Browsing by Issue Date, starting with "2020-05-02"
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- Finding value in wastewaters from the cork industry: carbon dots synthesis and fluorescence for hemeprotein detectionPublication . Alexandre, Marta R.; Costa, Alexandra I.; Berberan-Santos, Mario; Prata, José V.Valorisation of industrial low-value waste residues was preconized. Hence, carbon dots (C-dots) were synthesized from wastewaters of the cork industry—an abundant and a_ordable, but environmentally-problematic industrial e_uent. The carbon nanomaterials were structurally and morphologically characterised, and their photophysical properties were analysed by an ensemble of spectroscopy techniques. Afterwards, they were successfully applied as highly-sensitive fluorescence probes for the direct detection of haemproteins. Haemoglobin, cytochrome c and myoglobin were selected as specific targets owing to their relevant roles in living organisms, wherein their deficiencies or surpluses are associated with several medical conditions. For all of them, remarkable responses were achieved, allowing their detection at nanomolar levels. Steady-state and time-resolved fluorescence, ground-state UV–Vis absorption and electronic circular dichroism techniques were used to investigate the probable mechanisms behind the fluorescence turn-o_ of C-dots. Extensive experimental evidence points to a static quenching mechanism. Likewise, resonance energy transfer and collisional quenching have been discarded as excited-state deactivating mechanisms. It was additionally found that na oxidative, photoinduced electron transfer occurs for cytochrome c, the most electron-deficient protein Besides, C-dots prepared from citric acid/ethylenediamine were comparatively assayed for protein detection and the di_erences between the two types of nanomaterials highlighted.
- Highly sensitive and selective fluorescent probes for Cu(II) detection based on calix[4]arene-oxacyclophane architecturesPublication . Costa, Alexandra I.; Barata, Patrícia; Fialho, Carina; Prata, José V.A new topological design of fluorescent probes for sensing copper ion is disclosed. The calix[4]arene-oxacyclophane (Calix-OCP) receptor, either wired-in-series in arylene-alt-ethynylene conjugated polymers or standing alone as a sole molecular probe, display a remarkable a_nity and selectivity for Cu(II). The unique recognition properties of Calix-OCP system toward copper cation stem from its pre-organised cyclic array of O-ligands at the calixarene narrow rim, which is kept in a conformational rigid arrangement by a tethered oxacyclophane sub-unit. The magnitude of the binding constants (Ka = 5.30 8.52 _ 104 M1) and the free energy changes for the inclusion complexation (DG = 27.0 28.1 kJmol1), retrieved from fluorimetric titration experiments, revealed a high sensitivity of Calix-OCP architectures for Cu(II) species. Formation of supramolecular inclusion complexes was evidenced from UV-Vis spectroscopy. The new Calix-OCP-conjugated polymers (polymers 4 and 5), synthesized in good yields by Sonogashira–Hagihara methodologies, exhibit high fluorescence quantum yields (_F = 0.59 0.65). Density functional theory (DFT) calculations were used to support the experimental findings. The fluorescence on–o_ behaviour of the sensing systems is tentatively explained by a photoinduced electron transfer mechanism.