Raspberry-like Nanoheterostructures Comprising Glutathione-Capped Gold Nanoclusters Grown on the Lanthanide Nanoparticle Surface.

Bare lanthanide-doped nanoparticles (LnNPs), in particular, NaYF4:Yb3+,Tm3+ NPs (UCTm), have been seeded in situ with gold cations to be used in the subsequent growth of gold nanoclusters (AuNCs) in the presence of glutathione (GSH) to obtain a novel UCTm@AuNC nanoheterostructure (NHS) with a raspberry-like morphology. UCTm@AuNC displays unique optical properties (multiple absorption and emission wavelengths). Specifically, upon 350 nm excitation, it exhibits AuNC photoluminescence (PL) (500-1200 nm, λmax 650 nm) and Yb emission (λmax 980 nm); this is the first example of Yb sensitization in a UCTm@AuNC NHS. Moreover, under 980 nm excitation, it displays (i) upconverting PL of the UCTm (at the blue, red and NIR-I, ca. 800 nm, regions); (ii) two-photon PL of AuNC; and (iii) down-shifting PL of thulium (around 1470 nm). The occurrence of energy transfer from UCTm to AuNCs in the UCTm@AuNC NHS was evidenced by the drastic lengthening of the AuNC PL lifetime (τPL) (from few hundred nanoseconds to more than one hundred microseconds). Initial biological assessment of UCTm@AuNC NHSs in vitro revealed high biocompatibility and bioimaging capabilities upon near-infrared excitation.

Harnessing sustainable nanoclusters for sensitive optical detection of tetracyclines and the underlying mechanism.

Simple and rapid sensing methods for the detection of antibiotics in drinks and foods are highly desirable due to the presence of these drugs in food products, as a consequence of extensive abuse of antibiotics in livestock production. In this study, we report a facile synthesis strategy of gold nanoclusters (AuNCs) passivated with N-acetyl-l-cysteine (AuNC@NAC). This nanocluster exhibits a fluorescence emission peak at 700 nm, which gradually decreases at increasing concentrations of antibiotics, such as tetracyclines. The limit of detection (LOD) was determined to be 0.8 ppm with a linear range of 0.1-140 µM (0.04-62 ppm). This method showcased exceptional selectivity in the detection of tetracyclines compared to anions, metallic cations and amino acids. The underlying mechanism has been elucidated, and the fluorescence quenching was found to be a combination of dynamic and static quenching mechanisms, with photoinduced electron transfer (PET) identified as the primary process for dynamic quenching.

Flavin adenine dinucleotide-capped gold nanoclusters: biocompatible photo-emissive nanomaterial and reservoir of lumichrome.

A novel biocompatible nanohybrid consisting of gold nanoclusters (AuNCs) capped with FAD cofactor molecules exhibits distinctive and unique features compared to those of free FAD. The spherical shape of the AuNC provides a large surface to volume ratio, thereby enabling a huge amount of FAD on the AuNC surface while, in basic media and under nitrogen atmosphere, the considerable curvature of its surface enables light-triggered delivery of lumichrome, which is an effective photosensitizer and fluorescent probe.

Gold nanoclusters for ratiometric sensing of pH in extremely acidic media.

AuNCs capped with ß-nicotinamide adenine dinucleotide phosphate exhibit an outstanding performance as fluorescent pH sensors; specifically they exhibit a high emission in strongly acidic media and linear dependence on pH in extremely acidic media (0.6-2.7) as well as in the 7.0-9.2 pH range, while they are unresponsive at intermediate pH values. Remarkably, these AuNCs make ratiometric sensing possible in extremely acidic media with a single fluorophore, specifically the nanocluster itself.

Solvent-modulation of the structure and dimensionality in lanthanoid-anilato coordination polymers.

We show the key role that the size and shape of the solvent molecules may play in the dimensionality and structure of a series of lanthanoid-chloranilato coordination polymers. We report the synthesis, structure and magnetic properties of six different coordination polymers prepared with Er(iii) and chloranilato (C6O4Cl22- = 3,6-dichloro-2,5-dihydroxy-1,4-benzoquinone) and six different solvents: [Er2(C6O4Cl2)3(H2O)6]·10H2O (1), [Er2(C6O4Cl2)3(FMA)6]·4FMA·2H2O (2) (FMA = formamide = NH2CHO), [Er2(C6O4Cl2)3(DMSO)4]·2DMSO·2H2O (3) (DMSO = dimethy sulfoxide = Me2SO), [Er2(C6O4Cl2)3(DMF)6] (4) (DMF = dimethylformamide = Me2NCHO), [Er2(C6O4Cl2)3(DMA)4] (5) (DMA = dimethylacetamide = Me2NC(Me)O) and [Er2(C6O4Cl2)3(HMPA)(H2O)3]·H2O (6) (HMPA = hexamethylphosphormamide = (Me2N)3PO). We show how the different solvent molecules modulate and determine important structural parameters such as the coordination number and geometry, the shape and distortions of the cavities, the presence of solvent molecules in these cavities, the interlayer space and even the dimensionality of the structure.