Pub Date : 2025-01-30DOI: 10.1016/j.jphotochem.2025.116317
Deniz Kilic Ozturk , Demet Karaca Balta , Binnur Aydogan Temel , Gokhan Temel
This work describes a straightforward technique for preparing single–chain polymeric nanoparticles by photodimerization of pendant anthracene moieties on the side chain of styrenic and acrylic based linear polymers. The resulting single–chain polymeric nanoparticles (SCNPs) are then converted into pyrene functional nanoparticles through the simple Diels–Alder post–functionalization method. Polymeric nanoparticles containing maleimide and pyrene entities were deployed as a chemosensor capable of selectively detecting Fe3+ ions. Adding Fe3+ ions into achieved nanoparticle medium, color change is readily visible with unaided eye. The chemosensor’s ability to sense Fe3+ ions remained unaltered by the presence of other metal ions, such as Al3+, Ba2+, Ca2+, Cr3+, K+, Mg2+, Na+, NH4+, Ni2+, and Sn2+. These results suggest that functional SCNP is a potential probe of Fe3+ ions and it will be beneficial for future SCNP sensor design. They exhibit high sensitivity and selectivity for the detection of Fe3+ in the micromolar concentration range, making it a promising tool for Fe3+ detection even in the presence of other common interfering metal ions.
{"title":"Highly sensitive fluorescent single-chain polymeric nanoparticles as chemosensors for selective Fe3+ detection","authors":"Deniz Kilic Ozturk , Demet Karaca Balta , Binnur Aydogan Temel , Gokhan Temel","doi":"10.1016/j.jphotochem.2025.116317","DOIUrl":"10.1016/j.jphotochem.2025.116317","url":null,"abstract":"<div><div>This work describes a straightforward technique for preparing single–chain polymeric nanoparticles by photodimerization of pendant anthracene moieties on the side chain of styrenic and acrylic based linear polymers. The resulting single–chain polymeric nanoparticles (SCNPs) are then converted into pyrene functional nanoparticles through the simple Diels–Alder post–functionalization method. Polymeric nanoparticles containing maleimide and pyrene entities were deployed as a chemosensor capable of selectively detecting Fe<sup>3+</sup> ions. Adding Fe<sup>3+</sup> ions into achieved nanoparticle medium, color change is readily visible with unaided eye. The chemosensor’s ability to sense Fe<sup>3+</sup> ions remained unaltered by the presence of other metal ions, such as Al<sup>3+</sup>, Ba<sup>2+</sup>, Ca<sup>2+</sup>, Cr<sup>3+</sup>, K<sup>+</sup>, Mg<sup>2+</sup>, Na<sup>+</sup>, NH<sub>4</sub><sup>+</sup>, Ni<sup>2+</sup>, and Sn<sup>2+</sup>. These results suggest that functional SCNP is a potential probe of Fe<sup>3+</sup> ions and it will be beneficial for future SCNP sensor design. They exhibit high sensitivity and selectivity for the detection of Fe<sup>3+</sup> in the micromolar concentration range, making it a promising tool for Fe<sup>3+</sup> detection even in the presence of other common interfering metal ions.</div></div>","PeriodicalId":16782,"journal":{"name":"Journal of Photochemistry and Photobiology A-chemistry","volume":"464 ","pages":"Article 116317"},"PeriodicalIF":4.1,"publicationDate":"2025-01-30","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143230431","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 : 2025-01-30DOI: 10.1016/j.jphotochem.2025.116313
M.Paula Militello , Micaela E. Grassano , Ernesto M. Arbeloa , Sonia G. Bertolotti , Carlos M. Previtali
The photopolymerization of acrylamide in water under visible irradiation was initiated by the system eosin B/triethanolamine in deaerated conditions. In order to understand the mechanism of photoinitiation, the photophysics of the dye in the absence and presence of the amine was studied. The absorption and fluorescence properties in ethanol–water mixtures were determined. The fluorescence quantum yields were 0.003 and 0.02 in water and ethanol, respectively. The triplet state was observed by laser flash photolysis only in the alcohol. In water, the transient signal could not be detected. The triplet quantum yield was estimated at 0.08. In the absence of the amine or in air equilibrated solutions the polymer was not formed. Since no triplet is detected by laser flash photolysis in water, the question regarding the photoinitiation mechanism arises. It is suggested that, despite the lack of transient signal with our laser photolysis system, the triplet is formed in very low yield. Since the dye is photostable under the irradiation conditions of the polymerization experiments, in the long term polymerization could take place initiated by the triplet.
{"title":"Eosin B/amine as photoinitiator system of vinyl polymerization. A photophysical study of the dye","authors":"M.Paula Militello , Micaela E. Grassano , Ernesto M. Arbeloa , Sonia G. Bertolotti , Carlos M. Previtali","doi":"10.1016/j.jphotochem.2025.116313","DOIUrl":"10.1016/j.jphotochem.2025.116313","url":null,"abstract":"<div><div>The photopolymerization of acrylamide in water under visible irradiation was initiated by the system eosin B/triethanolamine in deaerated conditions. In order to understand the mechanism of photoinitiation, the photophysics of the dye in the absence and presence of the amine was studied. The absorption and fluorescence properties in ethanol–water mixtures were determined. The fluorescence quantum yields were 0.003 and 0.02 in water and ethanol, respectively. The triplet state was observed by laser flash photolysis only in the alcohol. In water, the transient signal could not be detected. The triplet quantum yield was estimated at 0.08. In the absence of the amine or in air equilibrated solutions the polymer was not formed. Since no triplet is detected by laser flash photolysis in water, the question regarding the photoinitiation mechanism arises. It is suggested that, despite the lack of transient signal with our laser photolysis system, the triplet is formed in very low yield. Since the dye is photostable under the irradiation conditions of the polymerization experiments, in the long term polymerization could take place initiated by the triplet.</div></div>","PeriodicalId":16782,"journal":{"name":"Journal of Photochemistry and Photobiology A-chemistry","volume":"463 ","pages":"Article 116313"},"PeriodicalIF":4.1,"publicationDate":"2025-01-30","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143142538","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 : 2025-01-30DOI: 10.1016/j.jphotochem.2025.116292
Peng Liu , Tengfei Zhao , Bingqian Li , Menghan Hou , Xue Zhang , Xiaofeng Yang , Guangyou Zhang , Na Jiang
A new multi-target sensor, (E)-2-(benzo[d]isoxazol-3-yl)-N’-(4-(diethylamino)-2-hydroxybenzylidene)acetohydrazide (BIDA), was designed using benzoisoxazole, characterized by its simplicity and ease of synthesis. An “off-on” effect towards Ga3+ ions in DMSO/H2O tris buffer and an “off-on-off” effect towards Mg2+ and Mn2+ ions in ACN/H2O tris buffer were exhibited by BIDA. Simultaneously, Ga3+, Mg2+ and Mn2+ ions were detected by BIDA, with lower detection limits of 1.91 × 10−8 M, 6.30 × 10−9 M and 1.95 × 10−8 M. The 1:2 chelation stoichiometry of the complexes formed between the sensor and Ga3+, Mg2+ and Mn2+ was confirmed using analysis of Job’s plot and mass spectrometry. Different concentrations of analyte ions in environment water samples were effectively identified by the BIDA sensor, and an independent, user-friendly paper sensor was successfully developed for their detection.
{"title":"A new multifunctional fluorescent sensor based on benzoisoxazol derivatives for monitoring Ga3+, Mg2+ and Mn2+ ions in different solvents","authors":"Peng Liu , Tengfei Zhao , Bingqian Li , Menghan Hou , Xue Zhang , Xiaofeng Yang , Guangyou Zhang , Na Jiang","doi":"10.1016/j.jphotochem.2025.116292","DOIUrl":"10.1016/j.jphotochem.2025.116292","url":null,"abstract":"<div><div>A new multi-target sensor, (<em>E</em>)-2-(benzo[<em>d</em>]isoxazol-3-yl)-N’-(4-(diethylamino)-2-hydroxybenzylidene)acetohydrazide (<strong>BIDA</strong>), was designed using benzoisoxazole, characterized by its simplicity and ease of synthesis. An “off-on” effect towards Ga<sup>3+</sup> ions in DMSO/H<sub>2</sub>O tris buffer and an “off-on-off” effect towards Mg<sup>2+</sup> and Mn<sup>2+</sup> ions in ACN/H<sub>2</sub>O tris buffer were exhibited by <strong>BIDA</strong>. Simultaneously, Ga<sup>3+</sup>, Mg<sup>2+</sup> and Mn<sup>2+</sup> ions were detected by <strong>BIDA</strong>, with lower detection limits of 1.91 × 10<sup>−8</sup> M, 6.30 × 10<sup>−9</sup> M and 1.95 × 10<sup>−8</sup> M. The 1:2 chelation stoichiometry of the complexes formed between the sensor and Ga<sup>3+</sup>, Mg<sup>2+</sup> and Mn<sup>2+</sup> was confirmed using analysis of Job’s plot and mass spectrometry. Different concentrations of analyte ions in environment water samples were effectively identified by the <strong>BIDA</strong> sensor, and an independent, user-friendly paper sensor was successfully developed for their detection.</div></div>","PeriodicalId":16782,"journal":{"name":"Journal of Photochemistry and Photobiology A-chemistry","volume":"464 ","pages":"Article 116292"},"PeriodicalIF":4.1,"publicationDate":"2025-01-30","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143230432","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 : 2025-01-30DOI: 10.1016/j.jphotochem.2025.116306
Awad I. Said , Desislava Staneva , Daniela Atanasova , Albena Jordanova , Ivo Grabchev
Antimicrobial photodynamic therapy is one of the effective strategies for facing the resistance of pathogenic microorganisms of traditional antibiotics. In connection with this, new effective compounds are being sought, increasing their biological activity upon irradiation. In this work, a new polypropylene imine (PPI) from the first generation was synthesized and modified with 1,8-naphthalimide, to which a sulfonyl chloride group (D1) was introduced at the C-4 atom, from which after interaction with glucosamine, a dendrimer containing a sulphonamide group (D2) was obtained. The photophysical characteristics of dendrimer D2 were investigated in five organic solvents of different polarity and aqueous media. It was found that the absorption and fluorescence maxima are slightly affected by the polarity of the solvents. Excimer and monomeric fluorescence were also recorded with dendrimer D2 in an aqueous solution. Dendrimer D2 was deposited on the surface of the cotton fabric, and its release from the cotton fabric was studied for 4 h in a phosphate buffer at 37 °C. The antimicrobial activity of dendrimer D2 was investigated in meat-peptone broth (MPB) against Gram-positive B. cereus and Gram-negative P. aeruginosa and on cotton fabric compared in the dark and after irradiation with sunlight. It has been found that after irradiation with light, the activity of D2 and cotton fabrics is enhanced due to their antimicrobial photodynamic activity. Additionally, light can be utilized to self-sterilize cotton fabrics when treated with D2.
{"title":"A new photoactive water-soluble polypropylene imine dendrimer modified with 1,8-naphthalimide and N-glucosamine for light-driven self-sterilizing cotton fabrics","authors":"Awad I. Said , Desislava Staneva , Daniela Atanasova , Albena Jordanova , Ivo Grabchev","doi":"10.1016/j.jphotochem.2025.116306","DOIUrl":"10.1016/j.jphotochem.2025.116306","url":null,"abstract":"<div><div>Antimicrobial photodynamic therapy is one of the effective strategies for facing the resistance of pathogenic microorganisms of traditional antibiotics. In connection with this, new effective compounds are being sought, increasing their biological activity upon irradiation. In this work, a new polypropylene imine (PPI) from the first generation was synthesized and modified with 1,8-naphthalimide, to which a sulfonyl chloride group (D1) was introduced at the C-4 atom, from which after interaction with glucosamine, a dendrimer containing a sulphonamide group (D2) was obtained. The photophysical characteristics of dendrimer D2 were investigated in five organic solvents of different polarity and aqueous media. It was found that the absorption and fluorescence maxima are slightly affected by the polarity of the solvents. Excimer and monomeric fluorescence were also recorded with dendrimer D2 in an aqueous solution. Dendrimer D2 was deposited on the surface of the cotton fabric, and its release from the cotton fabric was studied for 4 h in a phosphate buffer at 37 °C. The antimicrobial activity of dendrimer D2 was investigated in meat-peptone broth (MPB) against Gram-positive <em>B. cereus</em> and Gram-negative <em>P. aeruginosa</em> and on cotton fabric compared in the dark and after irradiation with sunlight. It has been found that after irradiation with light, the activity of D2 and cotton fabrics is enhanced due to their antimicrobial photodynamic activity. Additionally, light can be utilized to self-sterilize cotton fabrics when treated with D2.</div></div>","PeriodicalId":16782,"journal":{"name":"Journal of Photochemistry and Photobiology A-chemistry","volume":"464 ","pages":"Article 116306"},"PeriodicalIF":4.1,"publicationDate":"2025-01-30","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143157977","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"OA","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Pub Date : 2025-01-30DOI: 10.1016/j.jphotochem.2025.116312
Carolina Vesga-Hernández , Rafael dos Santos Carvalho , Arthur Barreto , Marlin Jeannette Pedrozo Peñafiel , Julia Rodrigues de Noronha , Luís Maqueira , Davi Back , Dayvid Mello Nascimento , Leandro H. Zucolotto Cocca , Ricardo Queiroz Aucélio , Leonardo de Boni , Marco Cremona , Jones Limberger
Novel phenylpyridylcarbodinitrile (PPC) derivatives were synthesized to develop materials whose emission properties can be tuned by changes in their dissolving/dispersing environment. In solution these compounds exhibit blue to green fluorescence with quantum yields between 0.01 and 0.70. The large Stokes shifts, along with the significant rotational freedom of the rings and computational data indicate twisted intramolecular charge transfer (TICT) excited states for these PPCs. The dimethylmethoxyaryl-substituted PPC (MT-PPC) exhibited distinctive emissive properties, featuring highly environment-dependent fluorescence in solution, with a Δλem = 118 nm. Additionally, this compound exhibits aggregation-induced enhanced emission (AIEE), with a 19-fold photoluminescence quantum yield enhancement upon aggregation, whose emission profile is very similar to those observed with MT-PPC as a pure thin film. Conversely, in SF3PO films doped with MT-PPC, the emission is dependent on MT-PPC percentage. Films with 5 % and 10 % exhibit blue-shifted fluorescence (433 and 436 nm) compared to the 20 % film (445 nm), and especially compared to the pure film (468 nm). Interestingly, OLEDs with the same doped films also present environment-dependent behavior, with similar trends regarding the emission maximum. OLEDs with 5 % and 10 % show electroluminescence maxima at 437 nm, while the OLED with 20 % MT-PPC exhibits emission centered at 463 nm. Furthermore, these changes in dopant content shift the chromaticity coordinates from (0.18, 0.15) to (0.20, 0.26), demonstrating that the emissive properties of MT-PPC are environment-dependent, and consequently tunable in solution, thin films, and OLEDs.
{"title":"Aggregation-Induced enhanced emission and twisted intramolecular charge transfer in a pyridylcarbodinitrile with tunable photoluminescence in solution, films, and OLEDs","authors":"Carolina Vesga-Hernández , Rafael dos Santos Carvalho , Arthur Barreto , Marlin Jeannette Pedrozo Peñafiel , Julia Rodrigues de Noronha , Luís Maqueira , Davi Back , Dayvid Mello Nascimento , Leandro H. Zucolotto Cocca , Ricardo Queiroz Aucélio , Leonardo de Boni , Marco Cremona , Jones Limberger","doi":"10.1016/j.jphotochem.2025.116312","DOIUrl":"10.1016/j.jphotochem.2025.116312","url":null,"abstract":"<div><div>Novel phenylpyridylcarbodinitrile (<strong>PPC</strong>) derivatives were synthesized to develop materials whose emission properties can be tuned by changes in their dissolving/dispersing environment. In solution these compounds exhibit blue to green fluorescence with quantum yields between 0.01 and 0.70. The large Stokes shifts, along with the significant rotational freedom of the rings and computational data indicate twisted intramolecular charge transfer (TICT) excited states for these <strong>PPCs</strong>. The dimethylmethoxyaryl-substituted <strong>PPC</strong> (<strong>MT-PPC</strong>) exhibited distinctive emissive properties, featuring highly environment-dependent fluorescence in solution, with a <strong>Δλ<sub>em</sub></strong> = 118 nm. Additionally, this compound exhibits aggregation-induced enhanced emission (AIEE), with a 19-fold photoluminescence quantum yield enhancement upon aggregation, whose emission profile is very similar to those observed with <strong>MT-PPC</strong> as a pure thin film. Conversely, in SF3PO films doped with <strong>MT-PPC</strong>, the emission is dependent on <strong>MT-PPC</strong> percentage. Films with 5 % and 10 % exhibit blue-shifted fluorescence (433 and 436 nm) compared to the 20 % film (445 nm), and especially compared to the pure film (468 nm). Interestingly, OLEDs with the same doped films also present environment-dependent behavior, with similar trends regarding the emission maximum. OLEDs with 5 % and 10 % show electroluminescence maxima at 437 nm, while the OLED with 20 % <strong>MT-PPC</strong> exhibits emission centered at 463 nm. Furthermore, these changes in dopant content shift the chromaticity coordinates from (0.18, 0.15) to (0.20, 0.26), demonstrating that the emissive properties of <strong>MT-PPC</strong> are environment-dependent, and consequently tunable in solution, thin films, and OLEDs.</div></div>","PeriodicalId":16782,"journal":{"name":"Journal of Photochemistry and Photobiology A-chemistry","volume":"464 ","pages":"Article 116312"},"PeriodicalIF":4.1,"publicationDate":"2025-01-30","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143158009","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}
The detection of Ochratoxin A (OTA) in wine samples is crucial for ensuring the safety and quality of wine products. Addressing this need, a photoelectrochemical aptasensor composed of electrochemically synthesized zinc oxide nanorods (ZnO-NRs), cadmium sulfide nanofibers (CdS) deposited via chemicalp bath deposition, gold nanoparticles (Au-NPs) obtained through electrochemical reduction and selective aptamers added by drop casting has been developed. The ZnO-NRs provide a high surface area, while CdS nanofibers enhance photoelectrochemical properties, Au-NPs facilitate electron transfer, and the aptamers offer high selectivity towards OTA. The morphology and structure of the synthesized compounds were characterized using Scanning Electron Microscopy (SEM), Transmission Electron Microscopy (TEM), and X-ray diffraction (XRD). Evaluation of the aptasensor’s performance in synthetic wine samples demonstrated that the photocurrent signal significantly improves sensor sensitivity compared to dark conditions, owing to the enhanced electron transfer upon photoexcitation of the CdS semiconductor. The aptasensor achieved a limit of detection (LOD) and limit of quantification (LOQ) of 0.5 μg/L and 1.8 μg/L, respectively, surpassing the European Union’s OTA threshold of 2 μg/L in wines. These findings highlight the potential application of the developed aptasensor in the wine export industry and open new avenues for the development of photoelectrochemical biosensors for various analytes by modifying the aptamer.
{"title":"Photoelectrochemical aptasensor for detection of Ochratoxin A in synthetic red wine samples","authors":"Nicole Briones , Humberto Gómez , Rodrigo Henríquez , Víctor Rojas , María Villarroel","doi":"10.1016/j.jphotochem.2025.116311","DOIUrl":"10.1016/j.jphotochem.2025.116311","url":null,"abstract":"<div><div>The detection of Ochratoxin A (OTA) in wine samples is crucial for ensuring the safety and quality of wine products. Addressing this need, a photoelectrochemical aptasensor composed of electrochemically synthesized zinc oxide nanorods (ZnO-NRs), cadmium sulfide nanofibers (CdS) deposited via chemicalp bath deposition, gold nanoparticles (Au-NPs) obtained through electrochemical reduction and selective aptamers added by drop casting has been developed. The ZnO-NRs provide a high surface area, while CdS nanofibers enhance photoelectrochemical properties, Au-NPs facilitate electron transfer, and the aptamers offer high selectivity towards OTA. The morphology and structure of the synthesized compounds were characterized using Scanning Electron Microscopy (SEM), Transmission Electron Microscopy (TEM), and X-ray diffraction (XRD). Evaluation of the aptasensor’s performance in synthetic wine samples demonstrated that the photocurrent signal significantly improves sensor sensitivity compared to dark conditions, owing to the enhanced electron transfer upon photoexcitation of the CdS semiconductor. The aptasensor achieved a limit of detection (LOD) and limit of quantification (LOQ) of 0.5 μg/L and 1.8 μg/L, respectively, surpassing the European Union’s OTA threshold of 2 μg/L in wines. These findings highlight the potential application of the developed aptasensor in the wine export industry and open new avenues for the development of photoelectrochemical biosensors for various analytes by modifying the aptamer.</div></div>","PeriodicalId":16782,"journal":{"name":"Journal of Photochemistry and Photobiology A-chemistry","volume":"463 ","pages":"Article 116311"},"PeriodicalIF":4.1,"publicationDate":"2025-01-30","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143142537","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 : 2025-01-30DOI: 10.1016/j.jphotochem.2025.116303
Yeon Gyo Shim , Jong Young Ko , Ji Hyun Kim , Seung Hyeon Jeong , Woon Yong Sohn
We fabricated hematite (α-Fe2O3)-based photoanodes with TiO2 underlayer to reveal the origin of the unexpected anodic shift of the onset potential. We demonstrated that, particularly at the relatively low applied bias voltage, the TiO2 underlayer played a significant role in Fermi level pinning, resulting in the reduction of the photovoltage. The back recombination between the long-lived holes surviving at the surface of α-Fe2O3 and the free electrons in the conductive substrate was retarded in the presence of the TiO2 underlayer, implying that it acted as a blocking layer, but the trap-mediated recombination could be accelerated, resulting in the reduction of the photocurrent at the low applied bias condition.
{"title":"Investigation of the role of TiO2 underlayer in the anodic potential shift of the onset potential in hematite photoanode","authors":"Yeon Gyo Shim , Jong Young Ko , Ji Hyun Kim , Seung Hyeon Jeong , Woon Yong Sohn","doi":"10.1016/j.jphotochem.2025.116303","DOIUrl":"10.1016/j.jphotochem.2025.116303","url":null,"abstract":"<div><div>We fabricated hematite (α-Fe<sub>2</sub>O<sub>3</sub>)-based photoanodes with TiO<sub>2</sub> underlayer to reveal the origin of the unexpected anodic shift of the onset potential. We demonstrated that, particularly at the relatively low applied bias voltage, the TiO<sub>2</sub> underlayer played a significant role in Fermi level pinning, resulting in the reduction of the photovoltage. The back recombination between the long-lived holes surviving at the surface of α-Fe<sub>2</sub>O<sub>3</sub> and the free electrons in the conductive substrate was retarded in the presence of the TiO<sub>2</sub> underlayer, implying that it acted as a blocking layer, but the trap-mediated recombination could be accelerated, resulting in the reduction of the photocurrent at the low applied bias condition.</div></div>","PeriodicalId":16782,"journal":{"name":"Journal of Photochemistry and Photobiology A-chemistry","volume":"464 ","pages":"Article 116303"},"PeriodicalIF":4.1,"publicationDate":"2025-01-30","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143158010","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}
Chiral and non-conjugated C2-spirooxindole substituted at the C3 position by a phenyl ring has been studied for its unusual photoluminescence behaviour. The spectral results showed positive solvatochromism in absorption and visible emission with large Stokes shifts up to 5000 cm−1 and good quantum yield. The C3-phenyl ring was found to play a central role in the unusual visible emission, allowing rotation through a single bond. Ground-state and excited-state DFT calculations revealed that the twisted phenyl plays a crucial role in the orbital interaction through space. Experiments with binary mixtures of MeCN/H2O (v/v %), which are usually associated with aggregate formation and restriction of molecular rotation, clearly showed a gradual decrease in emission with increasing water fraction. Therefore, the excited state rotation of the phenyl ring is the key factor for the observed visible emission, and the quenched emission in the binary mixture of MeCN/H2O is a result of the restricted rotation, which is incapable of effective through-space conjugation.
{"title":"Intramolecular through-space conjugation of chiral C2-spirooxindole","authors":"Kosuke Nakashima , Aoi Imamura , Yasuyuki Matsushima , Shin-ichi Hirashima , Dancho Yordanov , Tsuyoshi Miura , Anton Georgiev","doi":"10.1016/j.jphotochem.2025.116316","DOIUrl":"10.1016/j.jphotochem.2025.116316","url":null,"abstract":"<div><div>Chiral and non-conjugated C2-spirooxindole substituted at the C3 position by a phenyl ring has been studied for its unusual photoluminescence behaviour. The spectral results showed positive solvatochromism in absorption and visible emission with large Stokes shifts up to 5000 cm<sup>−1</sup> and good quantum yield. The C3-phenyl ring was found to play a central role in the unusual visible emission, allowing rotation through a single bond. Ground-state and excited-state DFT calculations revealed that the twisted phenyl plays a crucial role in the orbital interaction through space. Experiments with binary mixtures of MeCN/H<sub>2</sub>O (v/v %), which are usually associated with aggregate formation and restriction of molecular rotation, clearly showed a gradual decrease in emission with increasing water fraction. Therefore, the excited state rotation of the phenyl ring is the key factor for the observed visible emission, and the quenched emission in the binary mixture of MeCN/H<sub>2</sub>O is a result of the restricted rotation, which is incapable of effective through-space conjugation.</div></div>","PeriodicalId":16782,"journal":{"name":"Journal of Photochemistry and Photobiology A-chemistry","volume":"463 ","pages":"Article 116316"},"PeriodicalIF":4.1,"publicationDate":"2025-01-29","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143142533","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 : 2025-01-29DOI: 10.1016/j.jphotochem.2024.116250
Chen Luo , Huijin Lin , Huihui Cai , Chaobiao Huang
Anionic cyanine is an organic fluorescent dye with excellent optical properties. Compared to cationic cyanine, anionic cyanine has been less studied and applied due to the lack of modification sites. However, when the cyclohexene ring in the anionic cyanine skeleton is replaced by a tetrahydropyridine ring, the modification site will be added, forming a novel cyanine dye AHC-N-R with NIR emission. Photophysical properties show that this anionic cyanine retains the excellent optical properties of conventional cyanine and is expected to adjust the fluorescence emission by changing the substituent groups. Acrylates were introduced in this dye to synthesize the cysteine fluorescent probe AHC-NBn-AE. The amino and sulfhydryl groups in cysteine condense with acrylate to form 1,4-thiazepane analogs and release fluorophores AHC-NBn-OH, restoring fluorescence at 650 nm. The fluorescence recovery of the probe was linearly related to the concentration of cysteine for 0.3–50.0 μmol/L. The detection limit was 0.1 μmol/L (S/N = 3, n = 9). There was almost no interference with DL-homocysteine, glutathione and several common amino acids to cysteine. The cysteine content of the L-cysteine capsule was successfully tested. The recovery rate was 94.4 %–101.5 %.
{"title":"Modification of anionic cyanine dyes and application in cysteine detection","authors":"Chen Luo , Huijin Lin , Huihui Cai , Chaobiao Huang","doi":"10.1016/j.jphotochem.2024.116250","DOIUrl":"10.1016/j.jphotochem.2024.116250","url":null,"abstract":"<div><div>Anionic cyanine is an organic fluorescent dye with excellent optical properties. Compared to cationic cyanine, anionic cyanine has been less studied and applied due to the lack of modification sites. However, when the cyclohexene ring in the anionic cyanine skeleton is replaced by a tetrahydropyridine ring, the modification site will be added, forming a novel cyanine dye AHC-N-R with NIR emission. Photophysical properties show that this anionic cyanine retains the excellent optical properties of conventional cyanine and is expected to adjust the fluorescence emission by changing the substituent groups. Acrylates were introduced in this dye to synthesize the cysteine fluorescent probe AHC-NBn-AE. The amino and sulfhydryl groups in cysteine condense with acrylate to form 1,4-thiazepane analogs and release fluorophores AHC-NBn-OH, restoring fluorescence at 650 nm. The fluorescence recovery of the probe was linearly related to the concentration of cysteine for 0.3–50.0 μmol/L. The detection limit was 0.1 μmol/L (S/N = 3, n = 9). There was almost no interference with DL-homocysteine, glutathione and several common amino acids to cysteine. The cysteine content of the L-cysteine capsule was successfully tested. The recovery rate was 94.4 %–101.5 %.</div></div>","PeriodicalId":16782,"journal":{"name":"Journal of Photochemistry and Photobiology A-chemistry","volume":"464 ","pages":"Article 116250"},"PeriodicalIF":4.1,"publicationDate":"2025-01-29","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143387795","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 : 2025-01-29DOI: 10.1016/j.jphotochem.2025.116318
Hany M. Abd El-Lateef , Mai M. Khalaf , Manal F. Abou Taleb , Ahmed Mohajja Alshammari , Mohamed Gouda
Smart adhesive was developed toward a simple preparation of photoluminescent and water-resistant products. The formulated adhesive persisted to emit light for up to 90 min after the lighting source was switched off. Rare-earth aluminate (SrAl2O4:Eu2+,Dy3+; SAO) nanoparticles (5–12 nm) and glass nanofibers (GNF) were distributed in liquid volcanized silicone rubber (VSR; polysiloxane) to produce a nanocomposite adhesive. Electrospun glass nanofibers (GNF) were used as a reinforcement agent, displaying diameters of 50–125 nm. SAO was evenly distributed without agglomeration in the polysiloxane matrix by using nanoparticles, allowing the resultant nanocomposite adhesive to be transparent. The applied adhesives exhibited an emission band at 519 nm when excited at 365 nm. According to the SAO concentration, the photoluminescence spectra exhibited either fluorescence or afterglow emission. Photochromism was observed transitioning from translucent to green under an ultraviolet source and yellowish-green in a dark room. The developed adhesives showed scratch and water resistance owing to the incorporation of SAO nanoparticles (NPs) into the polysiloxane matrix. The SAO@VSR nanocomposite exhibited significant durability and photostability. This study demonstrated the viability of industrial production of intelligent adhesives for various uses, such as safety signs and smart windows.
{"title":"Facile strategy toward smart nanocomposite glass nanofiber-reinforced polysiloxane adhesives with superhydrophobic and photoluminescence properties","authors":"Hany M. Abd El-Lateef , Mai M. Khalaf , Manal F. Abou Taleb , Ahmed Mohajja Alshammari , Mohamed Gouda","doi":"10.1016/j.jphotochem.2025.116318","DOIUrl":"10.1016/j.jphotochem.2025.116318","url":null,"abstract":"<div><div>Smart adhesive was developed toward a simple preparation of photoluminescent and water-resistant products. The formulated adhesive persisted to emit light for up to 90 min after the lighting source was switched off. Rare-earth aluminate (SrAl<sub>2</sub>O<sub>4</sub>:Eu<sup>2+</sup>,Dy<sup>3+</sup>; SAO) nanoparticles (5–12 nm) and glass nanofibers (GNF) were distributed in liquid volcanized silicone rubber (VSR; polysiloxane) to produce a nanocomposite adhesive. Electrospun glass nanofibers (GNF) were used as a reinforcement agent, displaying diameters of 50–125 nm. SAO was evenly distributed without agglomeration in the polysiloxane matrix by using nanoparticles, allowing the resultant nanocomposite adhesive to be transparent. The applied adhesives exhibited an emission band at 519 nm when excited at 365 nm. According to the SAO concentration, the photoluminescence spectra exhibited either fluorescence or afterglow emission. Photochromism was observed transitioning from translucent to green under an ultraviolet source and yellowish-green in a dark room. The developed adhesives showed scratch and water resistance owing to the incorporation of SAO nanoparticles (NPs) into the polysiloxane matrix. The SAO@VSR nanocomposite exhibited significant durability and photostability. This study demonstrated the viability of industrial production of intelligent adhesives for various uses, such as safety signs and smart windows.</div></div>","PeriodicalId":16782,"journal":{"name":"Journal of Photochemistry and Photobiology A-chemistry","volume":"463 ","pages":"Article 116318"},"PeriodicalIF":4.1,"publicationDate":"2025-01-29","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143142532","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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