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This paper presents the fabrication and characterization of new gold–silver core–shell nanoparticles labeled with para-mercaptobenzoic acid (4MBA) molecules and demonstrates their use as surface-enhanced Raman spectroscopy (SERS)-nanotags with ultra-bright traceability inside cells and ability to convey spectrally-coded information about the intracellular pH by means of SERS. Unlike previous reported studies, our fabrication procedure includes in the first step the synthesis of chitosan-coated gold nanoparticles as a seed material with subsequent growing of a silver shell. The bimetallic core–shell structure is revealed by transmission electron microscopy, high-angle annular dark field scanning transmission electron microscopy, energy-dispersive x-ray elemental mapping and the presence of two interacting localized surface plasmon resonance modes in UV–vis extinction spectrum. The high SERS activity and sensitivity of as fabricated 4MBA-chit-Au–AgNPs nano-constructs to different pH in solution is investigated under 532 and 633 nm laser lines excitation. Next, in view of future studies in cancer diagnosis, the in vitro antiproliferative effects of SERS-nanotags against human ovarian adenocarcinoma cells (NIH:OVCAR-3) are evaluated. The capacity to operate as bright SERS nanotags with precise localization at a single cell level as well as intracellular pH indicators is clearly demonstrated by performing cell imaging under scanning confocal Raman microscopy.

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To understand the photochemical behaviour of the polydopamine polymer in detail, one would also need to know the behaviour of its building blocks. The electronic absorption, as well as the fluorescence emission and excitation spectra of the dopamine were experimentally and theoretically investigated considering time-resolved fluorescence spectroscopy and first-principles quantum theory methods. The shape of the experimental absorption spectra obtained for different dopamine species with standard, zwitterionic, protonated, and deprotonated geometries was interpreted by considering the advanced equation-of-motion coupled-cluster theory of DLPNO-STEOM. Dynamical properties such as fluorescence lifetimes or quantum yield were also experimentally investigated and compared with theoretically predicted transition rates based on Fermi’s Golden Rule-like equation. The results show that the photochemical behaviour of dopamine is strongly dependent on the concentration of dopamine, whereas in the case of a high concentration, the zwitterionic form significantly affects the shape of the spectrum. On the other hand, the solvent pH is also a determining factor for the absorption, but especially for the fluorescence spectrum, where at lower pH (5.5), the protonated and, at higher pH (8.0), the deprotonated forms influence the shape of the spectra. Quantum yield measurements showed that, besides the radiative deactivation mechanism characterized by a relatively small QY value, non-radiative deactivation channels are very important in the relaxation process of the electronic excited states of different dopamine species.

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Herein is presented a novel and efficient portable paper-based sensing platform using paper-incorporated histidine stabilized gold nanoclusters (His-AuNCs), for the sensitive and selective detection of Fe ions from low-volume real water samples based on photoluminescence (PL) quenching. Highly photoluminescent colloidal His-AuNCs are obtained via a novel microwave-assisted method. The His-AuNCs-based sensor reveals a limit of detection (LOD) as low as 0.2 μM and a good selectivity towards Fe ions, in solution. Further, the fabricated portable sensing device based on paper impregnated with His-AuNCs proves to be suitable for the easy detection of hazardous Fe levels from real water samples, under UV light exposure, through evaluating the level of PL quenching on paper. Photographic images are thereafter captured with a smartphone camera and the average blue intensity ratio (I/I0) of the His-AuNCs-paper spots is plotted against [Fe2+] revealing a LOD of 3.2 μM. Moreover, selectivity and competitivity assays performed on paper-based sensor prove that the proposed platform presents high selectivity and accuracy for the detection of Fe ions from water samples. To validate the platform, sensing assays are performed on real water samples from local sources, spiked with 35 μM Fe ions (i.e., Fe2+). The obtained recoveries prove the high sensitivity and accuracy of the proposed His-AuNCs-paper-based sensor pointing towards its applicability as an easy-to-use, fast, quantitative and qualitative sensor suitable for on-site detection of toxic levels of Fe ions in low-volume real water samples.

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