Metallic nanoparticles show plasmon resonance phenomena when irradiated with electromagnetic radiation of a suitable wavelength, whose value depends on their composition, size, and shape. The damping of the surface electron oscillation causes a release of heat, which causes a large increase in local temperature. Furthermore, this increase is enhanced when nanoparticle aggregation phenomena occur. Local temperature increase is extensively exploited in photothermal therapy, where light is used to induce cellular damage. To activate the plasmon in the visible range, we synthesized 50 nm diameter spherical gold nanoparticles (AuNP) coated with polyethylene glycol and administered them to an E. coli culture. The experiments were carried out, at different gold nanoparticle concentrations, in the dark and under irradiation. In both cases, the nanoparticles penetrated the bacterial wall, but a different toxic effect was observed; while in the dark we observed an inhibition of bacterial growth of 46%, at the same concentration, under irradiation, we observed a bactericidal effect (99% growth inhibition). Photothermal measurements and SEM observations allowed us to conclude that the extraordinary effect is due to the formation, at low concentrations, of a light-induced cluster of gold nanoparticles, which does not form in the absence of bacteria, leading us to the conclusion that the bacterium wall catalyzes the formation of these clusters which are ultimately responsible for the significant increase in the measured temperature and cause of the bactericidal effect. This photothermal effect is achieved by low-power irradiation and only in the presence of the pathogen: in its absence, the lack of gold nanoparticles clustering does not lead to any phototoxic effect. Therefore, it may represent a proof of concept of an innovative nanoscale pathogen responsive system against bacterial infections.
Until now, the ability to form a self-assembled monolayer (SAM) on a surface has been investigated according to deposition techniques, which in turn depend on surface-coater interactions. In this paper, we pursued two goals: to form a SAM on a gold nanosurface and to correlate its formation to the nanosurface curvature. To achieve these objectives, gold nanoparticles of different shapes (spheres, rods, and triangles) were functionalized with a luminescent thiolated bipyridine (Bpy-SH), and the SAM formation was studied by investigating the photo-physics of Bpy-SH. We have shown that emission wavelength and excited-state lifetime of Bpy-SH are strongly correlated to the formation of specific aggregates within SAMs, the nature of these aggregates being in close correlation to the shape of the nanoparticles. Micro-Raman spectroscopy investigation was used to test the SERS effect of gold nanoparticles on thiolated bipyridine forming SAMs.
11 November 2021 in Journal of Materials Chemistry C
Three room-temperature metallomesogens based on Zn(II) cations pentacoordinated by different chelating N^N^N terpyridines and two monodentate gallate co-ligands were designed and synthesized. Depending on the terpyridine ligand's tip functionality, the complexes self-assemble into either a 3D hexagonal mesophase or into a columnar hexagonal mesophase. A systematic study between the structure (molecular architecture, arrangement of the molecules and columns, and chains in both types of mesophases) and photophysical properties (emission maxima and yields, lifetimes of the excited states in the mesophase), correlated with investigations of single molecules in solution, was conducted. Remarkably, one complex exhibited a record quantum yield of 95.0% in solution, while in the mesophase, despite quenching due to the radiative deactivation from the ILCT state, still retained a considerable emission yield of ϕ = 20.2%. The polarized emission of an oriented film, determined for the first time in columnar metallomesogens, shows a dichroic emission ratio (I||/I⊥) of 1.30. DFT and TDDFT computational studies confirmed the origin of the observed fluorescence anisotropy from the transition dipole moment oriented along the C2 symmetry axis of the molecule combined with a high level of order in the 3D mesophase.
The transitioning of nanotechnology from laboratory to industrial-scale manufacturing poses various challenges in nanoparticle realization. From this perspective, beside the conventional synthetic procedure, based on the seed-mediated growth approach, a reshaping thermal strategy has been investigated to improve the control on gold nanorods aspect ratio, with the aim to point out a potential and encouraging way to better manage the scalability and reproducibility of nanoparticles. For this purpose, nanorods covered with CTAB and nanorods enclosed within a silica shell of tuned thickness have been synthesized and submitted to a post-thermal treatment at various temperatures, up to 300 °C for CTAB recovered gold nanorods (AuNR@CTAB), and up to 500 °C for silica-shell embedded gold nanorods (AuNR@SiO2). For AuNR@CTAB, through accurate temperature control, the longitudinal plasmonic band can be moved very close to the transversal one upon slight reduction of their length. Instead, for AuNR@SiO2, owing to the fully inorganic shell, a higher temperature of treatment can be reached leading to the possibility of reshaping the nanorods into spheres without the observation of any by-products.
A series of novel cationic curcumin-based Pt(II) complexes with neutral (N^N) ligands and triflate anions as counterions, [(N^N)Pt(curc)]CF3SO3, 1–4, were synthesised and fully characterised. The antioxidant radical scavenging activity of complexes 1–4 was measured spectrophotometrically using DPPH as the internal probe. Computational strategies have been exploited to ascertain the mechanism of antioxidant action of curcumin (H(curc)) and its Pt(II) complexes. Finally, compounds 1–4 were tested in vitro for their growth inhibitory activity against two bacteria (Staphylococcus aureus and Escherichia coli) by the disk diffusion technique at different Pt(II) complex solution concentrations. The effect of the complexation of H(curc) was investigated.