Pub Date : 2025-01-20DOI: 10.1016/j.dyepig.2025.112666
Mewenn Yvin , Elise Michel , Rémi Métivier , Laurent Galmiche , Lucas Frédéric , Clémence Allain , Pierre Audebert
Fluorogenic probes that can selectively target molecules or materials thanks to click chemistry are promising tools for labelling or functionalization. Heptazines are heterocycles that gather appealing electrochemical and photophysical properties, combining high photooxidation potentials with long fluorescence lifetimes. However, selective grafting of molecular heptazines on a substrate is still underdeveloped. In this work, we report the synthesis, photophysical and electrochemical properties of two heptazine derivatives conjugated with one and three tetrazine rings respectively. These heptazines conjugated to tetrazines are very weakly fluorescent. We demonstrate that they can react in a fast manner with a strained alkyne, through an Inverse Electron Demand Diels-Alder reaction. This reaction has been followed thanks to a home-built photokinetics setup: in a timecale of a few seconds blue emitting heptazine pyridazine conjugates are generated with an 8.6 to 13.6 fluorescence turn-on.
{"title":"Fluorogenic heptazines functionalized with tetrazine rings for conjugation through inverse Electron Demand Diels-Alder reaction","authors":"Mewenn Yvin , Elise Michel , Rémi Métivier , Laurent Galmiche , Lucas Frédéric , Clémence Allain , Pierre Audebert","doi":"10.1016/j.dyepig.2025.112666","DOIUrl":"10.1016/j.dyepig.2025.112666","url":null,"abstract":"<div><div>Fluorogenic probes that can selectively target molecules or materials thanks to click chemistry are promising tools for labelling or functionalization. Heptazines are heterocycles that gather appealing electrochemical and photophysical properties, combining high photooxidation potentials with long fluorescence lifetimes. However, selective grafting of molecular heptazines on a substrate is still underdeveloped. In this work, we report the synthesis, photophysical and electrochemical properties of two heptazine derivatives conjugated with one and three tetrazine rings respectively. These heptazines conjugated to tetrazines are very weakly fluorescent. We demonstrate that they can react in a fast manner with a strained alkyne, through an Inverse Electron Demand Diels-Alder reaction. This reaction has been followed thanks to a home-built photokinetics setup: in a timecale of a few seconds blue emitting heptazine pyridazine conjugates are generated with an 8.6 to 13.6 fluorescence turn-on.</div></div>","PeriodicalId":302,"journal":{"name":"Dyes and Pigments","volume":"236 ","pages":"Article 112666"},"PeriodicalIF":4.1,"publicationDate":"2025-01-20","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143167914","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"工程技术","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"OA","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Pub Date : 2025-01-20DOI: 10.1016/j.dyepig.2025.112661
Ying Sun, Ying An, Jiajun Huang, Zhenming Yin
Three bis-arylazo-naphthobipyrrole compounds (1–3) with different substituents (-H, -Cl, and –OCH3) have been synthesized. The planar structure of compound 1 was characterized by X-ray crystallography. All compounds exhibit λmax absorption at the range of 534–549 nm, and weakly fluorescence at the range of 599–628 nm due to the extended π-conjugation. All the compounds also show solvatochromic properties to chlorinated solvents. DFT calculations indicated that the compounds prefer to adopt planar E-syn/E-syn configuration. The frontier molecular orbitals (FMOs), energy gaps (ΔE) and UV–Vis spectra of these compounds were also evaluated by DFT calculations. UV–Vis titration experiments revealed that all the compounds can selectively sensing fluoride ion in DMSO solution.
{"title":"Bis-arylazo-naphthobipyrrole: Synthesis, structure, photophysical properties, DFT calculations and anions sensing","authors":"Ying Sun, Ying An, Jiajun Huang, Zhenming Yin","doi":"10.1016/j.dyepig.2025.112661","DOIUrl":"10.1016/j.dyepig.2025.112661","url":null,"abstract":"<div><div>Three bis-arylazo-naphthobipyrrole compounds (<strong>1</strong>–<strong>3</strong>) with different substituents (-H, -Cl, and –OCH<sub>3</sub>) have been synthesized. The planar structure of compound <strong>1</strong> was characterized by X-ray crystallography. All compounds exhibit <em>λ</em><sub>max</sub> absorption at the range of 534–549 nm, and weakly fluorescence at the range of 599–628 nm due to the extended π-conjugation. All the compounds also show solvatochromic properties to chlorinated solvents. DFT calculations indicated that the compounds prefer to adopt planar <em>E</em>-<em>syn</em>/<em>E</em>-<em>syn</em> configuration. The frontier molecular orbitals (FMOs), energy gaps (ΔE) and UV–Vis spectra of these compounds were also evaluated by DFT calculations. UV–Vis titration experiments revealed that all the compounds can selectively sensing fluoride ion in DMSO solution.</div></div>","PeriodicalId":302,"journal":{"name":"Dyes and Pigments","volume":"236 ","pages":"Article 112661"},"PeriodicalIF":4.1,"publicationDate":"2025-01-20","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143167864","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"工程技术","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
A new family of 6-aryl-2,4-bis(2′-hydroxyphenyl)pyrimidines has been efficiently synthesized and characterized using Suzuki-Miyaura reactions, demonstrating their ability to function as rigid tridentate O^N^O chelating ligands for the preparation of four-coordinate organoboron compounds. Similar to related structures, the uncoordinated compounds do not exhibit fluorescence in either solution or the solid state. The intramolecular hydrogen bonds in their molecular structure promote an excited-state intramolecular proton transfer (ESIPT) process, leading to an excited keto tautomer that deactivates through non-radiative decay. Protonation and boron complexation can successfully inhibit the ESIPT process, resulting in fluorescence recovery, which can be finely tuned by modifying the substituents on the aryl group. Advanced techniques, including X-ray diffraction, density functional theory (DFT), and time-dependent DFT (TD-DFT), provide critical insights into the electronic structure and emission properties. This work offers a deeper understanding of the role of boron chelation in modulating emission properties, opening new avenues for the design of functional fluorescent materials.
{"title":"Synthesis and photophysical properties of 6-aryl-2,4-bis(2′-hydroxyphenyl)pyrimidines ligands and their boron fluoride complexes","authors":"Clément Diguet , Amparo Navarro , M. Paz Fernández-Liencres , Sonia B. Jiménez-Pulido , Nuria A. Illán-Cabeza , Julien Massue , Sébastien Gauthier , Françoise Robin-le Guen , Sylvain Achelle , Julián Rodríguez-López","doi":"10.1016/j.dyepig.2025.112660","DOIUrl":"10.1016/j.dyepig.2025.112660","url":null,"abstract":"<div><div>A new family of 6-aryl-2,4-bis(2′-hydroxyphenyl)pyrimidines has been efficiently synthesized and characterized using Suzuki-Miyaura reactions, demonstrating their ability to function as rigid tridentate O^N^O chelating ligands for the preparation of four-coordinate organoboron compounds. Similar to related structures, the uncoordinated compounds do not exhibit fluorescence in either solution or the solid state. The intramolecular hydrogen bonds in their molecular structure promote an excited-state intramolecular proton transfer (ESIPT) process, leading to an excited keto tautomer that deactivates through non-radiative decay. Protonation and boron complexation can successfully inhibit the ESIPT process, resulting in fluorescence recovery, which can be finely tuned by modifying the substituents on the aryl group. Advanced techniques, including X-ray diffraction, density functional theory (DFT), and time-dependent DFT (TD-DFT), provide critical insights into the electronic structure and emission properties. This work offers a deeper understanding of the role of boron chelation in modulating emission properties, opening new avenues for the design of functional fluorescent materials.</div></div>","PeriodicalId":302,"journal":{"name":"Dyes and Pigments","volume":"236 ","pages":"Article 112660"},"PeriodicalIF":4.1,"publicationDate":"2025-01-20","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143167865","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"工程技术","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"OA","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Pub Date : 2025-01-19DOI: 10.1016/j.dyepig.2025.112663
Xiuqian Ding , Yong Wang , Jingxi Nan , Xue Wu , Xin Zhou
Photothermal therapy (PTT) can effectively ablate hypoxic tumors in deep issue under the near-infrared (NIR) irradiation. The development of novel NIR photothermal agents with high molar absorption coefficient and photothermal conversion efficiency is highly demanded. In this work, two phosphate-substituted xanthene dyes (POM and P7) were synthesized, and their stability and photothermal conversion efficiency were investigated. Both of them showed board absorption around 700 nm in the aqueous solution. In comparison with the rigid POM, P7 with flexible and twisted core displayed a higher photothermal conversion efficiency. The nanoparticle encapsulated in amphiphilic polymers (P7 NPs) was further used in the photoacoustic imaging-guided photothermal therapy in vivo.
{"title":"Synthesis of phosphate-substituted near-infrared dyes for photoacoustic imaging and photothermal therapy","authors":"Xiuqian Ding , Yong Wang , Jingxi Nan , Xue Wu , Xin Zhou","doi":"10.1016/j.dyepig.2025.112663","DOIUrl":"10.1016/j.dyepig.2025.112663","url":null,"abstract":"<div><div>Photothermal therapy (PTT) can effectively ablate hypoxic tumors in deep issue under the near-infrared (NIR) irradiation. The development of novel NIR photothermal agents with high molar absorption coefficient and photothermal conversion efficiency is highly demanded. In this work, two phosphate-substituted xanthene dyes (<strong>POM</strong> and <strong>P7</strong>) were synthesized, and their stability and photothermal conversion efficiency were investigated. Both of them showed board absorption around 700 nm in the aqueous solution. In comparison with the rigid <strong>POM</strong>, <strong>P7</strong> with flexible and twisted core displayed a higher photothermal conversion efficiency. The nanoparticle encapsulated in amphiphilic polymers (<strong>P7 NPs</strong>) was further used in the photoacoustic imaging-guided photothermal therapy <em>in vivo</em>.</div></div>","PeriodicalId":302,"journal":{"name":"Dyes and Pigments","volume":"236 ","pages":"Article 112663"},"PeriodicalIF":4.1,"publicationDate":"2025-01-19","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143167863","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"工程技术","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Pub Date : 2025-01-19DOI: 10.1016/j.dyepig.2025.112662
Teófanes B. Serna, Dora G. Felipe, Acácio A. Andrade, Viviane Pilla
This work evaluated the thermo-optical characterization of several vegetable oils such as Persea gratissima (avocado oil, AO), Mauritia flexuosa Linnaeus filius (buriti oil, BO), Passiflora edulis (passion fruit oil, PFO), and Plukenetia volubilis L. (Sacha inchi oil, SIO). Vegetable oils are nontoxic, nonvolatile, nondepletable, and biodegradable resources used for several applications, such as in the foods, cosmetic, lubricant, coating, and pharmaceutical industries, due to their possible antioxidant and antimicrobial activities. In this work, the refractive index temperature coefficients (dn/dT) of AO, BO, PFO, and SIO were characterized as a function of temperature (296-329 K−1) via a Mach–Zehnder interferometer. The thermal diffusivity (D) and fluorescence quantum efficiency (η) were determined via the dual-beam mode-mismatched thermal lens (TL) technique. Fluorescence and time-resolved fluorescence measurements corroborate the TL results. AO presented a relatively higher η value than other vegetable oils did (BO, PFO, and SIO), and avocado oil was heat treated at 180 °C for the synthesis of carbon dots (CAO-dots). The η and fluorescence lifetime (τ) results obtained for the avocado-based nanoparticles were compared with those of other C-dots using oil as a carbon source, aiming at potential bioapplications.
{"title":"Thermo-optical characterization of fluorescent materials based on edible vegetable oils","authors":"Teófanes B. Serna, Dora G. Felipe, Acácio A. Andrade, Viviane Pilla","doi":"10.1016/j.dyepig.2025.112662","DOIUrl":"10.1016/j.dyepig.2025.112662","url":null,"abstract":"<div><div>This work evaluated the thermo-optical characterization of several vegetable oils such as <em>Persea gratissima</em> (avocado oil, AO), <em>Mauritia flexuosa Linnaeus filius</em> (buriti oil, BO), <em>Passiflora edulis</em> (passion fruit oil, PFO), and <em>Plukenetia volubilis</em> L. (Sacha inchi oil, SIO)<em>.</em> Vegetable oils are nontoxic, nonvolatile, nondepletable, and biodegradable resources used for several applications, such as in the foods, cosmetic, lubricant, coating, and pharmaceutical industries, due to their possible antioxidant and antimicrobial activities. In this work, the refractive index temperature coefficients (<em>dn/dT</em>) of AO, BO, PFO, and SIO were characterized as a function of temperature (296-329 K<sup>−1</sup>) via a Mach–Zehnder interferometer. The thermal diffusivity (<em>D</em>) and fluorescence quantum efficiency (<em>η</em>) were determined via the dual-beam mode-mismatched thermal lens (TL) technique. Fluorescence and time-resolved fluorescence measurements corroborate the TL results. AO presented a relatively higher <em>η</em> value than other vegetable oils did (BO, PFO, and SIO), and avocado oil was heat treated at 180 °C for the synthesis of carbon dots (C<sub>AO</sub>-dots). The <em>η</em> and fluorescence lifetime (<em>τ</em>) results obtained for the avocado-based nanoparticles were compared with those of other C-dots using oil as a carbon source, aiming at potential bioapplications.</div></div>","PeriodicalId":302,"journal":{"name":"Dyes and Pigments","volume":"236 ","pages":"Article 112662"},"PeriodicalIF":4.1,"publicationDate":"2025-01-19","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143167915","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"工程技术","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Pub Date : 2025-01-17DOI: 10.1016/j.dyepig.2025.112656
Yutian Jiao, Yu Liu, Gongli Wei, Ce Wang, Baocai Xu, Li Zhao
In this study, we present an amphiphilic aggregation-induced emission fluorescent probe based on tetraphenylbenzene. The probe exhibited sensitive and selective detection of protamine through a “turn-on” fluorescence signal driven by electrostatic binding. A linear correlation was established between fluorescence intensity and protamine concentration in the range of 0.8–3 μg/mL in 4-(2-hydroxyethyl)piperazine-1-ethane-sulfonic acid (HEPES) buffer, with a limit of detection (LOD) of 6.65 ng/mL. Protamine detection was successfully demonstrated in a 0.3 % serum sample. Additionally, the electrostatic probe–protamine complex was able to detect heparin owing to the strong affinity between protamine and heparin, which was confirmed through a “turn-off” fluorescence response. The probe's sensitivity and selectivity for heparin detection were validated, with an LOD of 8.83 ng/mL and a linear working range of 1.0–2.2 μg/mL in HEPES buffer.
{"title":"A novel tetraphenylbenzene-derived fluorescent probe for the detection of protamine and heparin","authors":"Yutian Jiao, Yu Liu, Gongli Wei, Ce Wang, Baocai Xu, Li Zhao","doi":"10.1016/j.dyepig.2025.112656","DOIUrl":"10.1016/j.dyepig.2025.112656","url":null,"abstract":"<div><div>In this study, we present an amphiphilic aggregation-induced emission fluorescent probe based on tetraphenylbenzene. The probe exhibited sensitive and selective detection of protamine through a “turn-on” fluorescence signal driven by electrostatic binding. A linear correlation was established between fluorescence intensity and protamine concentration in the range of 0.8–3 μg/mL in 4-(2-hydroxyethyl)piperazine-1-ethane-sulfonic acid (HEPES) buffer, with a limit of detection (LOD) of 6.65 ng/mL. Protamine detection was successfully demonstrated in a 0.3 % serum sample. Additionally, the electrostatic probe–protamine complex was able to detect heparin owing to the strong affinity between protamine and heparin, which was confirmed through a “turn-off” fluorescence response. The probe's sensitivity and selectivity for heparin detection were validated, with an LOD of 8.83 ng/mL and a linear working range of 1.0–2.2 μg/mL in HEPES buffer.</div></div>","PeriodicalId":302,"journal":{"name":"Dyes and Pigments","volume":"235 ","pages":"Article 112656"},"PeriodicalIF":4.1,"publicationDate":"2025-01-17","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143135025","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"工程技术","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
The nucleolus has emerged as a promising target for cancer diagnosis and therapy, with its imaging being crucial for both fundamental research and clinical applications. Fluorescence imaging is a powerful tool for this purpose. However, its use is limited by the scarcity of fluorescent agents that specifically target the nucleolus and have excellent biocompatibility. Carbon dots (CDs) are becoming a valuable tool for cellular imaging because of their excellent optical properties and low toxicity. In this work, for the first time, ultra-narrow bandwidth emission CDs were synthesized with nicotinamide (NAM) and o-phenylenediamine (o-PDA) for nucleolus imaging. The reaction was carried out at 180 °C for 8 h in a stainless-steel autoclave, using a facile, low-cost, and one-step solvothermal approach with H2O/H2SO4 as solvent. Prepared CDs emit red emission at 617 nm with an ultra-narrow full width at half maximum (FWHM) of 28.1 nm and quantum yield (QY) of 13 %. Moreover, the cytotoxicity assay demonstrated that CDs exhibited excellent biocompatibility with MCF-7 breast cancer cells, even at concentrations as high as 4.5 mg/mL. Finally, fixed and live cell imaging results indicate that prepared CDs show bright red fluorescence in the nucleoli of MCF-7 cells. Our results demonstrate the efficacy of prepared CDs in nucleolus imaging, offering a convenient and promising fluorescent probe that can be used for fixed and live cell nucleolus imaging.
{"title":"Simple and user-friendly nucleolus imaging with ultra-narrow bandwidth red emission carbon dots","authors":"Seyed-Omid Kalji , Majid Sadeghizadeh , Khosro Khajeh","doi":"10.1016/j.dyepig.2025.112659","DOIUrl":"10.1016/j.dyepig.2025.112659","url":null,"abstract":"<div><div>The nucleolus has emerged as a promising target for cancer diagnosis and therapy, with its imaging being crucial for both fundamental research and clinical applications. Fluorescence imaging is a powerful tool for this purpose. However, its use is limited by the scarcity of fluorescent agents that specifically target the nucleolus and have excellent biocompatibility. Carbon dots (CDs) are becoming a valuable tool for cellular imaging because of their excellent optical properties and low toxicity. In this work, for the first time, ultra-narrow bandwidth emission CDs were synthesized with nicotinamide (NAM) and o-phenylenediamine (o-PDA) for nucleolus imaging. The reaction was carried out at 180 °C for 8 h in a stainless-steel autoclave, using a facile, low-cost, and one-step solvothermal approach with H<sub>2</sub>O/H<sub>2</sub>SO<sub>4</sub> as solvent. Prepared CDs emit red emission at 617 nm with an ultra-narrow full width at half maximum (FWHM) of 28.1 nm and quantum yield (QY) of 13 %. Moreover, the cytotoxicity assay demonstrated that CDs exhibited excellent biocompatibility with MCF-7 breast cancer cells, even at concentrations as high as 4.5 mg/mL. Finally, fixed and live cell imaging results indicate that prepared CDs show bright red fluorescence in the nucleoli of MCF-7 cells. Our results demonstrate the efficacy of prepared CDs in nucleolus imaging, offering a convenient and promising fluorescent probe that can be used for fixed and live cell nucleolus imaging.</div></div>","PeriodicalId":302,"journal":{"name":"Dyes and Pigments","volume":"236 ","pages":"Article 112659"},"PeriodicalIF":4.1,"publicationDate":"2025-01-17","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143167866","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"工程技术","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Pub Date : 2025-01-16DOI: 10.1016/j.dyepig.2025.112653
Hai-Han Liu, Zhong-Min Su, Hong-Liang Xu
A series of clam-shaped supramolecules (AEM@2, AEM = Be, Mg and Ca) were designed and investigated on the basis of the "clam shell" (2) composed of two corannulene units (1). Among these structures, the novel structure-property relationships of Ca@2 might stem from the extraordinary interaction between Ca and the two "shell" fragments. Through structural optimization and multiple analyses, it is revealed that there is a novel interaction existing between Ca and the host in Ca@2. The natural population analyze (NPA) and the energy decomposition analysis (EDA) revealed that the charge transfer causes Ca to acquire the charge qM of +1.80, thus facilitating the formation of the organic salt Ca2⁺@22⁻ with a cation-π interaction. In comparison to other structures, Ca2⁺@22⁻ exhibits a significant second-order nonlinear optical response. Additionally, various properties such as the frontier molecular orbitals (FMOs) analysis, the nucleus-independent chemical shift (NICS) have been investigated. This study may provide a basis for exploring a new and promising area of research in designing high performance electro-optical materials.
{"title":"Construction and electro-optical property of the clam-shaped supramolecule with cation-π interaction","authors":"Hai-Han Liu, Zhong-Min Su, Hong-Liang Xu","doi":"10.1016/j.dyepig.2025.112653","DOIUrl":"10.1016/j.dyepig.2025.112653","url":null,"abstract":"<div><div>A series of clam-shaped supramolecules (AEM@<strong>2</strong>, AEM = Be, Mg and Ca) were designed and investigated on the basis of the \"clam shell\" (<strong>2</strong>) composed of two corannulene units (<strong>1</strong>). Among these structures, the novel structure-property relationships of Ca@<strong>2</strong> might stem from the extraordinary interaction between Ca and the two \"shell\" fragments. Through structural optimization and multiple analyses, it is revealed that there is a novel interaction existing between Ca and the host in Ca@<strong>2</strong>. The natural population analyze (NPA) and the energy decomposition analysis (EDA) revealed that the charge transfer causes Ca to acquire the charge q<sub>M</sub> of +1.80, thus facilitating the formation of the organic salt Ca<sup>2</sup>⁺@<strong>2</strong><sup>2</sup>⁻ with a cation-π interaction. In comparison to other structures, Ca<sup>2</sup>⁺@<strong>2</strong><sup>2</sup>⁻ exhibits a significant second-order nonlinear optical response. Additionally, various properties such as the frontier molecular orbitals (FMOs) analysis, the nucleus-independent chemical shift (NICS) have been investigated. This study may provide a basis for exploring a new and promising area of research in designing high performance electro-optical materials.</div></div>","PeriodicalId":302,"journal":{"name":"Dyes and Pigments","volume":"235 ","pages":"Article 112653"},"PeriodicalIF":4.1,"publicationDate":"2025-01-16","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143135221","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"工程技术","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Pub Date : 2025-01-16DOI: 10.1016/j.dyepig.2025.112658
Beatriz S. Cugnasca , Tharcísio C.T. Junior , Tatiana C. Penna , Norma L.B. Zuluaga , Silvina O. Bustos , Roger Chammas , Iolanda M. Cuccovia , Thiago C. Correra , Alcindo A. Dos Santos
Biothiols like cysteine and glutathione are involved in maintaining redox balance in living organisms and perform essential functions in pathological and physiological processes. Depending on the concentration they can be regarded as biomarkers for oxidative stress and be associated with diseases such as cancer, immune dysfunctions, among others. Herein, we report a synthetic route for a Seleno-BODIPY to act as a fluorescent probe by reaction with biological thiols in living cells. The probe presented high selectivity for biothiols between 26 analytes of biological interest. Distinct responses for Cys and GSH by colorimetric and fluorometric analysis in a turn-on fluorescent process were observed, with low detection limits (61.18 nM for Cys; 1.66 μM for GSH), ratiometric response by absorption for Cys, high fluorescence quantum yield after reaction (88.1 % for Cys and 31.8 % for GSH), high sensitivity, and fast response time for Cys. A mechanistic investigation was conducted, using N-ethylmaleimide as a thiol trapper. This strategy allowed us to conclude that the reaction between BODIPY and Cys gave an amino-BODIPY while the analogous reaction with GSH results in a thio-BODIPY with different spectral shifts, making possible the distinction and quantification of both analytes by fluorescence. Kinetic studies demonstrated that the reaction with Cys is much faster than with GSH, allowing them to be differentiated. A pH study showed that the probe behaves well at a physiological pH range (6.2–8.0). Finally, the Se-BODIPY was successfully used to detect biothiols in HeLa cells, demonstrating the sensor applicability in real systems, presenting high potential for both diagnostics and analytical (bio)chemistry areas.
{"title":"Seleno-BODIPY as a fluorescent sensor for differential and highly selective detection of Cysteine and Glutathione for bioimaging in HeLa cells","authors":"Beatriz S. Cugnasca , Tharcísio C.T. Junior , Tatiana C. Penna , Norma L.B. Zuluaga , Silvina O. Bustos , Roger Chammas , Iolanda M. Cuccovia , Thiago C. Correra , Alcindo A. Dos Santos","doi":"10.1016/j.dyepig.2025.112658","DOIUrl":"10.1016/j.dyepig.2025.112658","url":null,"abstract":"<div><div>Biothiols like cysteine and glutathione are involved in maintaining redox balance in living organisms and perform essential functions in pathological and physiological processes. Depending on the concentration they can be regarded as biomarkers for oxidative stress and be associated with diseases such as cancer, immune dysfunctions, among others. Herein, we report a synthetic route for a Seleno-BODIPY to act as a fluorescent probe by reaction with biological thiols in living cells. The probe presented high selectivity for biothiols between 26 analytes of biological interest. Distinct responses for Cys and GSH by colorimetric and fluorometric analysis in a turn-on fluorescent process were observed, with low detection limits (61.18 nM for Cys; 1.66 μM for GSH), ratiometric response by absorption for Cys, high fluorescence quantum yield after reaction (88.1 % for Cys and 31.8 % for GSH), high sensitivity, and fast response time for Cys. A mechanistic investigation was conducted, using <em>N</em>-ethylmaleimide as a thiol trapper. This strategy allowed us to conclude that the reaction between BODIPY and Cys gave an amino-BODIPY while the analogous reaction with GSH results in a thio-BODIPY with different spectral shifts, making possible the distinction and quantification of both analytes by fluorescence. Kinetic studies demonstrated that the reaction with Cys is much faster than with GSH, allowing them to be differentiated. A pH study showed that the probe behaves well at a physiological pH range (6.2–8.0). Finally, the Se-BODIPY was successfully used to detect biothiols in HeLa cells, demonstrating the sensor applicability in real systems, presenting high potential for both diagnostics and analytical (bio)chemistry areas.</div></div>","PeriodicalId":302,"journal":{"name":"Dyes and Pigments","volume":"236 ","pages":"Article 112658"},"PeriodicalIF":4.1,"publicationDate":"2025-01-16","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143167869","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"工程技术","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Pub Date : 2025-01-16DOI: 10.1016/j.dyepig.2025.112649
Maynne Duarte Suriani Franco , Thibault Joseph William Jacques Dit Lapierre , Ana Clara Cassiano Martinho , Naiara Cristina Bessas , Mayara Martins Caetano , Thiago Teixeira Tasso , Marcelo Emílio Beletti , Renata Galvão de Lima , Celso de Oliveira Rezende Júnior , Tayana Mazin Tsubone
Designing photosensitizers (PS) with ideal properties for Photodynamic Therapy (PDT) remains challenging, but crucial for advancing PDT as a viable anticancer treatment. Combining porphyrin with potent anticancer agents, such as piperazine and morpholine groups, has the potential to give rise to innovative photosensitizers that exhibit heightened PDT effects in cancer cells. Herein, we present two novel molecules bearing piperazine (PpIX-Pip) or morpholine (PpIX-Morp) groups conjugated to Protoporphyrin IX (PpIX), describing their photophysical and photodynamic characteristics. Analysis of the photophysical properties revealed similar fluorescence quantum yields and lifetimes between PpIX and the conjugated molecules. The PpIX-Pip showed higher production of singlet oxygen and better interaction with HSA in comparison to PpIX-Morp. Cellular uptake assays revealed a greater incorporation rate for PpIX-Pip (37 %) compared to PpIX-Morp (29 %) in HeLa cells. Essentially, both PpIX derivatives exhibited superior uptake efficiencies compared to PpIX alone (17 %). The descending order of IC50 values was PpIX > PpIX-Morp > PpIX-Pip, indicating that the introduction of piperazine and morpholine groups to PpIX elevated the toxicity in HeLa cells. When comparing IC50 values obtained under irradiation to the dark control, it was observed that PpIX-Pip demonstrated higher phototoxic effect (phototherapeutic index, PI > 5), whereas PpIX-Morp exhibits medium phototoxicity towards HeLa cells (PI > 2). Among the newly studied porphyrins, PpIX-Pip displayed a higher singlet oxygen generation rate, and improved cellular uptake as well as lower value of IC50 in the light. This is the first report highlighting the PDT activity of PpIX modified with the N-methylpiperazine group. Our findings open avenues for the design and development of photosensitizers linked to anticancer agent moieties, encompassing groups like piperazine and morpholine.
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