New ionic Cu(i) coordination complexes with 4,4′-bisubstituted-2,2′-biquinolines showing low temperature lamello-columnar and columnar hexagonal thermotropic mesomorphism, depending on the substituents, are synthesized and characterized.
Five‐ and six‐coordinated zinc(II) complexes, [Zn(QR)2(H2O)] (1–2) and [Zn(QR)2(L)] (3–8) {HQR = 4‐R(C=O)‐5‐pyrazolones in general, in detail HQC17, R = –(CH2)16CH3, HQCy, R = –C6H11; L = bipy, tmeda or en} have been synthesized and characterized by IR, 1H and 13C NMR, UV/Visible spectroscopy, elemental analysis, TGA and ESI mass spectrometry. The square pyramidal complex [Zn(QC17)2(H2O)] (1) has been structurally characterized, together with a trans octahedral [Zn(QCy)2(EtOH)2] (2b) species obtained by recrystallization of [Zn(QCy)2(H2O)] (2) from ethanol. Additionally, in both complexes [Zn(QCy)2(bipy)] (4) and [Zn(QC17)2(tmeda)] (5) structurally characterized by single crystal X ray diffraction, the same amount of Δ and Λ enantiomers are present, with the only difference related to the mutual disposition of the different type of the QR coordinated oxygen atoms. The cytotoxicity of the complexes [Zn(QCy)2(H2O)] (2), [Zn(QCy)2(bipy)] (4) and [Zn(QCy)2(en)] (8) has been evaluated in vitro against MCF‐7 human breast cancer cell line in a biohybrid membrane system. Results revealed that zinc complexes possess antiproliferative activity inducing apoptosis by activation of caspase‐3 and p‐JNK.
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.
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