Pub Date : 2026-09-01Epub Date: 2026-03-06DOI: 10.1016/j.jphotochem.2026.117156
Minoru Yamaji , Kengo Suzuki , Hideki Okamoto
We report the synthesis and photophysical characterization of a series of “all-naphthalene” multi-chromophore systems, ternaphthalenes (TNps), designed for efficient deep-blue solid-state emission. Unlike planar polycyclic aromatic hydrocarbons that suffer from aggregation-caused quenching (ACQ), the twisted molecular architecture of TNps effectively inhibits π-π stacking interactions. Consequently, several TNps exhibit crystallization-induced emission enhancement (CIEE) or retain high quantum yields (up to 0.94) in the solid state. Kinetic analysis revealed that this efficiency stems from the significant suppression of non-radiative rates (knr) due to the restricted intramolecular rotation in the rigid crystal lattice. Furthermore, a decisive topological effect on the radiative rate (kf) was demonstrated. The 1,4-, 1,5- and 2,6-linked isomers display allowed transitions with large oscillator strengths (f) and fast radiative rate (kf = ca. 5 × 108 s−1), whereas the 2,7-linked isomers exhibit forbidden-like character with prolonged lifetimes. A distinct linear correlation between the experimental and calculated values empirically supports the applicability of the Strickler-Berg relationship in both solution and solid states. These findings demonstrate that controlling the chromophore connectivity is a powerful strategy to tune excited-state dynamics for developing high-performance deep-blue organic emitters.
{"title":"Deep-blue solid-state emission from Ternaphthalene: Photophysical tuning via multi-chromophore architectures","authors":"Minoru Yamaji , Kengo Suzuki , Hideki Okamoto","doi":"10.1016/j.jphotochem.2026.117156","DOIUrl":"10.1016/j.jphotochem.2026.117156","url":null,"abstract":"<div><div>We report the synthesis and photophysical characterization of a series of “all-naphthalene” multi-chromophore systems, ternaphthalenes (TNps), designed for efficient deep-blue solid-state emission. Unlike planar polycyclic aromatic hydrocarbons that suffer from aggregation-caused quenching (ACQ), the twisted molecular architecture of TNps effectively inhibits π-π stacking interactions. Consequently, several TNps exhibit crystallization-induced emission enhancement (CIEE) or retain high quantum yields (up to 0.94) in the solid state. Kinetic analysis revealed that this efficiency stems from the significant suppression of non-radiative rates (<em>k</em><sub>nr</sub>) due to the restricted intramolecular rotation in the rigid crystal lattice. Furthermore, a decisive topological effect on the radiative rate (<em>k</em><sub>f</sub>) was demonstrated. The 1,4-, 1,5- and 2,6-linked isomers display allowed transitions with large oscillator strengths (<em>f</em>) and fast radiative rate (<em>k</em><sub>f</sub> = ca. 5 × 10<sup>8</sup> s<sup>−1</sup>), whereas the 2,7-linked isomers exhibit forbidden-like character with prolonged lifetimes. A distinct linear correlation between the experimental and calculated values empirically supports the applicability of the Strickler-Berg relationship in both solution and solid states. These findings demonstrate that controlling the chromophore connectivity is a powerful strategy to tune excited-state dynamics for developing high-performance deep-blue organic emitters.</div></div>","PeriodicalId":16782,"journal":{"name":"Journal of Photochemistry and Photobiology A-chemistry","volume":"478 ","pages":"Article 117156"},"PeriodicalIF":4.7,"publicationDate":"2026-09-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"147387902","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Pub Date : 2026-09-01Epub Date: 2026-02-26DOI: 10.1016/j.jphotochem.2026.117148
B. Venugopal, Nayela Javeed, G. Shanker, Ganga Periyasamy
This systematic study reports on the photophysical properties of perylene bisimide (PBI) and its derivatives substituted with pyridine (PDP) and cholesterol (PDC) groups using UV–Vis, fluorescence spectroscopy methods, alongside density functional theory (DFT) and time-dependent DFT (TDDFT) calculations. UV–Vis absorption and fluorescence spectroscopy show that PDP and PDC exhibit near mirror-image absorption and emission spectra with Stokes shifts of 29 and 19 nm, respectively. In contrast, PBI displays a negligible Stokes shift and lacks mirror symmetry due to strong excimer formation facilitated by its highly planar bisimide core. TDDFT computations accurately reproduce the main π → π* electronic transitions in high-energy (298–300 nm) and low-energy (430–454 nm) regions, in agreement with experimental absorption data. However, theoretical emission spectra indicate greater overlap between absorption and fluorescence than observed experimentally, reflecting limitations of the Franck–Condon approximation in accounting for excited-state relaxation. Dimer models reveal pronounced cofacial H-aggregate-like with shift characteristics, with PDC exhibiting the highest stability (binding energy of −6.46 eV), followed by PDP (−6.36 eV) and PBI (−5.48 eV). Despite its lower dimer stability, PBI shows the broadest excimer emission, attributed to its increased dipole moment and extended π-π interactions. Red-shifted electronic transitions in the dimers confirm excitonic coupling and reduced oscillator strengths typical of J-aggregates. The computational models, which omit the bulky cholesterol substituents, permit excimer stabilization in PDC. In contrast, in the experimental systems, steric hindrance imposed by the cholesterol groups restricts close π–π stacking and thus limits aggregation. This steric effect is further validated by calculations on the cholesterol-substituted PDC model, which exhibits a slip-stacked dimer configuration. During the dimer formation, the charge separation occurs, where one monomer act as Donor and other one as acceptor, where the hole migration dynamics are explored using the frozen nuclei treatment. This combined experimental and theoretical investigation highlights how molecular planarity, steric effects, and excitonic interactions govern the balance between excimer and J-aggregate emission in perylene derivatives. These insights will inform the rational design of organic semiconductors and fluorescence sensors employing PBI-based architectures in optoelectronic applications.
{"title":"Photophysical control of aggregation in Perylene Bisimide derivatives by molecular design","authors":"B. Venugopal, Nayela Javeed, G. Shanker, Ganga Periyasamy","doi":"10.1016/j.jphotochem.2026.117148","DOIUrl":"10.1016/j.jphotochem.2026.117148","url":null,"abstract":"<div><div>This systematic study reports on the photophysical properties of perylene bisimide (<strong>PBI</strong>) and its derivatives substituted with pyridine (<strong>PDP</strong>) and cholesterol (<strong>PDC</strong>) groups using UV–Vis, fluorescence spectroscopy methods, alongside density functional theory (<strong>DFT</strong>) and time-dependent DFT (<strong>TDDFT</strong>) calculations. UV–Vis absorption and fluorescence spectroscopy show that <strong>PDP</strong> and <strong>PDC</strong> exhibit near mirror-image absorption and emission spectra with Stokes shifts of 29 and 19 nm, respectively. In contrast, <strong>PBI</strong> displays a negligible Stokes shift and lacks mirror symmetry due to strong excimer formation facilitated by its highly planar bisimide core. <strong>TDDFT</strong> computations accurately reproduce the main π → π* electronic transitions in high-energy (298–300 nm) and low-energy (430–454 nm) regions, in agreement with experimental absorption data. However, theoretical emission spectra indicate greater overlap between absorption and fluorescence than observed experimentally, reflecting limitations of the Franck–Condon approximation in accounting for excited-state relaxation. Dimer models reveal pronounced cofacial <em>H</em>-aggregate-like with shift characteristics, with <strong>PDC</strong> exhibiting the highest stability (binding energy of −6.46 eV), followed by <strong>PDP</strong> (−6.36 eV) and <strong>PBI</strong> (−5.48 eV). Despite its lower dimer stability, <strong>PBI</strong> shows the broadest excimer emission, attributed to its increased dipole moment and extended π-π interactions. Red-shifted electronic transitions in the dimers confirm excitonic coupling and reduced oscillator strengths typical of <em>J</em>-aggregates. The computational models, which omit the bulky cholesterol substituents, permit excimer stabilization in <strong>PDC</strong>. In contrast, in the experimental systems, steric hindrance imposed by the cholesterol groups restricts close π–π stacking and thus limits aggregation. This steric effect is further validated by calculations on the cholesterol-substituted <strong>PDC</strong> model, which exhibits a slip-stacked dimer configuration. During the dimer formation, the charge separation occurs, where one monomer act as Donor and other one as acceptor, where the hole migration dynamics are explored using the frozen nuclei treatment. This combined experimental and theoretical investigation highlights how molecular planarity, steric effects, and excitonic interactions govern the balance between excimer and <em>J</em>-aggregate emission in perylene derivatives. These insights will inform the rational design of organic semiconductors and fluorescence sensors employing <strong>PBI</strong>-based architectures in optoelectronic applications.</div></div>","PeriodicalId":16782,"journal":{"name":"Journal of Photochemistry and Photobiology A-chemistry","volume":"478 ","pages":"Article 117148"},"PeriodicalIF":4.7,"publicationDate":"2026-09-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"147387904","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Pub Date : 2026-09-01Epub Date: 2026-03-07DOI: 10.1016/j.jphotochem.2026.117166
Kai Feng , Libing Qian , Pengwei Zeng , Chunhui Dai , Chao Zeng
Benefiting from the advantages of surface defects on promoting the three basic processes in photocatalysis, defect engineering is regarded as an efficient strategy to boost the photoactivity of semiconductor photocatalysts. However, the influence of the intrinsic defects in photocatalysts on photocatalysis is always ignored and rarely investigated, and the excessive defects can also lead to adverse effects. Herein, we provide a strategy to optimize the concentration of intrinsic surface defects for photocatalysts to obtain high performance. The treatment of electron beam irradiation on ZnS decreases its intrinsic surface sulfur vacancies (Vs), demonstrated by electron paramagnetic resonance (EPR) spectra and positron annihilation characterization. This modification leads to the enhanced photo-response in UV light region, charge separation and transfer efficiency, as well as hydrophilicity, hence boosting the photocatalytic performance on H2 evolution.
{"title":"Tuning the intrinsic surface sulfur vacancies in ZnS for achieving high performance H2 evolution","authors":"Kai Feng , Libing Qian , Pengwei Zeng , Chunhui Dai , Chao Zeng","doi":"10.1016/j.jphotochem.2026.117166","DOIUrl":"10.1016/j.jphotochem.2026.117166","url":null,"abstract":"<div><div>Benefiting from the advantages of surface defects on promoting the three basic processes in photocatalysis, defect engineering is regarded as an efficient strategy to boost the photoactivity of semiconductor photocatalysts. However, the influence of the intrinsic defects in photocatalysts on photocatalysis is always ignored and rarely investigated, and the excessive defects can also lead to adverse effects. Herein, we provide a strategy to optimize the concentration of intrinsic surface defects for photocatalysts to obtain high performance. The treatment of electron beam irradiation on ZnS decreases its intrinsic surface sulfur vacancies (Vs), demonstrated by electron paramagnetic resonance (EPR) spectra and positron annihilation characterization. This modification leads to the enhanced photo-response in UV light region, charge separation and transfer efficiency, as well as hydrophilicity, hence boosting the photocatalytic performance on H<sub>2</sub> evolution.</div></div>","PeriodicalId":16782,"journal":{"name":"Journal of Photochemistry and Photobiology A-chemistry","volume":"478 ","pages":"Article 117166"},"PeriodicalIF":4.7,"publicationDate":"2026-09-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"147387900","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Pub Date : 2026-09-01Epub Date: 2026-03-03DOI: 10.1016/j.jphotochem.2026.117159
Xinlin Yang, Tianyu Cui, Siqi Wang, Yinghe Jin, Hui Li
Positional substitution of functional groups plays a decisive role in modulating excited-state intramolecular proton transfer (ESIPT) and its coupling with singlet–triplet interactions, thereby directly impacting thermally activated delayed fluorescence (TADF) and the associated photophysical properties. Three novel derivatives (BrA-1-HBI, BrA-2-HBI, and BrA-3-HBI) were designed by systematically varying the positions of Br and –CHO substituents in the (2′-hydroxyphenyl)benzimidazole scaffold (BrA-HBI). Density functional theory (DFT) and time-dependent DFT (TD-DFT) methods were employed to investigate their ESIPT properties and photophysical responses. The results show that all positional isomers exhibit reduced ESIPT barriers and red-shifted emission spectra. Remarkably, BrA-3-HBI undergoes a two-step excited-state double proton transfer (ESDPT), yielding an exceptionally large Stokes shift of ∼1.24 × 104 cm−1. Moreover, positional substitution alters the transition character from weak n → π* to strong π → π*, thereby activating Enol-state emission, enabling dual fluorescence channels, and reprogramming ISC pathways from the Keto state toward the Enol state. These results show that the Br inductive effect and –CHO conjugation strengthen the intramolecular H-bond and promote ESIPT, offering a rational strategy for designing high-performance ESIPT-based optoelectronic materials.
{"title":"Mechanistic insights into substituent position effects on ESIPT and singlet–triplet interactions in BrA-HBI","authors":"Xinlin Yang, Tianyu Cui, Siqi Wang, Yinghe Jin, Hui Li","doi":"10.1016/j.jphotochem.2026.117159","DOIUrl":"10.1016/j.jphotochem.2026.117159","url":null,"abstract":"<div><div>Positional substitution of functional groups plays a decisive role in modulating excited-state intramolecular proton transfer (ESIPT) and its coupling with singlet–triplet interactions, thereby directly impacting thermally activated delayed fluorescence (TADF) and the associated photophysical properties. Three novel derivatives (<strong>BrA-1-HBI, BrA-2-HBI, and BrA-3-HBI</strong>) were designed by systematically varying the positions of <img>Br and –CHO substituents in the <strong>(2′-hydroxyphenyl)benzimidazole scaffold</strong> (<strong>BrA-HBI</strong>). Density functional theory (DFT) and time-dependent DFT (TD-DFT) methods were employed to investigate their ESIPT properties and photophysical responses. The results show that all positional isomers exhibit reduced ESIPT barriers and red-shifted emission spectra. Remarkably, <strong>BrA-3-HBI</strong> undergoes a two-step excited-state double proton transfer (ESDPT), yielding an exceptionally large Stokes shift of ∼1.24 × 10<sup>4</sup> cm<sup>−1</sup>. Moreover, positional substitution alters the transition character from weak n → π* to strong π → π*, thereby activating Enol-state emission, enabling dual fluorescence channels, and reprogramming ISC pathways from the Keto state toward the Enol state. These results show that the <img>Br inductive effect and –CHO conjugation strengthen the intramolecular H-bond and promote ESIPT, offering a rational strategy for designing high-performance ESIPT-based optoelectronic materials.</div></div>","PeriodicalId":16782,"journal":{"name":"Journal of Photochemistry and Photobiology A-chemistry","volume":"478 ","pages":"Article 117159"},"PeriodicalIF":4.7,"publicationDate":"2026-09-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"147387944","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Pub Date : 2026-09-01Epub Date: 2026-02-26DOI: 10.1016/j.jphotochem.2026.117144
Nan Zhao , Liang Pei , Jianjiao Xin , Xiuwen Wang , Li Sun , Xiaoming Huang , Bing Zhao
The synergistic integration of light energy harvesting and mechanical energy conversion is posited as a transformative approach to enhance environmental stewardship while advancing sustainable energy solutions. This work demonstrates the first successful hydrothermal synthesis of BaTiO3/TiO2 double-shelled hollow sphere heterostructures for synergistic piezo-photocatalysis. Their piezo-photocatalytic activity was comprehensively assessed using methylene blue aqueous dye decomposition tests. Under combined ultrasound and visible light exposure, the BaTiO3/TiO2 double-shelled hollow spheres achieved a degradation efficiency of 95.8% within 60 min, surpassing both pure-phase BaTiO3 nanoparticles (64.8%) and BaTiO3 double-shelled hollow spheres (89.9%). The enhanced performance originates from three synergistic mechanisms: (1) The unique double-shelled architecture demonstrates amplified structural deformability under mechanical stress, significantly increasing specific surface area and light-harvesting efficiency; (2) Z-Scheme heterojunction at the BaTiO3/TiO2 interface facilitates spatial separation of photogenerated carriers and maximizes the preservation of their redox ability; (3) Oxygen vacancies at interfacial regions serve as electron traps, effectively suppressing charge recombination. This work demonstrates that microstructural engineering coupled with heterojunction design creates synergistic piezo-photocatalytic effects, providing a novel strategy for developing high-efficiency energy-conversion catalysts.
{"title":"Double-shelled BaTiO3/TiO2 hollow spheres: Structural synergy driven enhancement in piezo-photocatalytic dye degradation","authors":"Nan Zhao , Liang Pei , Jianjiao Xin , Xiuwen Wang , Li Sun , Xiaoming Huang , Bing Zhao","doi":"10.1016/j.jphotochem.2026.117144","DOIUrl":"10.1016/j.jphotochem.2026.117144","url":null,"abstract":"<div><div>The synergistic integration of light energy harvesting and mechanical energy conversion is posited as a transformative approach to enhance environmental stewardship while advancing sustainable energy solutions. This work demonstrates the first successful hydrothermal synthesis of BaTiO<sub>3</sub>/TiO<sub>2</sub> double-shelled hollow sphere heterostructures for synergistic piezo-photocatalysis. Their piezo-photocatalytic activity was comprehensively assessed using methylene blue aqueous dye decomposition tests. Under combined ultrasound and visible light exposure, the BaTiO<sub>3</sub>/TiO<sub>2</sub> double-shelled hollow spheres achieved a degradation efficiency of 95.8% within 60 min, surpassing both pure-phase BaTiO<sub>3</sub> nanoparticles (64.8%) and BaTiO<sub>3</sub> double-shelled hollow spheres (89.9%). The enhanced performance originates from three synergistic mechanisms: (1) The unique double-shelled architecture demonstrates amplified structural deformability under mechanical stress, significantly increasing specific surface area and light-harvesting efficiency; (2) <em>Z</em>-Scheme heterojunction at the BaTiO<sub>3</sub>/TiO<sub>2</sub> interface facilitates spatial separation of photogenerated carriers and maximizes the preservation of their redox ability; (3) Oxygen vacancies at interfacial regions serve as electron traps, effectively suppressing charge recombination. This work demonstrates that microstructural engineering coupled with heterojunction design creates synergistic piezo-photocatalytic effects, providing a novel strategy for developing high-efficiency energy-conversion catalysts.</div></div>","PeriodicalId":16782,"journal":{"name":"Journal of Photochemistry and Photobiology A-chemistry","volume":"478 ","pages":"Article 117144"},"PeriodicalIF":4.7,"publicationDate":"2026-09-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"147387846","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Pub Date : 2026-09-01Epub Date: 2026-03-02DOI: 10.1016/j.jphotochem.2026.117145
Mohammed A.I. Shaikh , Mhejabeen Sayed
Polyglutamic acid (PGA), a biodegradable and multifunctional biopolymer rich in carboxylate groups, holds strong promise for designing supramolecular sensing systems to address the urgent problem of heavy metal contamination. This study presents a systematic investigation of the detailed photophysical behaviour of acridine orange (AO) upon interaction with PGA, combined with the application of an indicator displacement assay (IDA) strategy using a PGA-based complex for heavy metal ion recognition. Spectroscopic investigations revealed distinct spectroscopic alterations, including a ∼ 34 nm blue shift in absorption, pronounced fluorescence quenching, a bisignate CD signal, and longer fluorescence lifetime, indicative of AO aggregate formation on the PGA scaffold. Harnessing these photophysical changes, the aggregated AO–PGA complex was applied for ratiometric turn-on sensing of Cd2+, Pb2+, and Cu2+ via indicator displacement mechanism, wherein metal ion binding triggers the dissociation of AO aggregates and restores the monomeric AO spectral features. The system exhibited detection limits of 0.19 μM for Cd2+, 0.29 μM for Pb2+, and 0.47 μM for Cu2+ in nanopure water, with the enhanced sensitivity towards Cd2+. Its practical applicability was further validated in tap water and 2% seawater, demonstrating the potential of this complex for environmental monitoring of heavy metal ion contamination.
{"title":"Photophysical insights into acridine orange–polyglutamic acid interaction and its application in ratiometric turn-on heavy metal ion recognition","authors":"Mohammed A.I. Shaikh , Mhejabeen Sayed","doi":"10.1016/j.jphotochem.2026.117145","DOIUrl":"10.1016/j.jphotochem.2026.117145","url":null,"abstract":"<div><div>Polyglutamic acid (PGA), a biodegradable and multifunctional biopolymer rich in carboxylate groups, holds strong promise for designing supramolecular sensing systems to address the urgent problem of heavy metal contamination. This study presents a systematic investigation of the detailed photophysical behaviour of acridine orange (AO) upon interaction with PGA, combined with the application of an indicator displacement assay (IDA) strategy using a PGA-based complex for heavy metal ion recognition. Spectroscopic investigations revealed distinct spectroscopic alterations, including a ∼ 34 nm blue shift in absorption, pronounced fluorescence quenching, a bisignate CD signal, and longer fluorescence lifetime, indicative of AO aggregate formation on the PGA scaffold. Harnessing these photophysical changes, the aggregated AO–PGA complex was applied for ratiometric turn-on sensing of Cd<sup>2+</sup>, Pb<sup>2+</sup>, and Cu<sup>2+</sup> via indicator displacement mechanism, wherein metal ion binding triggers the dissociation of AO aggregates and restores the monomeric AO spectral features. The system exhibited detection limits of 0.19 μM for Cd<sup>2+</sup>, 0.29 μM for Pb<sup>2+</sup>, and 0.47 μM for Cu<sup>2+</sup> in nanopure water, with the enhanced sensitivity towards Cd<sup>2+</sup>. Its practical applicability was further validated in tap water and 2% seawater, demonstrating the potential of this complex for environmental monitoring of heavy metal ion contamination.</div></div>","PeriodicalId":16782,"journal":{"name":"Journal of Photochemistry and Photobiology A-chemistry","volume":"478 ","pages":"Article 117145"},"PeriodicalIF":4.7,"publicationDate":"2026-09-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"147387901","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Pub Date : 2026-09-01Epub Date: 2026-02-26DOI: 10.1016/j.jphotochem.2026.117151
Mónica Moral , Antonio Fernández , Luis Manuel Frutos , Andrés Garzón-Ruiz
This is a DFT study on selenium-substituted meso-aryl-BODIPYs aimed at designing novel singlet‑oxygen photosensitizers with potential biomedical applicability. Three different selenium-containing heterocycles (2,3-dihydro-1,3-selenazole, 1,3-oxaselenole and 1,3-thiaselenole) were combined with diverse types of meso-aryl-BODIPYs. The incorporation of selenium atoms into BODIPYs is a novel strategy to enhance the photosensitizer performance, reducing the toxicity associated with the use of metal atoms. The present study provides new perspectives on the use of these novel agents which have been scarcely developed to date. Diverse electronic descriptors such as the absorption maxima wavelength, singlet-triplet energy gap and spin-orbit coupling were used in subsequent screening steps to select the most suitable candidates as photosensitizers with biomedical applicability. These descriptors are related to the light absorption within the therapeutic window, the triplet-state formation efficiency, the triplet-state lifetime and the energy transfer to the molecular oxygen.
{"title":"Theoretical design of novel selenium-substituted meso-aryl-BODIPYs as singlet‑oxygen photosensitizers with biomedical applicability","authors":"Mónica Moral , Antonio Fernández , Luis Manuel Frutos , Andrés Garzón-Ruiz","doi":"10.1016/j.jphotochem.2026.117151","DOIUrl":"10.1016/j.jphotochem.2026.117151","url":null,"abstract":"<div><div>This is a DFT study on selenium-substituted <em>meso</em>-aryl-BODIPYs aimed at designing novel singlet‑oxygen photosensitizers with potential biomedical applicability. Three different selenium-containing heterocycles (2,3-dihydro-1,3-selenazole, 1,3-oxaselenole and 1,3-thiaselenole) were combined with diverse types of <em>meso</em>-aryl-BODIPYs. The incorporation of selenium atoms into BODIPYs is a novel strategy to enhance the photosensitizer performance, reducing the toxicity associated with the use of metal atoms. The present study provides new perspectives on the use of these novel agents which have been scarcely developed to date. Diverse electronic descriptors such as the absorption maxima wavelength, singlet-triplet energy gap and spin-orbit coupling were used in subsequent screening steps to select the most suitable candidates as photosensitizers with biomedical applicability. These descriptors are related to the light absorption within the therapeutic window, the triplet-state formation efficiency, the triplet-state lifetime and the energy transfer to the molecular oxygen.</div></div>","PeriodicalId":16782,"journal":{"name":"Journal of Photochemistry and Photobiology A-chemistry","volume":"478 ","pages":"Article 117151"},"PeriodicalIF":4.7,"publicationDate":"2026-09-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"147387917","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Pub Date : 2026-09-01Epub Date: 2026-03-08DOI: 10.1016/j.jphotochem.2026.117183
Yuxin Wang , Bingbing Huang , Tingting Huang , Xing Liu
To develop the efficient catalytic active sites for the reduction of O2 to H2O2 while ensuring their inertness to H2O2 decomposition is crucial for the photothermal catalytic synthesis of H2O2 process, but still faces challenges. Herein, Co single-atom-loaded carbon nitride porous nanotubes (CoSA/CN-PNTs) were prepared by self-assembled polymerization and calcined annealing. The Co single atom is not only Co single atom can not only form CoN bond with N in CN as an electron transport bridge, but also act as an active center in the photothermal catalytic O2 reduction for H2O2 synthesis. The porous tubular structure not only contributes to the enhancement of light absorption and utilization, but also facilitates the adsorption of O2 as well as the formation of the key intermediate *OOH on the Co sites. Notably, the thermal effect generated by CoSA/CN-PNT during photocatalysis contributes to the rapidity of the reaction and ensures that the rapidly adsorbed O2 on its surface inhibits the decomposition of H2O2. The results showed that the H₂O₂ generation rates of CoSA/CN-PNT reached 148.6 μmol L−1 h−1 and 169.6 μmol L−1 h−1 under visible light and solar radiation irradiation, respectively, which were 15 times and 16 times higher than those of the pristine CN material by a factor of 15.1 and 13.9, respectively. Therefore, this work improves the construction and understanding of the structure-efficacy relationship of catalysts at the atomic level by exploring the role of single atoms in the coordination shell layer and developing catalytic centers with unique single atoms.
{"title":"Co single atom loaded carbon nitride porous nanotube catalysts for efficient photothermal catalysis for H2O2 production","authors":"Yuxin Wang , Bingbing Huang , Tingting Huang , Xing Liu","doi":"10.1016/j.jphotochem.2026.117183","DOIUrl":"10.1016/j.jphotochem.2026.117183","url":null,"abstract":"<div><div>To develop the efficient catalytic active sites for the reduction of O<sub>2</sub> to H<sub>2</sub>O<sub>2</sub> while ensuring their inertness to H<sub>2</sub>O<sub>2</sub> decomposition is crucial for the photothermal catalytic synthesis of H<sub>2</sub>O<sub>2</sub> process, but still faces challenges. Herein, Co single-atom-loaded carbon nitride porous nanotubes (Co<sub>SA</sub>/CN-PNTs) were prepared by self-assembled polymerization and calcined annealing. The Co single atom is not only Co single atom can not only form Co<img>N bond with N in CN as an electron transport bridge, but also act as an active center in the photothermal catalytic O<sub>2</sub> reduction for H<sub>2</sub>O<sub>2</sub> synthesis. The porous tubular structure not only contributes to the enhancement of light absorption and utilization, but also facilitates the adsorption of O<sub>2</sub> as well as the formation of the key intermediate *OOH on the Co sites. Notably, the thermal effect generated by Co<sub>SA</sub>/CN-PNT during photocatalysis contributes to the rapidity of the reaction and ensures that the rapidly adsorbed O<sub>2</sub> on its surface inhibits the decomposition of H<sub>2</sub>O<sub>2</sub>. The results showed that the H₂O₂ generation rates of Co<sub>SA</sub>/CN-PNT reached 148.6 μmol L<sup>−1</sup> h<sup>−1</sup> and 169.6 μmol L<sup>−1</sup> h<sup>−1</sup> under visible light and solar radiation irradiation, respectively, which were 15 times and 16 times higher than those of the pristine CN material by a factor of 15.1 and 13.9, respectively. Therefore, this work improves the construction and understanding of the structure-efficacy relationship of catalysts at the atomic level by exploring the role of single atoms in the coordination shell layer and developing catalytic centers with unique single atoms.</div></div>","PeriodicalId":16782,"journal":{"name":"Journal of Photochemistry and Photobiology A-chemistry","volume":"478 ","pages":"Article 117183"},"PeriodicalIF":4.7,"publicationDate":"2026-09-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"147387948","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Pub Date : 2026-09-01Epub Date: 2026-02-25DOI: 10.1016/j.jphotochem.2026.117149
Neha Garg , Shalu Thakur , Armaandeep Kaur , Abhijit Dan , Savita Chaudhary , Aman Bhalla
Imperilling impact of heavy metal toxicity possessed serious threat to the wellbeing of our ecosystem. By utilizing the fluorescence abilities of 2,4,5-Tris phenylselanyl-1H-imidazole (3b) based probe, we developed high performing sensory probe for the accurate estimation of multiple metal ions. Under optimal conditions, our probe effectively detected Fe3+ and Cu2+ ions, distinguishing them from a wide array of other metals using UV–vis. and fluorescence measurements with wide linear ranges of 5 to 1000 μM. The respective limit of detection values are 0.40 μM and 0.23 μM for Fe3+ and Cu2+ ions respectively. Moreover, the complex of probe 3b with Fe3+/Cu2+ ions serve as a turn-on sensor for the detection of Ce3+ ions with LOD values of 0.14 μM and 0.31 μM in presence of Fe3+ and Cu2+ ions respectively. We performed a density functional theory (DFT) based computational study to gain crucial insights into how (3b) complexes with Fe3+ and Cu2+ ions. A logic gate was also designed to determine its potential in detection of Fe3+, Cu2+ and Ce3+ ions in an ‘off-on’ mode. This research provides a fresh perspective for creating innovative chemo-sensors. These sensors hold significant promise for selective and sensitive detection of multiple metal ions.
{"title":"Multi-ion sensing profiling using imidazole-based sensory probe","authors":"Neha Garg , Shalu Thakur , Armaandeep Kaur , Abhijit Dan , Savita Chaudhary , Aman Bhalla","doi":"10.1016/j.jphotochem.2026.117149","DOIUrl":"10.1016/j.jphotochem.2026.117149","url":null,"abstract":"<div><div>Imperilling impact of heavy metal toxicity possessed serious threat to the wellbeing of our ecosystem. By utilizing the fluorescence abilities of 2,4,5-Tris phenylselanyl-1H-imidazole (<strong>3b</strong>) based probe, we developed high performing sensory probe for the accurate estimation of multiple metal ions. Under optimal conditions, our probe effectively detected Fe<sup>3+</sup> and Cu<sup>2+</sup> ions<strong>,</strong> distinguishing them from a wide array of other metals using UV–vis. and fluorescence measurements with wide linear ranges of 5 to 1000 μM. The respective limit of detection values are 0.40 μM and 0.23 μM for Fe<sup>3+</sup> and Cu<sup>2+</sup> ions respectively<strong>.</strong> Moreover, the complex of probe <strong>3b</strong> with Fe<sup>3+</sup>/Cu<sup>2+</sup> ions serve as a turn-on sensor for the detection of Ce<sup>3+</sup> ions with LOD values of 0.14 μM and 0.31 μM in presence of Fe<sup>3+</sup> and Cu<sup>2+</sup> ions respectively. We performed a density functional theory (DFT) based computational study to gain crucial insights into how (<strong>3b</strong>) complexes with Fe<sup>3+</sup> and Cu<sup>2+</sup> ions<strong>.</strong> A logic gate was also designed to determine its potential in detection of Fe<sup>3+</sup>, Cu<sup>2+</sup> and Ce<sup>3+</sup> ions in an ‘off-on’ mode. This research provides a fresh perspective for creating innovative chemo-sensors<strong>.</strong> These sensors hold significant promise for selective and sensitive detection of multiple metal ions.</div></div>","PeriodicalId":16782,"journal":{"name":"Journal of Photochemistry and Photobiology A-chemistry","volume":"478 ","pages":"Article 117149"},"PeriodicalIF":4.7,"publicationDate":"2026-09-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"147387919","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Reactive oxygen species (ROS) are produced as by-products of oxygen metabolism and play an essential role in biological systems. In the eye, ROS can also be generated through the photosensitizing action of natural pigments like riboflavin. Disruption of the balance between ROS production and the antioxidant defense system leads to oxidative stress, which contributes to the development and progression of ocular diseases such as glaucoma. Under these conditions, oxidative degradation may occur in ophthalmic drugs used to treat glaucoma, potentially reducing their therapeutic efficacy and generating toxic products.
This study investigates the ROS-mediated degradation of widely used antiglaucoma drugs dorzolamide (DZ), ethoxzolamide (ET) and brimonidine tartrate (BT) in the presence of riboflavin and rose bengal as photosensitizers. Photochemical and spectroscopic analyses confirmed that these drugs interact with the electronically excited states of riboflavin and with various photo-generated ROS from these states, undergoing oxidative degradation via Type I and Type II mechanisms. The antiglaucoma drugs also exhibited pro-oxidant capacity, being able to generate O2(1Δg) upon direct irradiation and self-degrading under these conditions.
Furthermore, the potential cytotoxic effects of the degradation products were evaluated using human MRC-5 cells. The results showed that neither the drugs nor their oxidation products were significantly cytotoxic under the current experimental conditions.
These findings emphasize the importance of considering oxidative stability when formulating ophthalmic drugs, offering valuable insights into their behavior under oxidative stress scenarios.
{"title":"Degradation of widely used antiglaucoma drugs mediated by photo-generated reactive oxygen species","authors":"Charis Parramón Jurado , Cecilia Liaudat , Marcela Altamirano , Cecilia Challier , Susana Criado","doi":"10.1016/j.jphotochem.2026.117158","DOIUrl":"10.1016/j.jphotochem.2026.117158","url":null,"abstract":"<div><div>Reactive oxygen species (ROS) are produced as by-products of oxygen metabolism and play an essential role in biological systems. In the eye, ROS can also be generated through the photosensitizing action of natural pigments like riboflavin. Disruption of the balance between ROS production and the antioxidant defense system leads to oxidative stress, which contributes to the development and progression of ocular diseases such as glaucoma. Under these conditions, oxidative degradation may occur in ophthalmic drugs used to treat glaucoma, potentially reducing their therapeutic efficacy and generating toxic products.</div><div>This study investigates the ROS-mediated degradation of widely used antiglaucoma drugs dorzolamide (DZ), ethoxzolamide (ET) and brimonidine tartrate (BT) in the presence of riboflavin and rose bengal as photosensitizers. Photochemical and spectroscopic analyses confirmed that these drugs interact with the electronically excited states of riboflavin and with various photo-generated ROS from these states, undergoing oxidative degradation <em>via</em> Type I and Type II mechanisms. The antiglaucoma drugs also exhibited pro-oxidant capacity, being able to generate O<sub>2</sub>(<sup>1</sup>Δ<sub>g</sub>) upon direct irradiation and self-degrading under these conditions.</div><div>Furthermore, the potential cytotoxic effects of the degradation products were evaluated using human MRC-5 cells. The results showed that neither the drugs nor their oxidation products were significantly cytotoxic under the current experimental conditions.</div><div>These findings emphasize the importance of considering oxidative stability when formulating ophthalmic drugs, offering valuable insights into their behavior under oxidative stress scenarios.</div></div>","PeriodicalId":16782,"journal":{"name":"Journal of Photochemistry and Photobiology A-chemistry","volume":"478 ","pages":"Article 117158"},"PeriodicalIF":4.7,"publicationDate":"2026-09-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"147387975","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
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