Pub Date : 2025-01-18DOI: 10.1016/j.jphotochem.2025.116274
Na Liu, Yanwei Su, Siyi Zheng, Yuchen Tang, Chunxia Yu, Yuangang Li, Lihua Shen
Sulfur nanosheets (S-NSs), as a novel photocatalyst, was designed to composite with graphite phase nitrogen carbide (g-C3N4) to form a kind of new S-NSs/g-C3N4 (CNS) photocatalyst. The modulating effect of bovine serum albumin (BSA) or poly (3,4-ethylenedioxythiao)-polystyrene sulfonic acid (PEDOT:PSS) ligands on the photocatalytic activity of CNS nanocomposite was studied. The ligands mainly affect the band gap and conduction band potential of the photocatalyst, leading to different photocatalytic activities. When BSA was used as a ligand, the combine of S-NSs and g-C3N4 (CNS-B) cannot improve the photocatalytic activity for the degradation of Rhodamine B (RhB). When PEDOT:PSS was used as a ligand, the composite catalysts of CNS-P significantly improved the photocatalytic activity. The degradation efficiency of composite material CNS-P for RhB and Doxycycline hydrochloride (DOX) can reach 97 % (90 min) and 78 % (90 min). Since the combine of S-NSs and g-C3N4, the photoelectric conversion ability was enhanced and the carrier mobility was accelerated. The composite catalyst enhanced the redox ability and suppressed the recombination of photo generated carriers through Z-type charge transfer. This study give a reference for designing a new photocatalysts of two dimensional materials and also provide a potential feasibility for antibiotic degradation application.
{"title":"Impact of ligand on layered sulfur nanosheets/g-C3N4 nanocomposite for photocatalytic degradation","authors":"Na Liu, Yanwei Su, Siyi Zheng, Yuchen Tang, Chunxia Yu, Yuangang Li, Lihua Shen","doi":"10.1016/j.jphotochem.2025.116274","DOIUrl":"10.1016/j.jphotochem.2025.116274","url":null,"abstract":"<div><div>Sulfur nanosheets (S-NSs), as a novel photocatalyst, was designed to composite with graphite phase nitrogen carbide (g-C<sub>3</sub>N<sub>4</sub>) to form a kind of new S-NSs/g-C<sub>3</sub>N<sub>4</sub> (CNS) photocatalyst. The modulating effect of bovine serum albumin (BSA) or poly (3,4-ethylenedioxythiao)-polystyrene sulfonic acid (PEDOT:PSS) ligands on the photocatalytic activity of CNS nanocomposite was studied. The ligands mainly affect the band gap and conduction band potential of the photocatalyst, leading to different photocatalytic activities. When BSA was used as a ligand, the combine of S-NSs and g-C<sub>3</sub>N<sub>4</sub> (CNS-B) cannot improve the photocatalytic activity for the degradation of Rhodamine B (RhB). When PEDOT:PSS was used as a ligand, the composite catalysts of CNS-P significantly improved the photocatalytic activity. The degradation efficiency of composite material CNS-P for RhB and Doxycycline hydrochloride (DOX) can reach 97 % (90 min) and 78 % (90 min). Since the combine of S-NSs and g-C<sub>3</sub>N<sub>4</sub>, the photoelectric conversion ability was enhanced and the carrier mobility was accelerated. The composite catalyst enhanced the redox ability and suppressed the recombination of photo generated carriers through Z-type charge transfer. This study give a reference for designing a new photocatalysts of two dimensional materials and also provide a potential feasibility for antibiotic degradation application.</div></div>","PeriodicalId":16782,"journal":{"name":"Journal of Photochemistry and Photobiology A-chemistry","volume":"463 ","pages":"Article 116274"},"PeriodicalIF":4.1,"publicationDate":"2025-01-18","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143142403","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 : 2025-01-18DOI: 10.1016/j.jphotochem.2025.116273
Muhammad Asad , Naeem Khan , Muslim Khan , Mohibullah Shah , Wei Sun , Xiaoping Zhang , Riaz Ullah , Essam A. Ali , Amir Badshah , Umar Nishan
Abnormal levels of uric acid in the human body lead to several diseases such as gout, diabetes, renal impairment, cardiovascular problems, etc. It is imperative to develop an easy-to-use and low-cost sensing platform. The present work reports on a non-enzymatic colorimetric sensor based on the peroxidase-like activity of ionic liquid-capped silver-zinc oxide-doped activated carbon (IL/Ag-ZnO@AC) for the detection of uric acid. The prepared nanocomposite was characterized by various spectroscopic techniques. The prepared nanozyme catalyzed the oxidation of the chromogenic substrate TMB (3,3′,5,5′-tetramethylbenzidine). Based on the redox chemistry of uric acid, it inhibited the peroxidase-like activity of the proposed nanozyme with a visible colorimetric change. Subsequently, various parameters such as time, pH, H2O2, and the amount of the nanozyme as well as TMB were optimized. The proposed assay showed linear detection of uric acid in the range of 0.5–180 μM. Other parameters, such as the limit of detection, limit of quantification, and R2 were computed to be 0.13 μM, 0.45 μM, and 0.999, respectively. Alongside its sensitivity, the developed assay was found to be highly selective in the presence of various potential interfering species. The proposed assay was successfully employed for the detection of uric acid in real samples under optimum experimental conditions. The proposed nanozyme has the potential to translate into a useful laboratory tool that can routinely be used for the sensing of uric acid in various diseases.
{"title":"Ionic liquid-capped silver-zinc oxide@activated carbon: A Powerful nanocomposite for colorimetric uric acid detection","authors":"Muhammad Asad , Naeem Khan , Muslim Khan , Mohibullah Shah , Wei Sun , Xiaoping Zhang , Riaz Ullah , Essam A. Ali , Amir Badshah , Umar Nishan","doi":"10.1016/j.jphotochem.2025.116273","DOIUrl":"10.1016/j.jphotochem.2025.116273","url":null,"abstract":"<div><div>Abnormal levels of uric acid in the human body lead to several diseases such as gout, diabetes, renal impairment, cardiovascular problems, etc. It is imperative to develop an easy-to-use and low-cost sensing platform. The present work reports on a non-enzymatic colorimetric sensor based on the peroxidase-like activity of ionic liquid-capped silver-zinc oxide-doped activated carbon (IL/Ag-ZnO@AC) for the detection of uric acid. The prepared nanocomposite was characterized by various spectroscopic techniques. The prepared nanozyme catalyzed the oxidation of the chromogenic substrate TMB (3,3′,5,5′-tetramethylbenzidine). Based on the redox chemistry of uric acid, it inhibited the peroxidase-like activity of the proposed nanozyme with a visible colorimetric change. Subsequently, various parameters such as time, pH, H<sub>2</sub>O<sub>2</sub>, and the amount of the nanozyme as well as TMB were optimized. The proposed assay showed linear detection of uric acid in the range of 0.5–180 μM. Other parameters, such as the limit of detection, limit of quantification, and R<sup>2</sup> were computed to be 0.13 μM, 0.45 μM, and 0.999, respectively. Alongside its sensitivity, the developed assay was found to be highly selective in the presence of various potential interfering species. The proposed assay was successfully employed for the detection of uric acid in real samples under optimum experimental conditions. The proposed nanozyme has the potential to translate into a useful laboratory tool that can routinely be used for the sensing of uric acid in various diseases.</div></div>","PeriodicalId":16782,"journal":{"name":"Journal of Photochemistry and Photobiology A-chemistry","volume":"463 ","pages":"Article 116273"},"PeriodicalIF":4.1,"publicationDate":"2025-01-18","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143142937","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 : 2025-01-17DOI: 10.1016/j.jphotochem.2025.116277
Carlos A. Ardila Padilla , M. José Sosa , María Noel Urrutia , Andrés H. Thomas , M. Laura Dántola , Virginie Lyria Lhiaubet , Mariana Vignoni
The isoalloxazine chromophore of riboflavin (Rf), or vitamin B2, has been exploited over the years for applications in many different areas including photocatalysis, photobiology, photomedicine, etc. We recently reported the biologically relevant features of a N3-alkylated Rf derivative, decyl-Rf, as a lipophilic sensitizer. This compound, which exhibits photophysical and photochemical properties similar to those of the parent isoalloxazine chromophore, induced an exacerbated UVA-photosensitized oxidation of the lipid bilayer. Here, we took advantage of the blue light absorption of decyl-Rf and studied the photochemistry of this lipophilic photosensitizer in non-aqueous solutions after excitation at 445 nm. Air-equilibrated and oxygen-free methanolic solutions of decyl-Rf were irradiated and the photodegradation products were characterized by mass spectrometry. We showed that substitution at N3 position by the decyl carbon chain stabilizes the isoalloxazine core. Indeed, besides the typical Rf photoproducts, lumichrome and lumiflavin derivatives, four photoproducts with a modified ribityl chain, but with intact decyl chain at N3 position and isoalloxazine chromophore, were detected. Therefore, these photoproducts, if formed in biological media, should preserve not only their lipophilicity and interaction with lipid membranes but also their photosensitizing properties.
{"title":"Blue light-promoted photodegradation of decyl-riboflavin in methanolic solutions","authors":"Carlos A. Ardila Padilla , M. José Sosa , María Noel Urrutia , Andrés H. Thomas , M. Laura Dántola , Virginie Lyria Lhiaubet , Mariana Vignoni","doi":"10.1016/j.jphotochem.2025.116277","DOIUrl":"10.1016/j.jphotochem.2025.116277","url":null,"abstract":"<div><div>The isoalloxazine chromophore of riboflavin (Rf), or vitamin B2, has been exploited over the years for applications in many different areas including photocatalysis, photobiology, photomedicine, etc. We recently reported the biologically relevant features of a <em>N</em><sup>3</sup>-alkylated Rf derivative, decyl-Rf, as a lipophilic sensitizer. This compound, which exhibits photophysical and photochemical properties similar to those of the parent isoalloxazine chromophore, induced an exacerbated UVA-photosensitized oxidation of the lipid bilayer. Here, we took advantage of the blue light absorption of decyl-Rf and studied the photochemistry of this lipophilic photosensitizer in non-aqueous solutions after excitation at 445 nm. Air-equilibrated and oxygen-free methanolic solutions of decyl-Rf were irradiated and the photodegradation products were characterized by mass spectrometry. We showed that substitution at <em>N</em><sup>3</sup> position by the decyl carbon chain stabilizes the isoalloxazine core. Indeed, besides the typical Rf photoproducts, lumichrome and lumiflavin derivatives, four photoproducts with a modified ribityl chain, but with intact decyl chain at <em>N</em><sup>3</sup> position and isoalloxazine chromophore, were detected. Therefore, these photoproducts, if formed in biological media, should preserve not only their lipophilicity and interaction with lipid membranes but also their photosensitizing properties.</div></div>","PeriodicalId":16782,"journal":{"name":"Journal of Photochemistry and Photobiology A-chemistry","volume":"463 ","pages":"Article 116277"},"PeriodicalIF":4.1,"publicationDate":"2025-01-17","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143142933","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 : 2025-01-16DOI: 10.1016/j.jphotochem.2025.116278
Huu-Tap Van , Mikhail Ivanov , Razzagh Rahimpoor , Nezamaddin Mengelizadeh , Marwah Mohammed hareeja , Neeti Misra , Saad Hayif Jasim Ali , Davoud Balarak
Antibiotics, categorized as emerging pollutants, present environmental challenges owing to their harmful and mutation-inducing properties, which hinder their removal. This study seeks to produce Fe3O4-SiO2-EN@Zn-Al layered double hydroxide (FSEZAL) nanocomposites for effectively degrading amoxicillin (AMX) through photocatalysis. The target nanocomposite was prepared using a sol–gel method and subsequently characterized in detail using SEM, XRD, FTIR, BET, PL, and VSM techniques. In this study, scavenger results showed that OH and O2− are both responsible for the AMX degradation. This study also showed that the energy consumed by visible light and UV light during 10–60 min was equal to 44.3 kWh/m3 to 18.5 and 10 to 20.6 kWh/m3, respectively. The reaction rate constant for the photocatalytic process with Fe3O4 and SiO2 nanoparticles, Fe3O4-SiO2-EN, and FSEZAL nanocomposite was 0.0045, 0.0059, 0.0084, and 0.116 1/min, respectively. Also, the half-life constant for nanocomposite was equal to 5.97 min. Ecotoxicity tests were performed using Daphnia magna, and the findings showed a significant reduction in the toxicity of AMX solution. In this study, three types of light were used, and the complete removal of AMX with UV and visible light required 40 min and 60 min, respectively. Also, using sunlight, 87.1 % of AMX was removed within one hour. The reaction rate constants for photocatalytic reactions with UV, visible, and solar lights were 0.116, 0.103, and 0.033 1/min, respectively. Biodegradability and mineralization tests also confirmed the efficacy of the photocatalytic system with synthesized nanocomposite. Therefore, the FSEZAL photocatalysts exhibit promising potential for use in water treatment, particularly in the mitigation of toxicity associated with antibiotic waste.
{"title":"Facile synthesis of Fe3O4-SiO2-EN@Zn-Al layered double hydroxide nanocomposites for degradation of amoxicillin under solar, visible and UV lights","authors":"Huu-Tap Van , Mikhail Ivanov , Razzagh Rahimpoor , Nezamaddin Mengelizadeh , Marwah Mohammed hareeja , Neeti Misra , Saad Hayif Jasim Ali , Davoud Balarak","doi":"10.1016/j.jphotochem.2025.116278","DOIUrl":"10.1016/j.jphotochem.2025.116278","url":null,"abstract":"<div><div>Antibiotics, categorized as emerging pollutants, present environmental challenges owing to their harmful and mutation-inducing properties, which hinder their removal. This study seeks to produce Fe<sub>3</sub>O<sub>4</sub>-SiO<sub>2</sub>-EN@Zn-Al layered double hydroxide (FSEZAL) nanocomposites for effectively degrading amoxicillin (AMX) through photocatalysis. The target nanocomposite was prepared using a sol–gel method and subsequently characterized in detail using SEM, XRD, FTIR, BET, PL, and VSM techniques. In this study, scavenger results showed that OH<sup><img></sup> and O<sub>2</sub><sup><img>−</sup> are both responsible for the AMX degradation. This study also showed that the energy consumed by visible light and UV light during 10–60 min was equal to 44.3 kWh/m<sup>3</sup> to 18.5 and 10 to 20.6 kWh/m<sup>3</sup>, respectively. The reaction rate constant for the photocatalytic process with Fe<sub>3</sub>O<sub>4</sub> and SiO<sub>2</sub> nanoparticles, Fe<sub>3</sub>O<sub>4</sub>-SiO<sub>2</sub>-EN, and FSEZAL nanocomposite was 0.0045, 0.0059, 0.0084, and 0.116 1/min, respectively. Also, the half-life constant for nanocomposite was equal to 5.97 min. Ecotoxicity tests were performed using <em>Daphnia magna</em>, and the findings showed a significant reduction in the toxicity of AMX solution. In this study, three types of light were used, and the complete removal of AMX with UV and visible light required 40 min and 60 min, respectively. Also, using sunlight, 87.1 % of AMX was removed within one hour. The reaction rate constants for photocatalytic reactions with UV, visible, and solar lights were 0.116, 0.103, and 0.033 1/min, respectively. Biodegradability and mineralization tests also confirmed the efficacy of the photocatalytic system with synthesized nanocomposite. Therefore, the FSEZAL photocatalysts exhibit promising potential for use in water treatment, particularly in the mitigation of toxicity associated with antibiotic waste.</div></div>","PeriodicalId":16782,"journal":{"name":"Journal of Photochemistry and Photobiology A-chemistry","volume":"462 ","pages":"Article 116278"},"PeriodicalIF":4.1,"publicationDate":"2025-01-16","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143166598","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 : 2025-01-16DOI: 10.1016/j.jphotochem.2025.116276
Qiujuan Ma , Junhong Xu , Shuzhen Liu , Guojiang Mao , Shuqi Hou , Yijie Ma , Yujie Lian
Cysteine is an essential thiol-containing amino acid in biological systems and is involved in several physiological processes in the human body. The Golgi apparatus is the main site of protein processing, and the normal concentration of cysteine is an important factor to maintain the homeostasis in Golgi apparatus. Once the Golgi apparatus homeostasis is disrupted, it will lead to the Golgi apparatus dysfunction, which will lead to a series of diseases. Herein a new Golgi-localized fluorescent probe was constructed for measuring cysteine. The developed probe was assembled by utilizing a 1,8-naphthalimide derivative as the fluorescent component, appending a phenylsulfonamide group to target the Golgi apparatus, and incorporating an acrylate recognition unit to interact with and detect cysteine. Within the concentration range of 2.0 × 10−7–1.0 × 10−5 mol·L−1, a favorable linear correlation was observed between the fluorescence intensity of the probe at 550 nm and the cysteine concentration. Furthermore, the detection limit was determined to be 1.56 × 10−8 mol·L−1. The proposed probe exhibited superior selectivity, swift response time, and wide pH operational scope. In addition, the proposed probe was almost non-cytotoxic and was able to localize to the Golgi apparatus and detect endogenous and exogenous cysteine in A549 cells.
{"title":"A Golgi-localized fluorescence probe for measuring cysteine based on a naphthalimide derivative","authors":"Qiujuan Ma , Junhong Xu , Shuzhen Liu , Guojiang Mao , Shuqi Hou , Yijie Ma , Yujie Lian","doi":"10.1016/j.jphotochem.2025.116276","DOIUrl":"10.1016/j.jphotochem.2025.116276","url":null,"abstract":"<div><div>Cysteine is an essential thiol-containing amino acid in biological systems and is involved in several physiological processes in the human body. The Golgi apparatus is the main site of protein processing, and the normal concentration of cysteine is an important factor to maintain the homeostasis in Golgi apparatus. Once the Golgi apparatus homeostasis is disrupted, it will lead to the Golgi apparatus dysfunction, which will lead to a series of diseases. Herein a new Golgi-localized fluorescent probe was constructed for measuring cysteine. The developed probe was assembled by utilizing a 1,8-naphthalimide derivative as the fluorescent component, appending a phenylsulfonamide group to target the Golgi apparatus, and incorporating an acrylate recognition unit to interact with and detect cysteine. Within the concentration range of 2.0 × 10<sup>−7</sup>–1.0 × 10<sup>−5</sup> mol·L<sup>−1</sup>, a favorable linear correlation was observed between the fluorescence intensity of the probe at 550 nm and the cysteine concentration. Furthermore, the detection limit was determined to be 1.56 × 10<sup>−8</sup> mol·L<sup>−1</sup>. The proposed probe exhibited superior selectivity, swift response time, and wide pH operational scope. In addition, the proposed probe was almost non-cytotoxic and was able to localize to the Golgi apparatus and detect endogenous and exogenous cysteine in A549 cells.</div></div>","PeriodicalId":16782,"journal":{"name":"Journal of Photochemistry and Photobiology A-chemistry","volume":"462 ","pages":"Article 116276"},"PeriodicalIF":4.1,"publicationDate":"2025-01-16","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143167324","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 : 2025-01-15DOI: 10.1016/j.jphotochem.2025.116275
Zhenbang Xie , Chao Wang , Fuqi Wu , Ruiyuan Hu , Jie Zhang , Hongfei Du , Shouchao Zhang , Yongzhu Zhou
Modification of semiconductor-based photocatalysts with nanoclusters is regarded as a key advancement in photocatalytic hydrogen production. This study successfully prepared g-C3N4-based photocatalysts loaded with small-sized silver nanoclusters (Ag NCs/CN) using formamide as a solvent and reducing agent. Through systematic characterization and density functional theory (DFT) calculations, we demonstrate that silver nanoclusters serve as charge-transfer channels, enhancing the generation and separation of photogenerated carriers and optimizing the surface properties of g-C3N4 to greatly improve its photocatalytic activity. The photocatalytic hydrogen production rate of Ag NCs/CN reaches 1439.77 μmol·g−1·h−1 significantly surpassing that of g-C3N4. Moreover, Ag NCs/CN maintains high photocatalytic activity even after 30 h of continuous cycling. This work reveals the role of silver nanocluster modification in photogenerated electron separation and transport, providing new insights into the application of metal nanocluster composite catalysts.
{"title":"Loading silver nanoclusters onto g-C3N4 by formamide-assisted in-situ strategy to achieve efficient photocatalytic water splitting for hydrogen production","authors":"Zhenbang Xie , Chao Wang , Fuqi Wu , Ruiyuan Hu , Jie Zhang , Hongfei Du , Shouchao Zhang , Yongzhu Zhou","doi":"10.1016/j.jphotochem.2025.116275","DOIUrl":"10.1016/j.jphotochem.2025.116275","url":null,"abstract":"<div><div>Modification of semiconductor-based photocatalysts with nanoclusters is regarded as a key advancement in photocatalytic hydrogen production. This study successfully prepared g-C<sub>3</sub>N<sub>4</sub>-based photocatalysts loaded with small-sized silver nanoclusters (Ag NCs/CN) using formamide as a solvent and reducing agent. Through systematic characterization and density functional theory (DFT) calculations, we demonstrate that silver nanoclusters serve as charge-transfer channels, enhancing the generation and separation of photogenerated carriers and optimizing the surface properties of g-C<sub>3</sub>N<sub>4</sub> to greatly improve its photocatalytic activity. The photocatalytic hydrogen production rate of Ag NCs/CN reaches 1439.77 μmol·g<sup>−1</sup>·h<sup>−1</sup> significantly surpassing that of g-C<sub>3</sub>N<sub>4</sub>. Moreover, Ag NCs/CN maintains high photocatalytic activity even after 30 h of continuous cycling. This work reveals the role of silver nanocluster modification in photogenerated electron separation and transport, providing new insights into the application of metal nanocluster composite catalysts.</div></div>","PeriodicalId":16782,"journal":{"name":"Journal of Photochemistry and Photobiology A-chemistry","volume":"462 ","pages":"Article 116275"},"PeriodicalIF":4.1,"publicationDate":"2025-01-15","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143166594","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}
In this study, we investigated the adsorption and photophysical behaviors of meso-tetra(N-methyl-4-pyridyl)porphyrin (m-TMPyP) and meso-tetra(N-butyl-4-pyridyl)porphyrin (m-TBPyP) molecules on the surface of a synthetic silicate nanosheet. The λmax of m-TMPyP and m-TBPyP on the synthetic clay nanosheet were 429 and 440 nm under the non-aggregation state, respectively. The spectroscopic analysis revealed that a flattening of the molecular structure of m-TBPyP upon adsorption is stronger than m-TMPyP. Compared to m-TMPyP, the fluorescence quenching of m-TBPyP was suppressed to some extent, especially at adsorption densities below 30 % vs. cation exchange capacity of the nanosheet, due to the steric effects of its longer alkyl chain reducing molecular contact. However, m-TBPyP suffered a 10 % self-fluorescence quenching rate at saturation adsorption as same as the case of m-TMPyP. Interestingly, mixing two dyes in a 1:1 ratio suppressed self-fluorescence quenching even at saturation adsorption. This indicates that the neighboring of same porphyrin, leading to the quenching, was suppressed in the mixture system. Thus, the arrangement of m-TMPyP and m-TBPyP is uniform and prevents molecular collisions between same species. The uniform arrangement and no-fluorescence quenching of m-TMPyP (energy donor) and m-TBPyP (acceptor) on clay nanosheet could facilitate efficient photochemical energy transfer between them. As a result, by suppressing self-fluorescence quenching, the efficient energy transfer between m-TMPyP and m-TBPyP was observed. It was determined that the energy transfer efficiency (ηET) is 85 %, with a self-fluorescence quenching efficiency (ϕq) of 0 %. These findings are beneficial to design more efficient systems for artificial light-harvesting systems by optimizing molecular interactions on clay surfaces.
{"title":"Elucidation of the dynamic quenching behavior of pyridinium porphyrin derivatives on clay nanosheet","authors":"Yiming Li , Yugo Hirade , Tamao Ishida , Tetsuya Shimada , Shinsuke Takagi","doi":"10.1016/j.jphotochem.2025.116266","DOIUrl":"10.1016/j.jphotochem.2025.116266","url":null,"abstract":"<div><div>In this study, we investigated the adsorption and photophysical behaviors of <em>meso</em>-tetra(<em>N</em>-methyl-4-pyridyl)porphyrin (<em>m</em>-TMPyP) and <em>meso</em>-tetra(<em>N</em>-butyl-4-pyridyl)porphyrin (<em>m</em>-TBPyP) molecules on the surface of a synthetic silicate nanosheet. The <em>λ</em><sub>max</sub> of <em>m</em>-TMPyP and <em>m</em>-TBPyP on the synthetic clay nanosheet were 429 and 440 nm under the non-aggregation state, respectively. The spectroscopic analysis revealed that a flattening of the molecular structure of <em>m</em>-TBPyP upon adsorption is stronger than <em>m</em>-TMPyP. Compared to <em>m</em>-TMPyP, the fluorescence quenching of <em>m</em>-TBPyP was suppressed to some extent, especially at adsorption densities below 30 % <em>vs</em>. cation exchange capacity of the nanosheet, due to the steric effects of its longer alkyl chain reducing molecular contact. However, <em>m</em>-TBPyP suffered a 10 % self-fluorescence quenching rate at saturation adsorption as same as the case of <em>m</em>-TMPyP. Interestingly, mixing two dyes in a 1:1 ratio suppressed self-fluorescence quenching even at saturation adsorption. This indicates that the neighboring of same porphyrin, leading to the quenching, was suppressed in the mixture system. Thus, the arrangement of <em>m</em>-TMPyP and <em>m</em>-TBPyP is uniform and prevents molecular collisions between same species. The uniform arrangement and no-fluorescence quenching of <em>m</em>-TMPyP (energy donor) and <em>m</em>-TBPyP (acceptor) on clay nanosheet could facilitate efficient photochemical energy transfer between them. As a result, by suppressing self-fluorescence quenching, the efficient energy transfer between <em>m</em>-TMPyP and <em>m</em>-TBPyP was observed. It was determined that the energy transfer efficiency (<em>η</em><sub>ET</sub>) is 85 %, with a self-fluorescence quenching efficiency (<em>ϕ</em><sub>q</sub>) of 0 %. These findings are beneficial to design more efficient systems for artificial light-harvesting systems by optimizing molecular interactions on clay surfaces.</div></div>","PeriodicalId":16782,"journal":{"name":"Journal of Photochemistry and Photobiology A-chemistry","volume":"463 ","pages":"Article 116266"},"PeriodicalIF":4.1,"publicationDate":"2025-01-13","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143142924","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 : 2025-01-13DOI: 10.1016/j.jphotochem.2025.116271
Barbora Walderova , Adela Paulusova , Lenka Belhacova , Libor Brabec , Petra Cihlarova , Jiri Rathousky , Martin Kuchar
Heterogeneous TiO2 photocatalysis is an efficient process to be added after standard wastewater treatment to ensure the complete removal of endocrine disruptors, toxic to humans and animals. To address the challenges of industrial-scale operation, an airbrush spraying immobilization method was developed, which provided layers with high stability, reusability, and repeatability. On these layers, an over 50 % conversion after 5 h was achieved for two structurally differing endocrine disrupting chemicals under standardized conditions. The experimental conditions were further optimized; for TiO2 areal density above 0.8 mg cm−2, the photocatalytic activity was independent on the used thickness range and proportional to the layer area. The optimization enabled 70 % conversion of 17α-ethinylestradiol after 5 h even when greywater was used as a matrix, with theoretical complete conversion within 24 h. Based on concentrations of identified transformation products of 17α-ethinylestradiol under different experimental conditions, an alternative to the dominant reaction mechanism is proposed.
{"title":"Airbrush-sprayed TiO2 layers for the photocatalytic degradation of endocrine disruptors: Performance, stability and applicability","authors":"Barbora Walderova , Adela Paulusova , Lenka Belhacova , Libor Brabec , Petra Cihlarova , Jiri Rathousky , Martin Kuchar","doi":"10.1016/j.jphotochem.2025.116271","DOIUrl":"10.1016/j.jphotochem.2025.116271","url":null,"abstract":"<div><div>Heterogeneous TiO<sub>2</sub> photocatalysis is an efficient process to be added after standard wastewater treatment to ensure the complete removal of endocrine disruptors, toxic to humans and animals. To address the challenges of industrial-scale operation, an airbrush spraying immobilization method was developed, which provided layers with high stability, reusability, and repeatability. On these layers, an over 50 % conversion after 5 h was achieved for two structurally differing endocrine disrupting chemicals under standardized conditions. The experimental conditions were further optimized; for TiO<sub>2</sub> areal density above 0.8 mg cm<sup>−2</sup>, the photocatalytic activity was independent on the used thickness range and proportional to the layer area. The optimization enabled 70 % conversion of 17<em>α</em>-ethinylestradiol after 5 h even when greywater was used as a matrix, with theoretical complete conversion within 24 h. Based on concentrations of identified transformation products of 17<em>α</em>-ethinylestradiol under different experimental conditions, an alternative to the dominant reaction mechanism is proposed.</div></div>","PeriodicalId":16782,"journal":{"name":"Journal of Photochemistry and Photobiology A-chemistry","volume":"463 ","pages":"Article 116271"},"PeriodicalIF":4.1,"publicationDate":"2025-01-13","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143142923","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}
Naturally occurring chlorophyll-a was chemically modified to give homo-dimers of methyl pyropheophorbide-a linked with or without a vinylidene group at the 3-vinyl terminal. Access to the hexatriene- and butadiene-linked dyads was achieved through the olefin metathesis of the vinyl group in the peripheral substituent on the chlorin π-system and successive dehydration in the resulting spacer between the chlorin cores. The conjugation of the two chlorin moieties via the oligoene linkers moved the visible absorption and fluorescence emission maxima in dichloromethane to longer wavelengths. Especially, the red-shifted and broadened Soret absorption bands reached to a green-light region around 500 nm, and the Qy absorption maxima were located at a far-red region around 700 nm. The dimerization enhanced the fluorescence emission efficiency with quantum yields of approximately 30%. The intramolecular through-bond interaction between the two chlorin π-systems in the dimers was revealed by comparison with the optical properties of their corresponding monomeric counterparts.
{"title":"Visible absorption and fluorescence emission of synthetic dimers of chlorophyll-a derivatives linked with a π-conjugated oligoene spacer at the peripheral 3-position","authors":"Hinako Sasakura, Yusuke Kinoshita, Hitoshi Tamiaki","doi":"10.1016/j.jphotochem.2025.116270","DOIUrl":"10.1016/j.jphotochem.2025.116270","url":null,"abstract":"<div><div>Naturally occurring chlorophyll-<em>a</em> was chemically modified to give homo-dimers of methyl pyropheophorbide-<em>a</em> linked with or without a vinylidene group at the 3-vinyl terminal. Access to the hexatriene- and butadiene-linked dyads was achieved through the olefin metathesis of the vinyl group in the peripheral substituent on the chlorin π-system and successive dehydration in the resulting spacer between the chlorin cores. The conjugation of the two chlorin moieties via the oligoene linkers moved the visible absorption and fluorescence emission maxima in dichloromethane to longer wavelengths. Especially, the red-shifted and broadened Soret absorption bands reached to a green-light region around 500 nm, and the Qy absorption maxima were located at a far-red region around 700 nm. The dimerization enhanced the fluorescence emission efficiency with quantum yields of approximately 30%. The intramolecular through-bond interaction between the two chlorin π-systems in the dimers was revealed by comparison with the optical properties of their corresponding monomeric counterparts.</div></div>","PeriodicalId":16782,"journal":{"name":"Journal of Photochemistry and Photobiology A-chemistry","volume":"462 ","pages":"Article 116270"},"PeriodicalIF":4.1,"publicationDate":"2025-01-11","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143166595","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 : 2025-01-10DOI: 10.1016/j.jphotochem.2025.116268
Navneet Kumar , Pawan Kumar Sada , Amit Kumar Kundan , Amit Bar , Amanpreet Kaur Jassal , Surya Prakash Rai , Vipendra Kumar Singh , Neha Garg , Alok Kumar Singh , Ankit Kumar Singh , Sumit Kumar , Laxman Singh , Abhishek Rai
A new fluorescein hydrazone (FA1) has been synthesized employing fluorescein hydrazide and 3,5-diiodosalicylaldehyde and its complete physiochemical characterization have been carried out. A single crystal XRD studies of FA1 has been performed. Among the tested metal ions FA1 significantly detects Cu2+ and Zn2+ in EtOH/H2O (8:2, v/v)). There is an emergence of a new absorbance peak at λmax 431 nm with Cu2+ ions. A “turn-on” behavior in fluorescence at λem510 nm was observed with Zn2+ ions owing to chelation enhanced fluorescence. This act of spectrophotometric changes and naked eye color variation from colorless to yellow is because of coordination with the metal ions rather than most common opening of spirolactum ring. FA1-Cu2+ and FA1-Zn2+ensembles display reversible behavior with EDTA2− ions. In a study on latent fingerprint detection using powder compounds, it was found that FA1 and FA1–Zn2+ showed excellent adherence to finger ridges and produced clear features without any background stains. The Hirshfeld surface and fingerprint analysis of FA1 offer a detailed examination of pairwise interactions between atoms. Additionally, topological analysis of FA1 has been conducted using NCI, AIM, ELF, and LOL methodologies. Alamar assay of FA1 on HEK-293 cell lines exhibited biocompatibility with minimal cytotoxicity. Hence, they were effectively applied for live cell imaging for intracellular sensing of Cu2+ and Zn2+ in HEK-293 cells.
{"title":"Exploring the recognition behavior of a fluorescein-based probe towards the significant detection of Cu2+ and Zn2+ ions: Experimental and computational studies","authors":"Navneet Kumar , Pawan Kumar Sada , Amit Kumar Kundan , Amit Bar , Amanpreet Kaur Jassal , Surya Prakash Rai , Vipendra Kumar Singh , Neha Garg , Alok Kumar Singh , Ankit Kumar Singh , Sumit Kumar , Laxman Singh , Abhishek Rai","doi":"10.1016/j.jphotochem.2025.116268","DOIUrl":"10.1016/j.jphotochem.2025.116268","url":null,"abstract":"<div><div>A new fluorescein hydrazone <strong>(FA1)</strong> has been synthesized employing fluorescein hydrazide and 3,5-diiodosalicylaldehyde and its complete physiochemical characterization have been carried out. A single crystal XRD studies of <strong>FA1</strong> has been performed. Among the tested metal ions <strong>FA1</strong> significantly detects Cu<sup>2+</sup> and Zn<sup>2+</sup> in EtOH/H<sub>2</sub>O (8:2, v/v)). There is an emergence of a new absorbance peak at λ<sub>max</sub> 431 nm with Cu<sup>2+</sup> ions. A “turn-on” behavior in fluorescence at λ<sub>em</sub>510 nm was observed with Zn<sup>2+</sup> ions owing to chelation enhanced fluorescence. This act of spectrophotometric changes and naked eye color variation from colorless to yellow is because of coordination with the metal ions rather than most common opening of spirolactum ring. <strong>FA1-</strong>Cu<sup>2+</sup> and <strong>FA1-</strong>Zn<sup>2+</sup>ensembles display reversible behavior with EDTA<sup>2−</sup> ions. In a study on latent fingerprint detection using powder compounds, it was found that <strong>FA1</strong> and <strong>FA1–</strong>Zn<sup>2+</sup> showed excellent adherence to finger ridges and produced clear features without any background stains. The Hirshfeld surface and fingerprint analysis of <strong>FA1</strong> offer a detailed examination of pairwise interactions between atoms. Additionally, topological analysis of <strong>FA1</strong> has been conducted using NCI, AIM, ELF, and LOL methodologies. Alamar assay of <strong>FA1</strong> on HEK-293 cell lines exhibited biocompatibility with minimal cytotoxicity. Hence, they were effectively applied for live cell imaging for intracellular sensing of Cu<sup>2+</sup> and Zn<sup>2+</sup> in HEK-293 cells.</div></div>","PeriodicalId":16782,"journal":{"name":"Journal of Photochemistry and Photobiology A-chemistry","volume":"462 ","pages":"Article 116268"},"PeriodicalIF":4.1,"publicationDate":"2025-01-10","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143166283","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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