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- Detection of azo dyes using carbon dots from olive mill wastesPublication . Sousa, Diogo A.; Berberan-Santos, Mario; Prata, José VirgílioAzo dyes are widely spread in our day life, being heavily used in cosmetics, healthcare products, textile industries, and as artificial food colorants. This intense industrial activity, which inherently includes their own production, inexorably leads to uncontrolled release of dyes into the environment. As emerging pollutants, their detection, particularly in water systems, is a priority. Herein, a fluorescence-based method was employed for the sensitive and selective detection of anionic and neutral azo dyes. Carbon dots (CDs) synthesized from wet pomace (WP), an abundant semi-solid waste of olive mills, were used as probes. An outstanding capability for detection of azo dyes methyl orange (MO) and methyl red (MR) in aqueous solutions was disclosed, which reached a limit of detection (LOD) of 151 ppb for MO. The selectivity of WP-CDs for the anionic azo dye (MO) was established through competitive experiments with other dyes, either anionic (indigo carmine) or cationic (fuchsin, methylene blue, and rhodamine 6G); perchlorate salts of transition metal cations (Cu(II), Co(II), Fe(II), Fe(III), Hg(II), and Pb(II)); and sodium salts of common anions (NO3-, CO32-, Cl-, and SO42-). Evidence has been collected that supports static quenching as the main transduction event underlying the observed quenching of the probe's fluorescence, combined with a dynamic resonance energy transfer (RET) mechanism at high MO concentrations.
- A solid-state fluorescence sensor for nitroaromatics and nitroanilines based on a conjugated Calix[4]arene polymerPublication . Prata, José V.; Costa, Alexandra I.; Teixeira, CarlosA new conjugated polymer possessing calix[4]arene-oxacyclophane units wired-in-series by phenyleneethynylene linkers was synthesized by a Sonogashira-Hagihara cross-coupling method in high yield. The polymer was structurally characterized by FTIR and 1H/13C/HSQC NMR techniques, and its average Mn (38.5 kDa) retrieved from GPC analysis. The polymer is highly emissive (ΦF =0.55) and exhibits a longer-than-usual excited-state lifetime (1.80 ns) for a phenyleneethynylene type polymer. Similar photo physical properties (absorption and fluorescence emission) were observed in solution and insolid-state. This stems from the presence of bulky calixarene moieties along the polymer chains which prevent interchain staking and the formation of ground-state aggregates and/or non-emissive exciplexes, both deleterious to solid-state materials envisioned for fluorescence sensing applications. Moreover, the intrinsic molecular recognition capabilities of its two rigid inner cavities (calixarene and cyclophane sub-units), allied with the high three-dimensionality of the macromolecule that creates additional interstitial voids around the molecular receptors, can boost its sensory responses towards specific analytes. A high sensitive response was observed in the detection of nitroaromatics and nitroanilines in neat vapour phases by casted films of the polymer. The largest sensitivitieswereobtainedfor2,4-dinitrotoluene (a taggant for the explosive TNT;>85% of fluorescence quenching upon 1 min exposure) and ortho-nitroaniline (90% of emission reduction in 30s).The sensory responses attained in solid-state are discussed on the basis of the electron affinities of the analytes and their electrostatic interactions with polymer films.
- Solid-state sensory properties of Calix-Poly(Phenylene Ethynylene)s toward nitroaromatic explosivesPublication . Costa, Alexandra; Pinto, Hugo D.; Ferreira, Luís F. V.; Prata, José VirgílioThis study is primarily focused in establishing the solid-state sensory abilities of several luminescent polymeric calix[4]arene-based materials toward selected nitroaromatic compounds (NACs), creating the foundations for their future application as high performance materials for detection of high explosives. The phenylene ethynylene-type polymers possessing bis-calix[4]arene scaffolds in their core were designed to take advantage of the known recognition abilities of calixarene compounds toward neutral guests, particularly in solid-state, therefore providing enhanced sensitivity and selectivity in the sensing of a given analyte. It was found that all the calix[4]arene-poly(para-phenylene ethynylene)s here reported displayed high sensitivities toward the detection of nitrobenzene, 2,4-dinitrotoluene and 2,4,6-trinitrotoluene (TNT). Particularly effective and significant was the response of the films (25-60 nm of thickness) upon exposure to TNT vapor (10 ppb): over 50% of fluorescence quenching was achieved in only 10 s. In contrast, a model polymer lacking the calixarene units showed only reduced quenching activity for the same set of analytes, clearly highlighting the relevance of the macrocyclics in promoting the signaling of the transduction event. The films exhibited high photostability (less than 0.5% loss of fluorescence intensity up to 15 min of continuous irradiation) and the fluorescence quenching sensitivity could be fully recovered after exposure of the quenched films to saturated vapors of hydrazine (the initial fluorescence intensities were usually recovered within 2-5 min of exposure to hydrazine).
- 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.
- Chiroptical and emissive properties of a calix[4]arene-containing chiral poly (P-phenylene ethynylene) with enantioselective recognition abilityPublication . Prata, José Virgílio; Costa, Alexandra; Pescitelli, Gennaro; Pinto, Hugo D.Supramolecular chirality was achieved in solutions and thin films of a calixarene-containing chiral aryleneethynylene copolymer. The observed chiroptical activity, which is primarily allied with the formation of aggregates of high molecular weight polymer chains, is the result of a combination of intrachain and interchain effects. The former arises by the adoption of an induced helix-sense by the polymer main-chain while the latter comes from the exciton coupling of aromatic backbone transitions. The co-existence of bulky bis-calixKlarene units and chiral side-chains on the polymer skeleton prevents efficient pi-stacking of neighbouring chains, keeping the chiral assembly highly emissive. In contrast, for a model polymer lacking calixarene moieties, the chiroptical activity is dominated by strong interchain exciton couplings as a result of more favourable packing of polymer chains, leading to a marked decrease of photoluminescence in the aggregate state. The enantiomeric recognition abilities of both polymers towards (R)- and (S)-alpha-methylbenzylamine were examined. It was found that a significant enantiodiscrimination is exhibited by the calixarene-based polymer in the aggregate state.
- Carbon dots synthesis from coffee grounds, and sensing of nitroanilinesPublication . Moraes, Bianca; Costa, Alexandra I.; Barata, Patrícia; Prata, José V.Fluorescent carbon dots (C-dots) were directly synthesized by a sustainable and eco friendly one-pot microwave-assisted hydrothermal carbonization method from coffee grounds waste. The coffee grounds obtained from automatic coffee machines, after being heated at 190 °C for 1–4 h in the presence of nitrogen additives, furnished the desired carbon nanomaterials. Struc tural and photophysical properties of the as-synthesized nanomaterials were evaluated by FTIR, 1H NMR, UV-Vis, and fluorescence spectroscopies. The ability of the C-dots to behave as probes for isomeric nitroanilines (ortho-, meta- and para-nitroaniline) was explored through fluorimetric titra tion experiments. High sensitivities and selectivities were obtained for the detection of nitroanilines in aqueous media.
- How an environmental issue could turn into useful high-valued products: the olive mill wastewater casePublication . Sousa, D. A.; Costa, Alexandra; Alexandre, M. R.; Prata, José VirgílioCarbon-based nanomaterials have been directly synthesized fromolivemillwastewaters (OMWWs) for the first time, using expedite and simple environmental-friendly procedures. The OMWWs collected from a mill operating by a two-phase centrifugation system, after being heated (150–300 °C) solely or in the presence of additives for 2–12 h, furnished nanostructuredmaterials in high yields. Under an optimised set of reaction conditions here described, the resultant as-synthetized aqueous dispersions of carbon nanoparticles exhibit outstanding fluorescence emission properties, which encompass an astonishing quantum yield (ΦF N 0.4). The as-prepared carbon nanomaterials show excitation-dependent emissions covering the whole visible spectrum, with a predominant high glow in the blue-green region, and a remarkable photostability. The relevant features attained by the nanomaterials here reported, allied to their easy synthesis and carbon source affordability, render them with unique capabilities to be used in several current and emerging technological applications, namely in bioimaging and nanomedicine, sensorial analysis, (photo)catalysis and optoelectronics. The as-synthesized nanoparticles show a remarkable high sensitivity and selectivity towards haemoglobin.
- Synthesis, structure, and optical properties of an alternating calix[4]arene-based meta-linked phenylene ethynylene copolymerPublication . D. Barata, Patrícia; Costa, Alexandra; Ferreira, Luis F. V.; Prata, José VirgílioNovel alternating copolymers comprising biscalix[4]arene-p-phenylene ethynylene and m-phenylene ethynylene units (CALIX-m-PPE) were synthesized using the Sonogashira-Hagihara cross-coupling polymerization. Good isolated yields (60-80%) were achieved for the polymers that show M-n ranging from 1.4 x 10(4) to 5.1 x 10(4) gmol(-1) (gel permeation chromatography analysis), depending on specific polymerization conditions. The structural analysis of CALIX-m-PPE was performed by H-1, C-13, C-13-H-1 heteronuclear single quantum correlation (HSQC), C-13-H-1 heteronuclear multiple bond correlation (HMBC), correlation spectroscopy (COSY), and nuclear overhauser effect spectroscopy (NOESY) in addition to Fourier transform-Infrared spectroscopy and microanalysis allowing its full characterization. Depending on the reaction setup, variable amounts (16-45%) of diyne units were found in polymers although their photophysical properties are essentially the same. It is demonstrated that CALIX-m-PPE does not form ground-or excited-state interchain interactions owing to the highly crowded environment of the main-chain imparted by both calix[4]arene side units which behave as insulators inhibiting main-chain pi-pi staking. It was also found that the luminescent properties of CALIX-m-PPE are markedly different from those of an all-p-linked phenylene ethynylene copolymer (CALIX-p-PPE) previously reported. The unexpected appearance of a low-energy emission band at 426 nm, in addition to the locally excited-state emission (365 nm), together with a quite low fluorescence quantum yield (Phi = 0.02) and a double-exponential decay dynamics led to the formulation of an intramolecular exciplex as the new emissive species.
- Carbon dots from coffee grounds: synthesis, characterization, and detection of noxious nitroanilinesPublication . Costa, Alexandra I.; Barata, Patrícia; Moraes, Bianca; Prata, José V.Coffee ground (CG) waste is generated in huge amounts all over the world, constituting a serious environmental issue owing to its low biodegradability. Therefore, processes that simultaneously aim for its valorization while reducing its environmental impact are in great demand. In the current approach, blue luminescent carbon dots (C-dots) were produced in good chemical yields from CGs following hydrothermal carbonization methods under an extended set of reaction parameters. The remarkable fluorescent properties of the synthesized C-dots (quantum yields up to 0.18) allied to their excellent water dispersibility and photostability prompted their use for the first time as sensing elements for detection of noxious nitroanilines (NAs) in aqueous media. Very high levels of NA detection were achieved (e.g., limit of detection of 68 ppb for p-nitroaniline), being the regioisomeric selectivity attributed to its higher hyperpolarizability and dipole moment. Through ground-state and time-resolved fluorescence assays, a static fluorescence quenching mechanism was established. H-1 NMR titration data also strongly suggested the formation of ground-state complexes between C-dots and NAs.
- Fluorescent bis-calix[4]arene-carbazole conjugates: synthesis and inclusion complexation studies with fullerenes C-60 and C-70Publication . Barata, Patrícia; Costa, Alexandra I.; Costa, Sérgio; Prata, José V.Supramolecular chemistry has become a central theme in chemical and biological sciences over the last decades. Supramolecular structures are being increasingly used in biomedical applications, particularly in devices requiring specific stimuli-responsiveness. Fullerenes, and supramolecular assemblies thereof, have gained great visibility in biomedical sciences and engineering. Sensitive and selective methods are required for the study of their inclusion in complexes in various application fields. With this in mind, two new fluorescent bis-calix[4]arene-carbazole conjugates (4 and 5) have been designed. Herein, their synthesis and ability to behave as specific hosts for fullerenes C-60 and C-70 is described. The optical properties of the novel compounds and their complexes with C-60 and C-70 were thoroughly studied by UV-Vis and steady-state and time-resolved fluorescence spectroscopies. The association constants (K-a) for the complexation of C-60 and C-70 by 4 and 5 were determined by fluorescence techniques. A higher stability was found for the C-70@4 supramolecule (K-a = 5.6 x 10(4) M-1; Delta G = -6.48 kcal/mol). Evidence for the formation of true inclusion complexes between the host 4 and C-60/C-70 was obtained from NMR spectroscopy performed at low temperatures. The experimental findings were fully corroborated by density functional theory (DFT) models performed on the host-guest assemblies (C-60@4 and C-70@4).