Directed Assembly of Au Nanostar@Ag Satellite Nanostructures for SERS-Based Sensing of Hg2+ Ions.

Embedding Raman reporters within nanosized gaps of metallic nanoparticles is an attractive route for surface-enhanced Raman spectroscopy (SERS) applications, although often this involves complex synthesis procedures that limit their practical use. Herein, we present the tip-selective direct growth of silver satellites surrounding gold nanostars (AuNSt@AgSAT), mediated by a dithiol Raman reporter 1,4-benzenedithiol (BDT). We propose that BDT is embedded within nanogaps which form between the AuNSt tips and the satellites, and plays a key role in mediating the satellite growth. Not only proposing a rationale for the mechanistic growth of the AuNSt@AgSAT, we also demonstrate an example for its use for the detection of Hg2+ ions in water. The presence of Hg2+ resulted in amalgamation of the AuNSt@AgSAT, which altered both its structural morphology and Raman enhancement properties. This provides a basis for the detection where the Raman intensity of BDT is inversely proportional to the Hg2+ concentrations. As a result, Hg2+ could be detected at concentrations as low as 0.1 ppb. This paper not only provides important mechanistic insight into the tip-selective direct growth of the anisotropic nanostructure but also proposes its excellent Raman enhancement capability for bioimaging as well as biological and chemical sensing applications.

Peroxidase-Mimicking Activity of Biogenic Gold Nanoparticles Produced from Prunus nepalensis Fruit Extract: Characterizations and Application for the Detection of Mycobacterium bovis.

In the present study, a facile, eco-friendly, and controlled synthesis of gold nanoparticles (Au NPs) using Prunus nepalensis fruit extract is reported. The biogenically synthesized Au NPs possess ultra-active intrinsic peroxidase-like activity for the oxidation of 3,3',5,5'-tetramethylbenzidine (TMB) in the presence of H2O2. Chemical analysis of the fruit extract demonstrated the presence of various bioactive molecules such as amino acids (l-alanine and aspartic acids), organic acids (benzoic acid and citric acid), sugars (arabinose and glucose), phenolic acid, and bioflavonoids (niacin and myo-inositol), which likely attributed to the formation of stable biogenic Au NPs with excellent peroxidase-mimicking activity. In comparison with the natural horseradish peroxidase (HRP) enzyme, the biogenic Au NPs displayed a 9.64 times higher activity with regard to the reaction velocity at 6% (v/v) H2O2, presenting a higher affinity toward the TMB substrate. The Michaelis-Menten constant (KM) values for the biogenic Au NPs and HRP were found to be 6.9 × 10-2 and 7.9 × 10-2 mM, respectively, at the same concentration of 100 pM. To investigate its applicability for biosensing, a monoclonal antibody specific for Mycobacterium bovis (QUBMA-Bov) was directly conjugated to the surface of the biogenic Au NPs. The obtained results indicate that the biogenic Au NPs-QUBMA-Bov conjugates are capable of detecting M. bovis based on a colorimetric immunosensing method within a lower range of 100 to 102 cfu mL-1 with limits of detection of ∼53 and ∼71 cfu mL-1 in an artificial buffer solution and in a soft cheese spiked sample, respectively. This strategy demonstrates decent specificity in comparison with those of other bacterial and mycobacterial species. Considering these findings together, this study indicates the potential for the development of a cost-effective biosensing platform with high sensitivity and specificity for the detection of M. bovis using antibody-conjugated Au nanozymes.

Stern-Volmer analysis of photocatalyst fluorescence quenching within hollow-core photonic crystal fibre microreactors.

We report the use of optofluidic hollow-core photonic crystal fibres as microreactors for Stern-Volmer (SV) luminescence quenching analysis of visible-light photocatalytic reactions. This technology enables measurements on nanolitre volumes and paves the way for automated SV analyses in continuous flow that minimise catalyst and reagent usage. The method is showcased using a recently developed photoredox-catalysed α-C-H alkylation reaction of unprotected primary alkylamines.