Ultrasound and defect engineering-enhanced nanozyme with high laccase-like activity for oxidation and detection of phenolic compounds and adrenaline.

Perusing metal-based redox nanozyme offers new opportunity for pollutant removal and biosensor, but ultrasound (US)-driven laccase-like nanozyme remains a significant challenge, especially in combination with defect engineering strategy. Herein, the Cu2Ov@Ce-TCPP was synthesized by doping Ce3+ on the surface of Cu2O nanocube and then coating with the porphyrin sonosensitizer. The Ce-doped porphyrin metal-structure in nanozyme was demonstrated to generate oxygen vacancy defects, which could obviously promote the laccase-like activity of Cu2Ov@Ce-TCPP nanozyme under US. XPS characterization and density functional theory (DFT) theoretical calculation revealed that the ultrasonic stimulation is beneficial to accelerate the electron transfer rate and O2 adsorption to improve catalytic activity, and Cu2Ov@Ce-TCPP nanozyme exhibits low adsorption energy and activation energy due to the presence of oxygen defect site, resulting in high laccase-like activity. The interaction between Ce atom and porphyrin structure also improved the sonocatalytic ability of the nanozyme. Meanwhile, Cu2Ov@Ce-TCPP nanozyme has been used for detecting and degrading a series of phenolic compounds. The detection adrenaline method has a linear range of 3.3-1000 µM and a detection limit as low as 0.96 µM with good reproducibility. The developed US-enhancing and recyclable laccase-like nanozyme system provides a promising strategy for the oxidation and detection of phenolic compounds.

Bifunctional drug delivery system with carbonic anhydrase IX targeting and glutathione-responsivity driven by host-guest amphiphiles for effective tumor therapy.

It remains a critical issue to deliver anticancer drugs to tumor tissues and reducing the toxic effects on normal tissues. The drug delivery system (DDS) based on self-assembly provides a multi-functional way for drug delivery. In this work, a supramolecular host (L-CD) with targeting function based on a ß-cyclodextrin (ß-CD) backbone was synthesized with carbonic anhydrase IX (CAIX) overexpressed on tumor cells as a target, and the methotrexate prodrug (MTX-SS-Ad) modified by adamantane and disulfide bond was prepared to be used as the guest. The amphiphilic complex was prepared between L-CD and MTX-SS-Ad through host-guest interactions and could further self-assemble into supramolecular nanoparticles (SNPs) with active targeting and stimulus release functions. The interaction between host and guest was investigated by UV, NMR, IR, XRD and TGA. The characteristic of SNPs was observed by DLS and TEM. Throng the study of molecular docking, in vitro inhibition, cell uptake experiments, and western blotting, SNPs have showed CAIX inhibitory effects both inside and outside the cells. The in vitro release experiments indicated that SNPs can undergo disintegration and release drugs under acidic and GSH conditions. Moreover, SNP can effectively inhibit the proliferation of cancer cells without generating additional toxic side effects on normal cells. So, we provide a strategy of bifunctional drug delivery system with targeting and glutathione-responsivity for effective tumor therapy.

Fluorescence detection of dopamine based on the peroxidase-like activity of Fe3O4-MWCNTs@Hemin.

A novel Fe3O4-MWCNTs@Hemin nanocomposite was synthesized using hemin and Fe3O4 with multi-walled carbon nanotubes (MWCNTs) by one-step hydrothermal methods. The as-prepared Fe3O4-MWCNTs@Hemin nanocomposites exhibited excellent peroxidase-like activities in the activation of H2O2. The mechanisms, kinetics, and catalytic performances of Fe3O4-MWCNTs@Hemin were systematically studied. Fe3O4-MWCNTs@Hemin can oxidize dopamine (DA) to dopaquinone in the presence of H2O2, and the intermediate products dopaquinone can further react with ß-naphthol to generate a highly fluorescent derivative at 415 nm excitation wavelength. Therefore, an innovative fluorescence platform for the detection of DA was developed. The fluorescence intensity increased linearly with DA concentration in the range 0.33 to 107 µM, with a low detection limit of 0.14 µM. Due to the excellent activity, substrate universality, fast response, high selectivity, and sensitivity of Fe3O4-MWCNTs@Hemin, the proposed fluorescence method was used to analyze complex biological blood samples with a satisfactory result. It demonstrated the significant potential for developing effective and dependable fluorescent analytical platforms for preserving human health.

SERS detection of Hg2+ and aflatoxin B1 through on-off strategy of oxidase-like Au@HgNPs/carbon dots.

In this work, cerium-doped carbon dots (Ce-CDs) both as a reducing agent and template hybrid gold nanoparticles (AuNPs) with weak oxidase-like (OXD) activity was synthesized for the detection of Hg2+ and aflatoxin B1 (AFB1). The AuNPs can catalyze efficiently mercury ion (Hg2+) reduction to the metallic (Hg0) to form Au-Hg amalgam (Au@HgNPs). The obtained Au@HgNPs with strong OXD-like activity oxidize without Raman-active leucomalachite green (LMG) into the Raman-active malachite green (MG) and simultaneously as the SERS substrates by the formed Raman "hot spot" through MG-induced Au@HgNPs aggregation. While AFB1 was introduced resulting in the SERS intensity decreasing due to Hg2+ with AFB1 via carbonyl group to inhibit the aggregation of Au@HgNPs. The work paves a new path for the design of a nanozyme-based SERS protocol for tracing Hg2+ and AFB1 residues in foodstuff analysis.

Fluorescence-SERS dual-mode for sensing histamine on specific binding histamine-derivative and gold nanoparticles.

Histamine (His) is used as an indicator of seafood quality, but it can be toxic at high intakes. A fluorescence (FL)-surface-enhanced Raman scattering (SERS) dual-mode assay system has been developed for His detection. The His detection method was established based on the specific binding capacity of gold nanoparticles (AuNPs) for the FL derivative of His and o-phthalaldehyde (OPA). In this strategy, His reacted with the OPA to form a Schiff base product (O-His) along with a change in FL and SERS activities. The usual nature of AuNPs could display a significant role both enhancement of SERS and quenching of FL signals. The current investigation displayed a good selectivity toward His over all other biogenic amines. Under the optimized analytical conditions, the SERS and FL intensity of the system were linearly proportional to the His concentration in the range of 0.05-4.5 mg/L and 1-20 mg/L with a detection limit of 0.04 mg/L and 0.32 mg/L, respectively. Moreover, the proposed method was successfully applied for His determination in seafood with promising results.