible absorption spectroscopy, high-resolution transmission electron microscopy (HRTEM), energy-dispersive X-ray spectroscopy (EDX) and selected area electron diffraction (SAED) patterns. Depending on the composition of the Ag/Au alloy NPs, the λ max values varied from 408 nm to 525 nm. FTIR measurements were used to evaluate the adsorption of the COCO gemini surfactant (16-6-16) on the Ag/Au alloy and Ag@Au core-shell surface. In this present work, we study how to achieve the stability and activity of the COCO gemini surfactant (16-6-16) capped Ag/Au alloy and Ag@Au core-shell NPs for developing novel anti-cancer agents by evaluating their potentials in the Hep-2 cell line model. Thus the developed core-shell NPs were possibly involved in inducing cytotoxicity followed by inhibition of cell proliferation to the cancer cells with apoptosis induction. The developed core-shell NPs might serve as highly applicable agents in the development of next-generation cancer chemotherapeutic agents.
Project description:In this work, a facile, environmentally friendly method was demonstrated for the synthesis of Ag-Au bimetallic nanoparticles (Ag-AuNPs) supported on reduced graphene oxide (RGO) with alginate as reductant and stabilizer. The prepared Ag-AuNPs/RGO was characterized by scanning electron microscope (SEM), transmission electron microscopy (TEM), X-ray diffraction (XRD), and X-ray photoelectron spectroscopy (XPS). The results indicated that uniform, spherical Ag-AuNPs was evenly dispersed on graphene surface and the average particle size is about 15 nm. Further, a non-enzymatic sensor was subsequently constructed through the modified electrode with the synthesized Ag-AuNPs/RGO. The sensor showed excellent performance toward H₂O₂ with a sensitivity of 112.05 μA·cm−2·mM−1, a linear range of 0.1⁻10 mM, and a low detection limit of 0.57 μM (S/N = 3). Additionally, the sensor displayed high sensitivity, selectivity, and stability for the detection of H₂O₂. The results demonstrated that Ag-AuNPs/RGO has potential applications as sensing material for quantitative determination of H₂O₂.
Project description:In this paper, Au and reduced graphene oxide (rGO) were successively deposited on fluorine-doped SnO₂ transparent conductive glass (FTO, 1 × 2 cm) via a facile and one-step electrodeposition method to form a clean interface and construct a three-dimensional network structure for the simultaneous detection of nitrite and hydrogen peroxide (H₂O₂). For nitrite detection, 3D Au-rGO/FTO displayed a sensitivity of 419 μA mM-1 cm-2 and a linear range from 0.0299 to 5.74 mM, while for the detection of H₂O₂, the sensitivity was 236 μA mM-1 cm-2 and a range from 0.179 to 10.5 mM. The combined results from scanning electron microscopy (SEM), transmission electron microscopy (TEM), Raman spectroscopy, X-ray diffraction measurements (XRD) and electrochemical tests demonstrated that the properties of 3D Au-rGO/FTO were attributabled to the conductive network consisting of rGO and the good dispersion of Au nanoparticles (AuNPs) which can provide better electrochemical properties than other metal compounds, such as a larger electroactive surface area, more active sites, and a bigger catalytic rate constant.
Project description:Au nanoparticles synthesized from colloidal techniques have the capability in many applications such as catalysis and sensing. Au nanoparticles function as both catalyst and highly sensitive SERS probe can be employed for sustainable and green catalytic process. However, capping ligands that are necessary to stabilize nanoparticles during synthesis are negative for catalytic activity. In this work, a simple effective mild thermal treatment to remove capping ligands meanwhile preserving the high SERS sensitivity of Au nanoparticles is reported. We show that under the optimal treatment conditions (250 °C for 2 h), 50 nm Au nanoparticles surfaces are free from any capping molecules. The catalytic activity of treated Au nanoparticles is studied through H2O2 decomposition, which proves that the treatment is favorable for catalytic performance improvement. A reaction intermediate during H2O2 decomposition is observed and identified.
Project description:Previously, an electrochemical bandage (e-bandage) that uses a three-electrode system to produce hydrogen peroxide (H2O2) electrochemically on its working electrode was developed as a potential strategy for treating biofilms; it showed activity in reducing biofilms in an agar biofilm model. Xanthan gum-based hydrogel, including NaCl, was used as the electrolyte. While H2O2 generated at the working electrode in the vicinity of a biofilm is a main mechanism of activity, the role of the counter electrode was not explored. The goal of this research was to characterize electrochemical reactions occurring on the counter electrode of the e-bandage. Counter electrode potential varied between 1.2 and 1.5 VAg/AgCl; ∼125 µM hypochlorous acid (HOCl) was generated within 24 h in the e-bandage system. When HOCl was not produced on the counter electrode (achieved by removing NaCl from the hydrogel), reduction of Acinetobacter baumannii BAA-1605 biofilm was 1.08 ± 0.38 log10 CFU/cm2 after 24 h treatment, whereas when HOCl was produced, reduction was 3.87 ± 1.44 log10 CFU/cm2. HOCl inhibited catalase activity, abrogating H2O2 decomposition. In addition to H2O2 generation, the previously described H2O2-generating e-bandage generates HOCl on the counter electrode, enhancing its biocidal activity.