Copper fumarate with high-bifunctional nanozyme activities at different pH values for glucose and epinephrine colorimetric detection in human serum.

Metal-organic frameworks (MOFs) have attracted extensive attention for the development of colorimetric detection methods due to their ease of modification and high density of active sites. However, most of the reported colorimetric sensors based on MOFs show only a single nanozyme activity. Herein, the bifunctional enzyme activities of a hexagonal prism Cu MOF with fumaric acid as the ligand (Cu FMA), namely laccase-like activity under alkaline conditions (pH = 8) and peroxidase-like activity under acidic conditions (pH = 4), were verified. The specificity of Cu FMA at different pH values may be due to the presence of the Cu+ active center introduced by the weak reducibility of FMA. At pH = 8, Cu+ active centers are beneficial for dissociating the H-O bonds of phenolic compounds for the laccase system. In contrast, the dissociation of H-O is weakened at pH = 4, which prompts the breaking of the O-O bonds of H2O2 as a Fenton-like reaction for the peroxidase system. Based on the dual enzyme activities, Cu FMA sensors exhibit outstanding detectability for epinephrine and glucose with linear ranges of 2.7-54.6 µM and 0.01-0.8 mM and detection limits of 1.1 µM and 2.28 × 10-7 M, respectively. The Cu FMA colorimetric sensor can be applied for detecting and measuring glucose and epinephrine in human serum samples. This work paves the way for Cu MOFs to be used as the basis for rational regulation of the activity of dual nanozymes and for multifunctional applications under completely independent conditions.

Spinel Zn3V3O8 nanosheets via a one-step hydrothermal synthesis with peroxidase-like activity for high sensitivity glucose colorimetric detection in synthetic perspiration.

Due to their specific spinel structure, ternary oxides with multi-catalytic sites on a highly active exposed surface are recommended as alternative bio-catalysts. Spinel zinc vanadate with two-dimensional nanosheets (Zn3V3O8 NSs) was synthesised using a one-step hydrothermal route with CTAB and glycine as a bi-surfactant, where each NS has a thin thickness (25 nm) and wide cross section (2 µm). As a key parameter for peroxidase-like activity, the Michaelis-Menten constant (Km) for Zn3V3O8 NSs was calculated to be 0.271 mM with TMB and 1.317 mM with H2O2 at optimum conditions, indicating a higher affinity for the exposed (011) facet towards horseradish peroxidases. This affinity is related to the geometric matching between V4+ active sites and the terminal amino groups of TMB. The V4+ ions on the (011) facet act as dangling bonds and readily react with H2O2 in a Fenton-like reaction. The peroxidase-like activity for Zn3V3O8 NSs is verified by the formation of [V(IV)-OO˙] by the ˙O2- and V5+ near V4+ sites, but oxidase activity for Zn3V3O8 NSs. Based on the peroxidase-like activity, Zn3V3O8 NSs were used as a colorimetric glucose sensor with a wide linear range from 0.01 to 0.5 mM and a detection limit (LOD = 3σ/S) of 2.81 × 10-7 M. The colorimetric sensor also exhibited high accuracy and selectivity in synthetic perspiration samples.

Meso-tetra(4-sulfonatophenyl)porphyrin silver/Ag nanoparticles/graphene-phase C3N4 with a sandwich-like structure and double-faced active centers via two-step room-temperature photocatalytic synthesis for ractopamine detection.

Photochemical synthesis under visible light irradiation is a novel approach in the field of green chemistry, and composites with abundant active centers for electrochemical detection are highly attractive. Herein, a meso-tetra(4-sulfonatophenyl)porphyrin silver/Ag nanoparticles/graphene phase C3N4 nanosheets (Ag2TPPS4/AgNPs/ng-C3N4) material with a sandwich-like structure was synthesized using a two-step photocatalytic reaction at room temperature (25 °C). In the first visible light irradiation step and in the presence of a hole capture agent, Ag+ ions were photocatalytically reduced onto the surface of ng-C3N4 that was used as a photocatalyst. Then, the protons (H+) in the core of H2TPPS4 were substituted in situ by photo-oxidized Ag+ during the second visible light irradiation step and in the presence of an electron capture agent. The electrochemical response of Ag2TPPS4 and ng-C3N4 to ractopamine (RAC) results in the unique double-faced active centers of Ag2TPPS4/AgNPs/ng-C3N4, and the cores (AgNPs) are beneficial as bridges for the connection between Ag2TPPS4 and ng-C3N4 and for high-efficiency electron transfer. Hence, as-synthesized Ag2TPPS4/AgNPs/ng-C3N4 exhibits high sensitivity (a low detection limit of 5.1 × 10-8 M, S/N = 3.0), a wide linear range (1 × 10-7 to 1.2 × 10-5 M), and long-term stability. Based on the experimental verification of the electrochemical dynamics and electrostatic attraction at the interface between the dual-active-center surface and RAC, the electrochemical mechanism has been clarified. Specifically, in the multi-cycle oxidation of RAC, the blue shift of specific UV-vis peaks also confirms the electrocatalytic oxidation of the two terminal hydroxyl groups of RAC. In brief, Ag2TPPS4/AgNPs/ng-C3N4 with a sandwich-like structure and double-faced active centers enhances the detection sensitivity and electrocatalytic efficiency towards RAC.

Photocatalytic reduction for graphene oxide by PbTiO3 with high polarizability and its electrocatalytic application in pyrrole detection.

Quick recombination of photogenerated electrons and holes in photocatalytic process remains a huge challenge. And the routine efforts are concentrated on heterojunction, metal decoration and surface defect strategies. PbTiO3 as a typical perovskite ferroelectrics is with a strong built-inelectric field as self-junction caused by internal spontaneous polarization, facilitating the charge separation in the photocatalytic process. Here, under UV irradiation, L-shaped PbTiO3 with active (1 1 0) facet as a photocatalyst was applied to photo-reduce graphene oxide (GO), where a specific reduced graphene oxide (rGO)/PbTiO3 composite was synthesized in presence of isopropanol, a hole-trapping agent. According to the linear optical properties, the polarizability of PbTiO3 is calculated to 1.01 × 10-23 cm3 (2.68 times that of P25 (TiO2)), inducing the photo-excited charge separation by PbTiO3. Based on XPS characterization, a TiOC chemical bond is identified on the interface between rGO and PbTiO3. The response peak current for an electrochemical sensor based on rGO/PbTiO3 was proportional to the concentration of pyrrole (6.6 × 10-9-3.1 × 10-7 M, R2 = 0.999), and an extremely low limit reaches to 2.38 × 10-9 M. In addition, polypyrrole during the pyrrole detection was realized by the multi-cycle oxidation process. And also, the electrochemical detection has been successfully applied for the pyrrole quantification in real samples.