An NIR Emissive Donor-π-Acceptor Dicyanomethylene-4H-Pyran Derivative as a Fluorescent Chemosensor System towards Copper (II) Detection

A.K. thanks the Erasmus+ Programme of the European Union for a student mobility fellowship. Publisher Copyright: © 2022 by the authors.A novel donor-π-acceptor fluorescent dye as a chemosensor for Cu2+ ions is herein presented. The fluorophoric core consists of a 3,5-diphenyl-dicyanomethylene-4H-pyran (DCM), with extended styryl chains on positions 2 and 6, bearing terminal di-(2-picolyl)amine (DPA) groups for metal coordination. Optical characterization of the chemosensor dye reveals an absorption maximum at ca. 500 nm and a strong bathochromic shift in the emission, reaching ca. 750 nm in polar solvents. This solvatochromic behavior, which yields very large Stokes shifts (up to ~6700 cm−1), is characteristic of the strong intramolecular Charge Transfer (CT) nature of this chromophoric system. While the chemosensor has demonstrated no changes in its optical properties over a wide pH range (2–12), a strong quenching effect was observed upon Cu2+ coordination, with a 1:1 binding stoichiometry, indicating that only one DPA unit is capable of effectively chelating Cu2+, rendering the second DPA motif inactive. The binding constant was determined to be 7.5 × 107 M−1, indicating a very high sensitivity, and an LOD of 90.1 nM. Competition assays have demonstrated that the chemosensor is highly selective towards Cu2+, even in the presence of excesses of other mono- and di-valent cations. Co2+ and Ni2+ proved to be the strongest interferents, particularly in the luminescent response. Paper test-strips prepared with the embedded sensor showed a fluorometric response in the presence of different copper (II) concentrations, which attested to the potential of this chemosensor to be used in the determination of Cu2+ content in aqueous media, for in-field applications.publishersversionpublishe

Design of fluorescent chemosensors for Naproxen and ATP and subsequent immobilization in nanoparticles

In this work, the design and characterization of two fluorescent chemosensor dyes for two distinct analytes, respectively Naproxen and adenosine triphosphate (ATP), is fully described. For the first case (Naproxen chemosensor), the chemosensor dye consisted of styrylpyridinium fluorophore and the synthesis was performed in two reaction steps with relatively good yield. The sensing mechanism was based on twisted intramolecular charge transfer (TICT), with Naproxen inducing a fluorescence enhancement on the chemosensor. The limit of detection (LOD) for Naproxen was 0.054 mM. The sensor dye was used for the synthesis of polyacrylamide nanoparticles, PAA-NPs, with a diameter of 34 nm. The sensitivity of the PAA-NPs to Naproxen was decreased when compared to the free dye in solution with a LOD of 0.50 mM. Selectivity and competitive assays were performed and the obtained results indicate that the synthesized PAA-NPs can be used for rapid diagnosis of Naproxen overdose in human plasma samples. For the second case (ATP chemosensor), the sensor dye was based on a naphthalimide fluorophore and the synthesis comprised four reaction steps. The chemosensor presented a dipicolylamine unit able to complex with metal ions which allowed ATP binding, translated in a fluorescence enhancement of 2.3 fold. Results suggested that adenine appeared to present a preference in interaction with the naphthalimide fluorophore, probably through stacking interactions. The chemosensor was covalently immobilized onto amine surface-functionalized silica nanoparticles through NHS-ester activation. The obtained nanoparticles were found to have a hydrodynamic diameter of 126 nm. Their sensing properties towards ATP showed a significant decrease in sensitivity when compared to the dye in solution although sensing of concentrations in the low micromolar range was also found possible

Selective Coordination of Cu2+ and Subsequent Anion Detection Based on a Naphthalimide-Triazine-(DPA)2 Chemosensor

UIDB/50006/2020 SFRH/BD/120985/2016 Project LISBOA-01-0145-FEDER-007660 PPBI-POCI-01-0145-FEDER-022122 DL 57-021/DL/2018 ROTEIRO/0031/2013-PINFRA/22161/2016A new fluorescent chemosensor for copper (II) and subsequent anion sensing was designed and fully characterized. The sensor consisted of a 1,8-naphthalimide core, bearing two terminal dipicolylamine (DPA) receptor units for binding metal cations, and an ethoxyethanol moiety for enhanced water solubility. The DPA units are connected to position 4 of the fluorophore via a triazine-ethylenediamine spacer. Fluorescence titration studies of the chemosensor revealed a high selectivity for Cu2+ over other divalent ions, the emissions were strongly quenched upon binding, and a stability constant of 5.52 log units was obtained. Given the distance from DPA chelating units and the fluorophore, quenching from the Cu2+ complexation suggests an electron transfer or an electronic energy transfer mechanism. Furthermore, the Cu2+-sensor complex proved to be capable of sensing anionic phosphate derivatives through the displacement of the Cu2+ cation, which translated into a full recovery of the luminescence from the naphthalimide. Super-resolution fluorescence microscopy studies performed in HeLa cells showed there was a high intracellular uptake of the chemosensor. Incubation in Cu2+ spiked media revealed a strong fluorescent signal from mitochondria and cell membranes, which is consistent with a high concentration of ATP at these intracellular sites.publishersversionpublishe

Toward Light-Controlled Supramolecular Peptide Dimerization

The selective photodeprotection of the NVoc-modified FGG tripeptide yields the transformation of its 1:1 receptor−ligand complex with cucurbit[8]uril into a homoternary FGG2@CB8 assembly. The resulting lightinduced dimerization of the model peptide provides a tool for the implementation of stimuli-responsive supramolecular chemistry in biologically relevant contexts.The work was supported by the Associate Laboratory for Green ChemistryLAQV (UIDB/50006/2020) and by the Applied Molecular Biosciences UnitUCIBIO (UIDB/ 04378/2020), both financed by FCT. FCT/MCTES is also acknowledged for supporting the National Portuguese NMR Network (ROTEIRO/0031/2013-PINFRA/22161/2016, cofinanced by FEDER through COMPETE 2020, POCI, PORL, and FCT through PIDDAC) and for the grants PTDC/QUICOL/32351/2017, PTDC/QUI-QFI/30951/2017, and CEECIND/00466/2017 (N.B.). U.P. thanks the Spanish Ministry of Science, Innovation, and Universities (CTQ2017-89832-P). We are grateful to Dr. J.P. Da Silva for the mass spectrometry data (equipment financed by CRESC Algarve 2020 and COMPETE 2020; project EMBRC.PT ALG-01-0145-FEDER022121). Funding for open access charge: Universidad de Huelva / CBU

Supramolecular tripodal Au(I) assemblies in water. Interactions with pyrene fluorescent probe

The synthesis of three gold(I) tripodal complexes derived from tripropargylamine and containing the water soluble phosphines PTA (1, 3,5-triaza-7-phosphaadamantane), DAPTA (3,7-diacetyl-1,3,7-triaza--phosphabicyclo[3.3.1]nonane) and TPPTS (triphenylphosfine-3,3',3''-trisulfonic acid trisodium salt) is here described. The three complexes are observed to give rise to the formation of supramolecular aggregates in water and very long fibers. This property has been analyzed by means of 1H-NMR spectroscopy at different concentrations and SAXS. The results point out the important role of the phosphine moieties as the main enthalpic or entropic contribution in the resulting Gibbs energy of aggregates formation. The tripodal structure of the three complexes together with the presence of gold(I) atoms make them ideal candidates to interact with hydrophobic molecules also in water. For this, the interaction with pyrene in this solvent has been evaluated with successful results in all three complexes. The highest association constant corresponds to 2 as the host. DFT studies indicates the location of pyrene in the tripodal cavity as the most stable conformation. The interaction with pyrene has been additionally studied within cholate hydrogel matrixes pointing out the stability of the resulting host:guest adducts in the different medium

Aggregation induced emission of a new naphthyridine-ethynyl-gold(I) complex as a potential tool for sensing guanosine nucleotides in aqueous media

A new organometallic alkynyl-gold(I) complex, capable of exhibiting Aggregation Induced Emission was designed and synthesized. The linear complex structure possesses a central Au(I) atom, bearing two axial ligands: (1) 1,3,5-Triaza-7-phosphaadamantane; and (2) 2- acetamido-7-ethynyl-1,8-naphthyridine. While the former accounts for its partial solubility in aqueous environment, the latter acts as a receptor unit for binding guanosine nucleotides and derivatives via multiple hydrogen bonding. At high concentrations, aggregation of the complex was observed by the formation of new absorption (λmax ~ 400 nm) and emission bands (550-700 nm). Formation of aggregates of ca. 60 nm diameter was confirmed with Small Angle X-Ray Scattering (SAXS). Disruption of the aggregates in the presence of guanosine derivatives resulted in a ratiometric signal with apparent association constants in the order of 105 M-1 and high sensitivity (around 63% signal change) which are, to the best of our knowledge, in line with the highest recorded for nucleotide sensing based on hydrogen bonding that are capable of working in water. Computational studies indicate the presence of additional hydrogen bonding interactions that account for the strong binding of the Au(I) complex to phosphorylated Guanosine nucleotides

Non-emissive RuII Polypyridyl Complexes as Efficient and Selective Photosensitizers for the Photooxidation of Benzylamines

RTI2018-100709-B-C21 CTQ (QMC)-RED2018-102471-T) Junta de Castilla y Leon (BU087G19 FEDER (BU042U16-BU305P18).Five new RuII polypyridyl complexes bearing N-(arylsulfonyl)-8-amidoquinolate ligands and three of their biscyclometalated IrIII congeners have been prepared and employed as photocatalysts (PCs) in the photooxidation of benzylamines with O2. In particular, the new RuII complexes do not exhibit photoluminescence, rather they harvest visible light efficiently and are very stable in solution under irradiation with blue light. Their non-emissive behavior has been related to the low electrochemical energy gaps and rationalized on the basis of theoretical calculations (DFT analysis) that predict low S0←T1 energy values. Moreover, the RuII complexes, despite being non-emissive, display excellent activities in the selective photocatalytic transformation of benzylamines into the corresponding imines. The presence of an electron-withdrawing group (-CF3) on the arene ring of the N-(arylsulfonyl)-8-amidoquinolate ligand improves the photocatalytic activity of the corresponding photocatalyst. Furthermore, all the experimental evidence, including transient absorption spectroscopy measurements suggest that singlet oxygen is the actual oxidant. The IrIII analogues are considerably more photosensitive and consequently less efficient photosensitizers (PSs).authorsversionpublishe

Ten golden rules for optimal antibiotic use in hospital settings: the WARNING call to action

Antibiotics are recognized widely for their benefits when used appropriately. However, they are often used inappropriately despite the importance of responsible use within good clinical practice. Effective antibiotic treatment is an essential component of universal healthcare, and it is a global responsibility to ensure appropriate use. Currently, pharmaceutical companies have little incentive to develop new antibiotics due to scientific, regulatory, and financial barriers, further emphasizing the importance of appropriate antibiotic use. To address this issue, the Global Alliance for Infections in Surgery established an international multidisciplinary task force of 295 experts from 115 countries with different backgrounds. The task force developed a position statement called WARNING (Worldwide Antimicrobial Resistance National/International Network Group) aimed at raising awareness of antimicrobial resistance and improving antibiotic prescribing practices worldwide. The statement outlined is 10 axioms, or “golden rules,” for the appropriate use of antibiotics that all healthcare workers should consistently adhere in clinical practice

Chalcone-based fluorescent chemosensors as new tools for detecting Cu2+ ions

The Spanish Ministerio de Ciencia e Innovación (Project PID2019-104121 GB-I00) is also aknowledged. Publisher Copyright: © 2021 Elsevier LtdThe design and full characterization of new fluorescent chemosensors for Cu2+ is herein presented. The structure of the sensors is based on a chalcone backbone as the chromophoric unit, with di-(2-picolyl)amine (DPA) as a receptor moiety. Two systems, bearing one or two chalcone-DPA units, were synthesized and fully characterized. UV–Vis titrations with several metal ions were performed and both chemosensors exhibited a strong hypsochromic shift in the absorption spectra upon Cu2+ addition, indicating a higher selectivity for this metal over other divalent cations. Additionally, fluorescent spectra recorded in the same conditions revealed a stronger quenching effect in the presence of Cu2+, even in the presence of other metal cations, with association constants above 106 M−1 and detection limits below the micromolar level for both chemosensors. Paper test-strips with one of the chemosensors were prepared to attest its possible application for detecting copper in aqueous samples.authorsversionpublishe