Development of fluorochromic polymer doped materials as platforms for temperature sensing using three dansyl derivatives bearing a sulfur bridge

PM003/2016. Funding Information: G. D. thanks to the European Regional Development Fund within the Operational Programme Science and Education for Smart Growth 2014 - 2020 under the Project Center of Excellence: National center of mechatronics and clean technologies - BG05M2OP001-1.001-0008 for the financial support. Publisher Copyright: © 2023 The Author(s)Three novel bis-dansyl derivatives bearing a sulfur bridge have been synthesized, fully characterized, and their photophysical characterization studied in solution, as well as, in the solid state. All compounds exhibit fluorescence emission with quantum yields up to 60%, which vary significantly depending on the solvent used, and the inherent molecular structure. Moreover, these compounds demonstrate positive solvatofluorochromic behaviour emitting from bluish-green to yellow. Kamlet-Taft studies were performed to better understand the solute–solvent interactions. Due to the intrinsic characteristics of the compounds, efforts were made to understand their potential usefulness for environmental remediation and thus metal ion sensing studies were investigated. Compounds L1 and L2 showed high sensitivity to Cu2+ and Hg2+ ions and were found to modulate their emission extensively, with L2 capable of detecting and quantifying up to 4 µM of Hg2+. Considering the solid-state emission of these compounds, the application towards temperature sensing was put forth. L3 was found to quench its emission in a linear relation with temperature up to 170 °C. Several doped polymer thin films were fabricated, which served as a platform to establish a linear relation with temperature beyond their melting point. Polymethylmetacrylate (PMMA) films emitted up to temperatures of 218 °C, which could be fully restored at room temperature. These results suggest the potential application of these bis-chromophoric compounds as molecular thermometers.publishersversionpublishe

Synthesis and Structural Characterization of Branched Bimetallic AuPd Nanoparticles with a Highly Tunable Optical Response

Funding Information: This work received financial support from Portugal national funds [Fundação para a Ciência e Tecnologia and Ministério da Ciência, Tecnologia e Ensino Superior (FCT/MCTES)] through the Projects UIDB/50006/2020 and UIDP/50006/2020. Silvia Nuti, Carlos Lodeiro, José-Luis Capelo-Martinez, Adrián Fernández-Lodeiro, and Javier Fernández-Lodeiro thank the financial support from national funds (FCT/MCTES) through Project Met4Cat (EXPL/QUI-COL/0263/2021). The authors thank the financial support by the PROTEOMASS Scientific Society (Portugal) (General Funding Grant 2023). The authors acknowledge funding from the European Union’s Horizon 2020 Research and Innovation Program under Grant 823717-ESTEEM3, and Ana B. Hungría thanks the financial support from Junta de Andalucía Project P20_00968. Silvia Nuti thanks FCT/MCTEC (Portugal) for her doctoral grant associated with the chemistry Ph.D. program (SFRH/BD/144618/2019). Javier Fernández-Lodeiro thanks FCT for the research contract through the Program DL 57/2016-Norma Transitória. The work was carried out partially through the INL User Facilities (Braga, Portugal) and the Electron Microscope Division (DME) of the Servicios Centrales de Investigación Científica y Tecnológica (SC-ICYT) at Cadiz University (Cadiz, Spain). The authors thank Dr. Jamila Djafari for the assistance with the design of the graphical abstract. Funding Information: This work received financial support from Portugal national funds [Fundação para a Ciência e Tecnologia and Ministério da Ciência, Tecnologia e Ensino Superior (FCT/MCTES)] through the Projects UIDB/50006/2020 and UIDP/50006/2020. Silvia Nuti, Carlos Lodeiro, José-Luis Capelo-Martinez, Adrián Fernández-Lodeiro, and Javier Fernández-Lodeiro thank the financial support from national funds (FCT/MCTES) through Project Met4Cat (EXPL/QUI-COL/0263/2021). The authors thank the financial support by the PROTEOMASS Scientific Society (Portugal) (General Funding Grant 2023). The authors acknowledge funding from the European Union’s Horizon 2020 Research and Innovation Program under Grant 823717-ESTEEM3, and Ana B. Hungría thanks the financial support from Junta de Andalucía Project P20_00968. Silvia Nuti thanks FCT/MCTEC (Portugal) for her doctoral grant associated with the chemistry Ph.D. program (SFRH/BD/144618/2019). Javier Fernández-Lodeiro thanks FCT for the research contract through the Program DL 57/2016–Norma Transitória. The work was carried out partially through the INL User Facilities (Braga, Portugal) and the Electron Microscope Division (DME) of the Servicios Centrales de Investigación Científica y Tecnológica (SC-ICYT) at Cadiz University (Cadiz, Spain). The authors thank Dr. Jamila Djafari for the assistance with the design of the graphical abstract. Publisher Copyright: © 2023 The Authors. Published by American Chemical Society.Bimetallic nanostructures composed of gold (Au) and palladium (Pd) have garnered increased interest for their applications in heterogeneous catalysis. This study reports a simple strategy for manufacturing Au@Pd bimetallic branched nanoparticles (NPs), which offer a tunable optical response, using polyallylamine-stabilized branched AuNPs as template cores for Pd overgrowth. The palladium content can be altered by manipulating the concentration of PdCl42- and ascorbic acid (AA) that are injected, which permit an overgrowth of the Pd shell up to ca. 2 nm thick. The homogeneous distribution of Pd at the surfaces of Au NPs can be carried out regardless of their size or branching degree, which allows for an adjustment of the plasmon response in the near-infrared (NIR) spectral range. As a proof of concept, the nanoenzymatic activity of pure gold and gold-palladium NPs was compared, exploring their peroxidase-like activity in the oxidation of 3,3′,5,5′-tetramethylbenzidine (TMB). The bimetallic AuPd NPs demonstrate an increase in the catalytic properties attributed to the presence of palladium at the surface of gold.publishersversionpublishe

Pollutant metal ions detection and preparation of water-soluble fluorescent polymeric particles

Funding Information: G.D. thanks to the European Regional Development Fund within the Operational Programme Science and Education for Smart Growth 2014–2020 under the Project Center of Exellence: National center of mechatronics and clean technologies - BG05M2OP001-1.001-0008 for the financial support. Funding Information: This work was supported by the Associate Laboratory for Green Chemistry - LAQV which is financed by national funds from FCT/MCTES ( UIDB/50006/2020 and UIDP/50006/2020 ) as well as the PROTEOMASS Scientific Society (Portugal) for funding support (General Funding Grant 2022–2023). F.D. thanks to FCT / MEC (Portugal) for his doctoral grant 2021.05161.BD . E.O thanks FCT / MEC (Portugal) for the individual contract, CEECIND/00648/2017. J.F-.L. thanks the FCT / MEC (Portugal) for the individual research contract DL57. HMS acknowledges the Associate Laboratory for Green Chemistry-LAQV ( LA/P/0008/2020 ) funded by FCT / MCTES for his research contract. Funding Information: The financial support by the Bulgarian National Science Fund (BNSF) under grant – “Novel styryl and polymethine fluorophores as potential theranostic agents “contract N◦ КП-06-М59/1 from 15.11.2021 is gratefully acknowledged by A.K. This work is also developed and acknowledged by A.K. as part of contract №: BG-RRP-2.004-0002-C01, Laboratory of Organic Functional Materials (Project BiOrgaMCT), Procedure BG-RRP-2.004, Establishing of a network of research higher education institutions in Bulgaria”, funded by BULGARIAN NATIONAL RECOVERY AND RESILIENCE PLAN ”. Publisher Copyright: © 2023 The AuthorsPolarity-sensitive dansyl derivatives L1 and L2 were synthesized and their ability to sense pollutant metal ions was investigated. All compounds were found to be highly sensitive towards Cu2+ and Hg2+ metal ions, while L2 being able to detect and quantify Hg2+ concentrations as low as 2.5 μM. Both L1 and L2 exhibit positive solvatofluorochromic behaviour, modulated in the presence of water, which in turn results in fluorescence enhancement via aggregation-induced emission (AIE). Seeking stability and water solubility, luminescent L1-based polystyrene-block-polybutadiene-block-polystyrene (SBS) microparticles (size: 520 ± 76 nm) were successfully prepared while maintaining the fluorescence emission of fluorophore L1 (φ = 22%). This work exemplifies the multiple properties of dansyl-derivatives and their promising applications in biomedicine and environmental fields.publishersversionpublishe

Copper(i) as a reducing agent for the synthesis of bimetallic PtCu catalytic nanoparticles

Funding Information: This work received financial support from PT national funds (FCT/MCTES, Fundação para a Ciência e Tecnologia and Ministério da Ciência, Tecnologia e Ensino Superior) through the projects UIDB/50006/2020 and UIDP/50006/2020. S. N., C. L., J. L. C., A. F. L., and J. F. L. are thankful for the financial support from national funds (FCT/MCTES, Fundação para a Ciência e Tecnologia and Ministério da Ciência, Tecnologia e Ensino Superior) through project Met4Cat, EXPL/QUI-COL/0263/2021. This work was supported by the Spanish Government and the Spanish National Research Council (CSIC) (project PIE 201980E081). We thank the financial support by the PROTEOMASS Scientific Society (Portugal) (General Funding Grant 2022). S. N. thanks FCT/MCTEC (Fundação para a Ciência e Tecnologia and Ministério da Ciência, Tecnologia e Ensino Superior) Portugal for her doctoral grant associated with the Chemistry PhD program (SFRH/ BD/144618/2019). J. F. L. thanks FCT for the research contract through the Program DL 57/2016–Norma Transitória. A. F. L., J. F. L., S. N., J. L. C., and C. L. thank FCT/MCTES (Fundação para a Ciência e Tecnologia and Ministério da Ciência, Tecnologia e Ensino Superior) for the national funds received through the project SiSi4Bacter PTDC/QUI-COL/1517/2020. This work was carried out in part through the use of the INL user facilities. The authors thank Dr Jamila Djafari for the conceptualization and design of the graphical abstract. We also thank Ramiro Martínez from Novozymes for the gift of enzymes. Funding Information: This work received financial support from PT national funds (FCT/MCTES, Fundação para a Ciência e Tecnologia and Ministério da Ciência, Tecnologia e Ensino Superior) through the projects UIDB/50006/2020 and UIDP/50006/2020. S. N., C. L., J. L. C., A. F. L., and J. F. L. are thankful for the financial support from national funds (FCT/MCTES, Fundação para a Ciência e Tecnologia and Ministério da Ciência, Tecnologia e Ensino Superior) through project Met4Cat, EXPL/QUI-COL/0263/2021. This work was supported by the Spanish Government and the Spanish National Research Council (CSIC) (project PIE 201980E081). We thank the financial support by the PROTEOMASS Scientific Society (Portugal) (General Funding Grant 2022). S. N. thanks FCT/MCTEC (Fundação para a Ciência e Tecnologia and Ministério da Ciência, Tecnologia e Ensino Superior) Portugal for her doctoral grant associated with the Chemistry PhD program (SFRH/ BD/144618/2019). J. F. L. thanks FCT for the research contract through the Program DL 57/2016-Norma Transitória. A. F. L., J. F. L., S. N., J. L. C., and C. L. thank FCT/MCTES (Fundação para a Ciência e Tecnologia and Ministério da Ciência, Tecnologia e Ensino Superior) for the national funds received through the project SiSi4Bacter PTDC/QUI-COL/1517/2020. This work was carried out in part through the use of the INL user facilities. The authors thank Dr Jamila Djafari for the conceptualization and design of the graphical abstract. We also thank Ramiro Martínez from Novozymes for the gift of enzymes. Publisher Copyright: © 2023 RSCThis work investigates the potential utilization of Cu(i) as a reducing agent for the transformation of the platinum salt K2PtCl4, resulting in the production of stable nanoparticles. The synthesized nanoparticles exhibit a bimetallic composition, incorporating copper within their final structure. This approach offers a convenient and accessible methodology for the production of bimetallic nanostructures. The catalytic properties of these novel nanomaterials have been explored in various applications, including their use as artificial metalloenzymes and in the degradation of dyes. The findings underscore the significant potential of Cu(i)-mediated reduction in the development of functional nanomaterials with diverse catalytic applications.publishersversionepub_ahead_of_prin

Exploring Coumarin-Based Boron Emissive Complexes as Temperature Thermometers in Polymer-Supported Materials

Three coumarin-based boron complexes (L1, L2 and L3) were designed and successfully incorporated into polymeric matrixes for evaluation as temperature probes. The photophysical properties of the complexes were carried out in different solvents and in the solid state. In solution, compound L1 exhibited the highest fluorescence quantum yield, 33%, with a positive solvatochromism also being observed on the absorption and emission when the polarity of the solvent increased. Additionally in the presence of anions, L1 showed a colour change from yellow to pink, followed by a quenching in the emission intensity, which is due to deprotonation with the formation of a quinone base. Absorption and fluorescence spectra of L1 were calculated at different temperatures by the DFT/B3LYP method. The decrease in fluorescence of compound L1 with an increase in temperature seems to be due to the presence of pronounced torsional vibrations of the donor and acceptor fragments relative to the single bond with C(carbonyl)-C (styrene fragment). L1, L2 and L3, through their incorporation into the polymeric matrixes, became highly emissive by aggregation. These dye@doped polymers were evaluated as temperature sensors, showing an excellent fluorescent response and reversibility after 15 cycles of heating and cooling

Bipolar Disorder: Recent Advances And Future Trends In Bioanalytical Developments For Biomarker Discovery.

In this manuscript we briefly describe bipolar disorder (a depressive and manic mental disease), its classification, its effects on the patient, which sometimes include suicidal tendencies, and the drugs used for treatment. We also address the status quo with regard to diagnosis of bipolar disorder and recent advances in bioanalytical approaches for biomarker discovery. These approaches focus on blood samples (serum and plasma) and proteins as the main biomarker targets, and use various strategies for protein depletion. Strategies include use of commercially available kits or other homemade strategies and use of classical proteomics methods for protein identification based on bottom-up or top-down approaches, which used SELDI, ESI, or MALDI as sources for mass spectrometry, and up-to-date mass analyzers, for example Orbitrap. We also discuss some future objectives for treatment of this disorder and possible directions for the correct diagnosis of this still-unclear mental illness.407661-

Copper(I) as reducing agent for the synthesis of bimetallic PtCu catalytic nanoparticles

Catalysis plays a significant role in modern science and technology and is considered a central pillar in green chemistry to preserve our environment. With the increases in pollutants, contamination leads to global climate change and an urgent need to find new, fast, and greener chemical processes and methodologies is needed. In the present work, we have explored the possibility of use Cu(I) to reduce the platinum salt K2PtCl4 to produce stable nanoparticles. The nanoparticles present copper in the final structure, making it one easy and accessible methodology to produce bimetallic nanostructures. The catalytic applications of the new nanomaterials have been exploited as artificial metalloenzymes and in dye degradation