Journal of Photochemistry and Photobiology A-chemistry最新文献

Optimizing photodynamic therapy: Talaporfin-encapsulated silica nanoparticles for red blood cell disruption in cancer treatment

IF 4.1 3区化学 Q2 CHEMISTRY, PHYSICAL

Journal of Photochemistry and Photobiology A-chemistry

Pub Date : 2025-02-24 DOI: 10.1016/j.jphotochem.2025.116356

Ghaseb N. Makhadmeh , Tariq AlZoubi , Samer H. Zyoud , Mahmoud Al-Gharram , M.H.A. Mhareb , Osama Abu Noqta , Abdulsalam Abuelsamen

Photodynamic therapy (PDT) is a highly effective cancer treatment that combines a photosensitizer (PS), and light for targeted cancer cell destruction in present of oxygen. However, the delivery of photosensitizers remains a challenge due to degradation risks and systemic toxicity. This study investigates the encapsulation of Talaporfin, a second-generation chlorin-based photosensitizer, within silica nanoparticles (SiNPs) to enhance PDT efficacy and safety. The research focuses on using red blood cells (RBCs) as a model system, highlighting their critical role in the tumor microenvironment. By targeting and destroying RBCs in proximity to tumors, PDT can disrupt the oxygen supply, indirectly leading to cancer cell death. Talaporfin-encapsulated SiNPs (T-SiNPs) were synthesized via a microemulsion method and characterized for size, morphology, and stability. The photodynamic effects of encapsulated versus naked Talaporfin were evaluated under varying concentrations and light exposure times. Results revealed that T-SiNPs achieved higher therapeutic efficacy, requiring lower concentrations and shorter exposure durations. This enhanced performance is attributed to improved light absorption and ROS production due to reduced aggregation of Talaporfin within SiNPs. Additionally, mathematical equations were developed to correlate the concentrations of encapsulated and naked Talaporfin with the 50% mortality rate (t₅₀) of RBCs. These equations provide a predictive framework for optimizing PDT protocols, enabling the determination of optimal drug concentrations and exposure times without extensive experimental trials. This study underscores the potential of silica nanoparticles as efficient carriers for photosensitizers, enhancing PDT outcomes by targeting both RBCs and cancer cells. The findings pave the way for innovative cancer therapies that leverage nanotechnology to achieve precise, effective, and safer treatments. Future applications of this approach may extend to broader therapeutic areas, further revolutionizing modern medicine.

{"title":"Optimizing photodynamic therapy: Talaporfin-encapsulated silica nanoparticles for red blood cell disruption in cancer treatment","authors":"Ghaseb N. Makhadmeh , Tariq AlZoubi , Samer H. Zyoud , Mahmoud Al-Gharram , M.H.A. Mhareb , Osama Abu Noqta , Abdulsalam Abuelsamen","doi":"10.1016/j.jphotochem.2025.116356","DOIUrl":"10.1016/j.jphotochem.2025.116356","url":null,"abstract":"<div><div>Photodynamic therapy (PDT) is a highly effective cancer treatment that combines a photosensitizer (PS), and light for targeted cancer cell destruction in present of oxygen. However, the delivery of photosensitizers remains a challenge due to degradation risks and systemic toxicity. This study investigates the encapsulation of Talaporfin, a second-generation chlorin-based photosensitizer, within silica nanoparticles (SiNPs) to enhance PDT efficacy and safety. The research focuses on using red blood cells (RBCs) as a model system, highlighting their critical role in the tumor microenvironment. By targeting and destroying RBCs in proximity to tumors, PDT can disrupt the oxygen supply, indirectly leading to cancer cell death. Talaporfin-encapsulated SiNPs (T-SiNPs) were synthesized via a microemulsion method and characterized for size, morphology, and stability. The photodynamic effects of encapsulated versus naked Talaporfin were evaluated under varying concentrations and light exposure times. Results revealed that T-SiNPs achieved higher therapeutic efficacy, requiring lower concentrations and shorter exposure durations. This enhanced performance is attributed to improved light absorption and ROS production due to reduced aggregation of Talaporfin within SiNPs. Additionally, mathematical equations were developed to correlate the concentrations of encapsulated and naked Talaporfin with the 50% mortality rate (t<sub>50</sub>) of RBCs. These equations provide a predictive framework for optimizing PDT protocols, enabling the determination of optimal drug concentrations and exposure times without extensive experimental trials. This study underscores the potential of silica nanoparticles as efficient carriers for photosensitizers, enhancing PDT outcomes by targeting both RBCs and cancer cells. The findings pave the way for innovative cancer therapies that leverage nanotechnology to achieve precise, effective, and safer treatments. Future applications of this approach may extend to broader therapeutic areas, further revolutionizing modern medicine.</div></div>","PeriodicalId":16782,"journal":{"name":"Journal of Photochemistry and Photobiology A-chemistry","volume":"465 ","pages":"Article 116356"},"PeriodicalIF":4.1,"publicationDate":"2025-02-24","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143488348","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}

引用次数: 0

Development and validation of a green spectrofluorimetric method for brivaracetam determination using N-doped graphene quantum dots: Mechanistic insights and bioanalytical applications

IF 4.1 3区化学 Q2 CHEMISTRY, PHYSICAL

Journal of Photochemistry and Photobiology A-chemistry

Pub Date : 2025-02-23 DOI: 10.1016/j.jphotochem.2025.116357

Reem M. Alnemari , Maram H. Abduljabbar , Yusuf S. Althobaiti , Sameer Alshehri , Farooq M. Almutairi , Humood Al Shmrany , Eid Semer Alatwi , Ahmed Serag , Atiah H. Almalki

Brivaracetam is an important antiepileptic drug, and its sensitive and selective determination in biological matrices is crucial for therapeutic drug monitoring and pharmacokinetic studies. However, the currently available analytical methods suffer from limitations such as low sensitivity, high environmental impact, and complex sample preparation. In this work, a highly sensitive and selective spectrofluorimetric method was developed for the determination of brivaracetam in human plasma and pharmaceutical formulations. The method is based on the interaction between brivaracetam and N-doped graphene quantum dots (GQDs) leading to fluorescence quenching. The quenching mechanism was investigated using density functional theory calculations, Stern-Volmer analysis and thermodynamic studies. A static quenching process was observed indicating complex formation between the analyte and nanomaterial. Different factors affecting the quenching efficiency were carefully optimized such as pH, GQDs concentration, and incubation time. The proposed method was validated according to the ICH M10 guidelines and showed excellent linearity in the concentration range of 0.1–2.5 μg/mL with a limit of detection of 0.033 μg/mL. Furthermore, the method displayed good precision and accuracy, and selectivity in the presence of common plasma/formulation excipients. Hence, the developed method was successfully applied for the determination of brivaracetam in pharmaceutical formulations as well as pharmacokinetic monitoring in human plasma samples. The “greenness”, “blueness” and “whiteness” of the proposed method was also evaluated using the AGREE, BAGI and RGB12 metrics, respectively, confirming its eco-friendly, high practicability and sustainable nature transcending the reported conventional analytical techniques, posing the developed method as a promising analytical tool for brivaracetam determination.

{"title":"Development and validation of a green spectrofluorimetric method for brivaracetam determination using N-doped graphene quantum dots: Mechanistic insights and bioanalytical applications","authors":"Reem M. Alnemari , Maram H. Abduljabbar , Yusuf S. Althobaiti , Sameer Alshehri , Farooq M. Almutairi , Humood Al Shmrany , Eid Semer Alatwi , Ahmed Serag , Atiah H. Almalki","doi":"10.1016/j.jphotochem.2025.116357","DOIUrl":"10.1016/j.jphotochem.2025.116357","url":null,"abstract":"<div><div>Brivaracetam is an important antiepileptic drug, and its sensitive and selective determination in biological matrices is crucial for therapeutic drug monitoring and pharmacokinetic studies. However, the currently available analytical methods suffer from limitations such as low sensitivity, high environmental impact, and complex sample preparation. In this work, a highly sensitive and selective spectrofluorimetric method was developed for the determination of brivaracetam in human plasma and pharmaceutical formulations. The method is based on the interaction between brivaracetam and N-doped graphene quantum dots (GQDs) leading to fluorescence quenching. The quenching mechanism was investigated using density functional theory calculations, Stern-Volmer analysis and thermodynamic studies. A static quenching process was observed indicating complex formation between the analyte and nanomaterial. Different factors affecting the quenching efficiency were carefully optimized such as pH, GQDs concentration, and incubation time. The proposed method was validated according to the ICH M10 guidelines and showed excellent linearity in the concentration range of 0.1–2.5 μg/mL with a limit of detection of 0.033 μg/mL. Furthermore, the method displayed good precision and accuracy, and selectivity in the presence of common plasma/formulation excipients. Hence, the developed method was successfully applied for the determination of brivaracetam in pharmaceutical formulations as well as pharmacokinetic monitoring in human plasma samples. The “greenness”, “blueness” and “whiteness” of the proposed method was also evaluated using the AGREE, BAGI and RGB12 metrics, respectively, confirming its eco-friendly, high practicability and sustainable nature transcending the reported conventional analytical techniques, posing the developed method as a promising analytical tool for brivaracetam determination.</div></div>","PeriodicalId":16782,"journal":{"name":"Journal of Photochemistry and Photobiology A-chemistry","volume":"465 ","pages":"Article 116357"},"PeriodicalIF":4.1,"publicationDate":"2025-02-23","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143487741","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}

引用次数: 0

Dynamic behavior of the fluorescence features of Eosin Y in PVA-Borax hydrogel

IF 4.1 3区化学 Q2 CHEMISTRY, PHYSICAL

Journal of Photochemistry and Photobiology A-chemistry

Pub Date : 2025-02-22 DOI: 10.1016/j.jphotochem.2025.116358

Soghra Mohammadzadeh, Ali Bavali, Ali Rahmatpanahi, Farzad Mokhtari

In most biophotonics applications of dye-gel blends, the gel is illuminated by a light source (usually a laser or LED) for a considerable period of time. Therefore, it is crucial to examine the temporal behavior of the corresponding luminescence features. In the present report, a photosensitive hydrogel was synthesized using Eosin Yellow (EY) as the dye, Polyvinyl Alcohol as the polymer and Borax as the cross-linking agent (EY-PVA-Borax hydrogel). Dynamic behavior of the corresponding fluorescence emission due to excitation of by a diode laser at λ = 445 nm (which is the isosbestic point of the EY absorption spectrum during the photodegradation process) were studied parametrically and evaluated using difference spectra analysis (DSA). In general, the wavelength at the fluorescence peak underwent hypsochromic shift with irradiation time, while the intensity increased in the first 9.0 s and then decreased gradually. Hydrogen bonding between the hydroxyl group of PVA and the carboxyl group of EY, aggregation of the EY molecules and debromination of the EY monomers under light irradiation were considered to explain the dynamic behavior of the fluorescence emission from the gel. Considering the use of hydrogels as photo-convertors, the influence of gel layer thickness on the fluorescence spectrum was examined. The results obtained are of particular importance for the design of fluorescence-based biosensors and also in the field of fluorescence biomodulation.

{"title":"Dynamic behavior of the fluorescence features of Eosin Y in PVA-Borax hydrogel","authors":"Soghra Mohammadzadeh, Ali Bavali, Ali Rahmatpanahi, Farzad Mokhtari","doi":"10.1016/j.jphotochem.2025.116358","DOIUrl":"10.1016/j.jphotochem.2025.116358","url":null,"abstract":"<div><div>In most biophotonics applications of dye-gel blends, the gel is illuminated by a light source (usually a laser or LED) for a considerable period of time. Therefore, it is crucial to examine the temporal behavior of the corresponding luminescence features. In the present report, a photosensitive hydrogel was synthesized using Eosin Yellow (EY) as the dye, Polyvinyl Alcohol as the polymer and Borax as the cross-linking agent (EY-PVA-Borax hydrogel). Dynamic behavior of the corresponding fluorescence emission due to excitation of by a diode laser at λ = 445 nm (which is the isosbestic point of the EY absorption spectrum during the photodegradation process) were studied parametrically and evaluated using difference spectra analysis (DSA). In general, the wavelength at the fluorescence peak underwent hypsochromic shift with irradiation time, while the intensity increased in the first 9.0 s and then decreased gradually. Hydrogen bonding between the hydroxyl group of PVA and the carboxyl group of EY, aggregation of the EY molecules and debromination of the EY monomers under light irradiation were considered to explain the dynamic behavior of the fluorescence emission from the gel. Considering the use of hydrogels as photo-convertors, the influence of gel layer thickness on the fluorescence spectrum was examined. The results obtained are of particular importance for the design of fluorescence-based biosensors and also in the field of fluorescence biomodulation.</div></div>","PeriodicalId":16782,"journal":{"name":"Journal of Photochemistry and Photobiology A-chemistry","volume":"465 ","pages":"Article 116358"},"PeriodicalIF":4.1,"publicationDate":"2025-02-22","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143479407","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}

引用次数: 0

B, S, N co-doped carbon dots-based highly sensitive and rapid nanoprobe for monitoring of pepsin activity in human saliva and its cell imaging

IF 4.1 3区化学 Q2 CHEMISTRY, PHYSICAL

Journal of Photochemistry and Photobiology A-chemistry

Pub Date : 2025-02-21 DOI: 10.1016/j.jphotochem.2025.116349

Haitham Saad Al-mashriqi , Pascaline Sanga , Eskandar Qaed , Jia Chen , Xin Li , Yunyun Zhang , Hongdeng Qiu

Gastroesophageal reflux disease (GERD) is widespread, but screening is difficult due to its non-specific symptoms. Detecting pepsin in saliva is a non-invasive and specific diagnostic method, yet it requires enhancements in reaction time, selectivity, and sensitivity. In this study, a highly sensitive detection method has been developed for monitoring pepsin activity in human saliva based on boron, sulfur, and nitrogen co-doped carbon dots (BSN-CDs) for the first time. The manufactured BSN-CDs exhibit exceptional photoluminescent properties, high water solubility, and stability in varying salt concentrations and pH levels. The nanoprobe shows a fast response time and a wide detection range from 0 to 60 µg/mL for pepsin with a detection limit of 0.24 µg/mL, making it a valuable tool for clinical diagnostics. To our knowledge, this is the most responsive material for pepsin activity reported to date. The method’s viability was confirmed by accurately measuring pepsin in human saliva samples, achieving recovery rates between 96.0 % to 108.5 %. Moreover, the study investigates using these carbon dots for imaging HepG2 and SiHa cells, highlighting their broader biomedical potential. It concludes that BSN-CDs are promising nanomaterials for sensitive biomolecule detection and advanced imaging techniques.

{"title":"B, S, N co-doped carbon dots-based highly sensitive and rapid nanoprobe for monitoring of pepsin activity in human saliva and its cell imaging","authors":"Haitham Saad Al-mashriqi , Pascaline Sanga , Eskandar Qaed , Jia Chen , Xin Li , Yunyun Zhang , Hongdeng Qiu","doi":"10.1016/j.jphotochem.2025.116349","DOIUrl":"10.1016/j.jphotochem.2025.116349","url":null,"abstract":"<div><div>Gastroesophageal reflux disease (GERD) is widespread, but screening is difficult due to its non-specific symptoms. Detecting pepsin in saliva is a non-invasive and specific diagnostic method, yet it requires enhancements in reaction time, selectivity, and sensitivity. In this study, a highly sensitive detection method has been developed for monitoring pepsin activity in human saliva based on boron, sulfur, and nitrogen co-doped carbon dots (BSN-CDs) for the first time. The manufactured BSN-CDs exhibit exceptional photoluminescent properties, high water solubility, and stability in varying salt concentrations and pH levels. The nanoprobe shows a fast response time and a wide detection range from 0 to 60 µg/mL for pepsin with a detection limit of 0.24 µg/mL, making it a valuable tool for clinical diagnostics. To our knowledge, this is the most responsive material for pepsin activity reported to date. The method’s viability was confirmed by accurately measuring pepsin in human saliva samples, achieving recovery rates between 96.0 % to 108.5 %. Moreover, the study investigates using these carbon dots for imaging HepG2 and SiHa cells, highlighting their broader biomedical potential. It concludes that BSN-CDs are promising nanomaterials for sensitive biomolecule detection and advanced imaging techniques.</div></div>","PeriodicalId":16782,"journal":{"name":"Journal of Photochemistry and Photobiology A-chemistry","volume":"465 ","pages":"Article 116349"},"PeriodicalIF":4.1,"publicationDate":"2025-02-21","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143479406","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}

引用次数: 0

Insights into catalytic activity and mechanism of BiVO4 modified by different cerium forms in collaboration with C3N4

IF 4.1 3区化学 Q2 CHEMISTRY, PHYSICAL

Journal of Photochemistry and Photobiology A-chemistry

Pub Date : 2025-02-18 DOI: 10.1016/j.jphotochem.2025.116327

Yanjun Zhao , Qian Luo , Minyue Zhou , Shirui Lv , Yuning Ma , Xintong Liu

Environmental photocatalysis is an effective technology to deal with environmental pollution. In this study, bismuth vanadate (BiVO₄), one of the most common photocatalysts, was used as the substrate material. Different states cerium (Ce) with multiple electron layers were firstly introduced, afterwards C₃N₄ was hybridized. The existence forms of Ce in semiconductor matrix lattice under different conditions were investigated by X-ray diffraction (XRD), X-ray photoelectron spectroscopy (XPS), scanning electron microscopy (SEM) and other characterization methods. Furthermore, quenching experiments and electron paramagnetic resonance (EPR) techniques were used to discuss the changes in the production of reactive oxygen species (ROS) by different forms of Ce electron layers. This study systematically summarized the relationship and rule of Ce and ROS formation. It provides the research basis and theoretical basis for exploring the mechanism of photocatalytic reaction and dealing with environmental problems in practice.

环境光催化是解决环境污染问题的有效技术。本研究采用最常见的光催化剂之一钒酸铋（BiVO4）作为基底材料。首先引入了具有多个电子层的不同状态的铈（Ce），然后杂化了 C3N4。通过 X 射线衍射 (XRD)、X 射线光电子能谱 (XPS)、扫描电子显微镜 (SEM) 等表征方法研究了不同条件下 Ce 在半导体基体晶格中的存在形式。此外，还利用淬火实验和电子顺磁共振（EPR）技术探讨了不同形式的 Ce 电子层在产生活性氧（ROS）方面的变化。该研究系统地总结了 Ce 与 ROS 形成的关系和规律。为探索光催化反应机理和解决实际环境问题提供了研究基础和理论依据。

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引用次数: 0

Synthesis and applications of a fluorescent cyan 2-aryl benzimidazole for environmental sensing, luminescent ink, and coating technologies

IF 4.1 3区化学 Q2 CHEMISTRY, PHYSICAL

Journal of Photochemistry and Photobiology A-chemistry

Pub Date : 2025-02-18 DOI: 10.1016/j.jphotochem.2025.116346

Vismaya Joseph, Muhammed Arshad, Athira Ajayan, Abraham Joseph

An efficient luminescence sensor, specifically 2-([1,1′-biphenyl]-4-yl)-1H-benzo[d]imidazole (BBI), has been synthesized through a one-pot green synthesis methodology to detect picric acid (PA) via turn-off quench, demonstrating superior performance relative to numerous nitro aromatic compounds. The compound was characterized using various spectroscopic techniques, in addition to absorption and fluorescence emission studies, to ascertain the sensitivity and selectivity of the probe. The sensor exhibits a limit of detection (LOD) of approximately 1.22 × 10⁻⁷ M and a quenching constant of 1.67 × 10⁵ M⁻¹, as determined by fluorescence measurements. The underlying mechanism of the sensing process was elucidated through both experimental and theoretical analyses. To augment its practical applicability, the sensor was formulated into luminescent ink and gel-based systems for various applications. Additionally, real-world detection capabilities were established by developing solid-contact mode paper strips and glass plate-based detection methods, facilitating the analysis of real-life samples such as soil and water.

{"title":"Synthesis and applications of a fluorescent cyan 2-aryl benzimidazole for environmental sensing, luminescent ink, and coating technologies","authors":"Vismaya Joseph, Muhammed Arshad, Athira Ajayan, Abraham Joseph","doi":"10.1016/j.jphotochem.2025.116346","DOIUrl":"10.1016/j.jphotochem.2025.116346","url":null,"abstract":"<div><div>An efficient luminescence sensor, specifically 2-([1,1′-biphenyl]-4-yl)-1H-benzo[d]imidazole (BBI), has been synthesized through a one-pot green synthesis methodology to detect picric acid (PA) via turn-off quench, demonstrating superior performance relative to numerous nitro aromatic compounds. The compound was characterized using various spectroscopic techniques, in addition to absorption and fluorescence emission studies, to ascertain the sensitivity and selectivity of the probe. The sensor exhibits a limit of detection (LOD) of approximately 1.22 × 10<sup>−7</sup> M and a quenching constant of 1.67 × 10<sup>5</sup> M<sup>−1</sup>, as determined by fluorescence measurements. The underlying mechanism of the sensing process was elucidated through both experimental and theoretical analyses. To augment its practical applicability, the sensor was formulated into luminescent ink and gel-based systems for various applications. Additionally, real-world detection capabilities were established by developing solid-contact mode paper strips and glass plate-based detection methods, facilitating the analysis of real-life samples such as soil and water.</div></div>","PeriodicalId":16782,"journal":{"name":"Journal of Photochemistry and Photobiology A-chemistry","volume":"465 ","pages":"Article 116346"},"PeriodicalIF":4.1,"publicationDate":"2025-02-18","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143453833","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}

引用次数: 0

Synthesis, physicochemical properties and infrared bioimaging of donor-acceptor (D-A) benzothiadiazole and diketopyrrolopyrrole macromolecules: A combined experimental and theoretical study

IF 4.1 3区化学 Q2 CHEMISTRY, PHYSICAL

Journal of Photochemistry and Photobiology A-chemistry

Pub Date : 2025-02-16 DOI: 10.1016/j.jphotochem.2025.116345

Jonatan Rodríguez-Rea , Marisol Güizado-Rodríguez , Sergio Romero-Servin , Gabriel Ramos-Ortiz , José Elías Guzmán-López , Victor Barba , Irán Fernando Hernández-Ahuactzi , Lerida Liss Flores-Villavicencio , Julio César Villagómez-Castro

Herein the synthesis of the polymer (PHB) and the oligomer (OHDPP) using the Fagnou-type direct arylation reaction with goods yields nearly to 63% is described. These macromolecules were envisioned comprising an electronic donor–acceptor (D-A) structure with 3,4-dihexylthiophene (H) as donor and benzothiadiazole (B) or diketopyrrolopyrrole (DPP) as acceptor moieties. Based on the implemented strategy of synthesis, the combination of H with B, or H with DPP, favored obtaining polymeric and oligomer structures, respectively. Taking advantage of the easy preparation and low cost provided by the arylation reaction compared with other polymerization methods, the strength of the D-A effect induced by B or DPP acceptor fragments was investigated experimentally and theoretically. As a polymer, PHB exhibited a higher thermal stability, but the oligomer OHDPP demonstrated higher intramolecular charge transfer (ICT) effects. Light emissive electronic states were generated in both materials by nonlinear absorption at infrared wavelengths with maximum two-photon absorption (TPA) cross sections of ∼900 GM. The light emission from the macromolecules in organic solutions was observed at the red and infrared wavelength range of the spectrum; when processed in the form of nanoparticles, these macromolecules were exploited as fluorescent labels for the bioimaging of the neuroblastoma cell line SH-SY5Y. Theoretical calculations provided insight into the molecular conformation in solution and generated data on intramolecular interactions. They show more intramolecular interactions in OHDPP due to its molecular planarity, which explains the more effective ICT compared with PHB.

本文介绍了利用法格努式直接芳基化反应合成聚合物（PHB）和低聚物（OHDPP）的方法，产率接近 63%。根据设想，这些大分子由电子供体-受体（D-A）结构组成，3,4-二己基噻吩（H）为供体，苯并噻二唑（B）或二酮吡咯（DPP）为受体分子。根据已实施的合成策略，H 与 B 或 H 与 DPP 的组合分别有利于获得聚合体和低聚物结构。与其他聚合方法相比，芳基化反应具有制备简便、成本低廉的优势，因此我们通过实验和理论研究了 B 或 DPP 受体片段诱导的 D-A 效应的强度。作为聚合物，PHB 表现出更高的热稳定性，但低聚物 OHDPP 则表现出更高的分子内电荷转移（ICT）效应。这两种材料都通过红外波长的非线性吸收产生了光发射电子态，其最大双光子吸收（TPA）截面为 ∼900 GM。在有机溶液中观察到大分子在光谱的红色和红外波长范围内发光；将这些大分子加工成纳米颗粒后，可作为荧光标签用于神经母细胞瘤细胞株 SH-SY5Y 的生物成像。理论计算深入揭示了溶液中的分子构象，并生成了分子内相互作用的数据。计算结果表明，由于 OHDPP 的分子平面性，其分子内相互作用更多，因此与 PHB 相比，其 ICT 效果更好。

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引用次数: 0

Excitation energy transfer from BODIPY to self-aggregate of zinc bacteriochlorophyll-d analog in supramolecule

IF 4.1 3区化学 Q2 CHEMISTRY, PHYSICAL

Journal of Photochemistry and Photobiology A-chemistry

Pub Date : 2025-02-15 DOI: 10.1016/j.jphotochem.2025.116344

Yuna Mori, Hitoshi Tamiaki

In the main light-harvesting antennas (chlorosomes) of anoxygenic photosynthetic green bacteria, photoexcited carotenoids absorbing green light donate singlet excitation energy to self-aggregates of bacteriochlorophylls(BChls)-c/d/e with their site energies in a far-red light region. To mimic the energy transfer systems, a zinc BChl-d analog covalently linked with a boron dipyrromethene (BODIPY) derivative was investigated in 1%(v/v) tetrahydrofuran and hexane. In the less polar organic solvent, the Zn-BChl-d part in the conjugate self-aggregated similarly as in chlorosomes and accepted excitation energy from the BODIPY part with absorption around 500 nm in a green light region. The excitation energy transfer from BODIPY* to (Zn-BChl-d)_n in the supramolecular self-assembly of the conjugate was analyzed by visible absorption and fluorescence emission spectroscopy.

引用次数: 0

Albumin amplifies the dioxetane (AMPPD) chemiluminescence triggered by alkaline phosphatase: Light emerging from protein cavities

IF 4.1 3区化学 Q2 CHEMISTRY, PHYSICAL

Journal of Photochemistry and Photobiology A-chemistry

Pub Date : 2025-02-15 DOI: 10.1016/j.jphotochem.2025.116339

Leonardo Almeida Barison , Maurício Ikeda Yoguim , Aguinaldo Robinson de Souza , Nelson Henrique Morgon , Valdecir Farias Ximenes

AMPPD is an abbreviation for 3-(2′-spiroadamantyl)-4-methoxy-4-(3-phosphoryloxy)-phenyl-1,2-dioxetane, a thermally stable 1,2-dioxetane derivative widely used as a chemiluminescent probe in clinical laboratories for enzyme immunoassays. AMPPD is a substrate for alkaline phosphatase (ALP), the enzyme that catalyzes the remotion of the phosphoryl group of AMPPD, triggering light emission. This study investigated the impact of albumins on the AMPPD:ALP system and found that human serum albumin (HSA) increases the light emission efficiency of AMPPD:ALP by around 100 times. The efficiency of light enhancement varied depending on the type of albumin, with bovine (BSA), porcine (PSA), and rabbit (RSA) serum albumins being less effective than HSA. We conducted experiments to demonstrate that once hydrolyzed by ALP, the dephosphorylated AMPPD diffuses to site I of HSA. By studying the photophysical properties of the phenol ester generated after AMPPD cleavage, we found that its complexation with HSA caused a significant increase in its fluorescent efficiency, which explains the amplification of the chemiluminescence. Resonance energy transfer from the excited phenol ester to coumarin-153 was detected, confirming the presence of both molecules in the protein cavity. Hence, introducing fluorescent acceptors into the reaction system can adjust the emission wavelength. Besides the first direct evidence of albumin as an enhancer for chemiluminescence, the results highlight the potential interference of albumins on AMPPD-mediated assays and new biotechnological applications.

{"title":"Albumin amplifies the dioxetane (AMPPD) chemiluminescence triggered by alkaline phosphatase: Light emerging from protein cavities","authors":"Leonardo Almeida Barison , Maurício Ikeda Yoguim , Aguinaldo Robinson de Souza , Nelson Henrique Morgon , Valdecir Farias Ximenes","doi":"10.1016/j.jphotochem.2025.116339","DOIUrl":"10.1016/j.jphotochem.2025.116339","url":null,"abstract":"<div><div>AMPPD is an abbreviation for 3-(2′-spiroadamantyl)-4-methoxy-4-(3-phosphoryloxy)-phenyl-1,2-dioxetane, a thermally stable 1,2-dioxetane derivative widely used as a chemiluminescent probe in clinical laboratories for enzyme immunoassays. AMPPD is a substrate for alkaline phosphatase (ALP), the enzyme that catalyzes the remotion of the phosphoryl group of AMPPD, triggering light emission. This study investigated the impact of albumins on the AMPPD:ALP system and found that human serum albumin (HSA) increases the light emission efficiency of AMPPD:ALP by around 100 times. The efficiency of light enhancement varied depending on the type of albumin, with bovine (BSA), porcine (PSA), and rabbit (RSA) serum albumins being less effective than HSA. We conducted experiments to demonstrate that once hydrolyzed by ALP, the dephosphorylated AMPPD diffuses to site I of HSA. By studying the photophysical properties of the phenol ester generated after AMPPD cleavage, we found that its complexation with HSA caused a significant increase in its fluorescent efficiency, which explains the amplification of the chemiluminescence. Resonance energy transfer from the excited phenol ester to coumarin-153 was detected, confirming the presence of both molecules in the protein cavity. Hence, introducing fluorescent acceptors into the reaction system can adjust the emission wavelength. Besides the first direct evidence of albumin as an enhancer for chemiluminescence, the results highlight the potential interference of albumins on AMPPD-mediated assays and new biotechnological applications.</div></div>","PeriodicalId":16782,"journal":{"name":"Journal of Photochemistry and Photobiology A-chemistry","volume":"464 ","pages":"Article 116339"},"PeriodicalIF":4.1,"publicationDate":"2025-02-15","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143420280","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}

引用次数: 0

Photocatalytic degradation of tetracycline by UiO-66-S-FeS composites for visible light: Mechanistic on compact interfacial and degradation pathways

IF 4.1 3区化学 Q2 CHEMISTRY, PHYSICAL

Journal of Photochemistry and Photobiology A-chemistry

Pub Date : 2025-02-14 DOI: 10.1016/j.jphotochem.2025.116343

Huimin Wen , Xueyao Wang , Xin Zhang , Xinyang Yao , Lihui Huang , Ting Sun , Zhenhui Gao

Photocatalysis encounters a major challenge in developing catalysts that are capable of functioning stably and efficiently absorbing visible light. In this study, we designed and synthesized the UiO-66-S-FeS photocatalyst, which featured a type I heterojunction. Its successful synthesis was validated by characterization analyses. The UiO-66-S-FeS catalyst exhibited a “shell-core” structure, with FeS firmly anchored to the surface of UiO-66-SH₂ via Fe-S bonds, creating a robust interface. The interface significantly enhanced the rate of photogenerated carrier transfer and separation during photocatalytic reactions. While retaining the original advantages of active site dispersion and high specific surface area of MOFs, the doping of FeS resulted in good visible light absorption performance. Ultraviolet–visible diffuse reflectance spectroscopy (UV–Vis DRS) revealed that the visible light absorption scope of UiO-66-S-FeS_0.5 was effectively broadened compared to UiO-66-SH₂. It resulted in a remarkable improvement in tetracycline degradation, achieving a degradation rate of 99.5 % under visible light. Electron spin resonance (ESR) and free radical scavenging experiments identified several reactive species, including ·O₂⁻, h⁺, ·OH and ¹O₂ playing roles in the degradation process. These findings supported the degradation mechanism as a type I heterojunction. This study demonstrated the potential of the UiO-66-S-FeS photocatalyst for effectively removing antibiotic contaminants.

{"title":"Photocatalytic degradation of tetracycline by UiO-66-S-FeS composites for visible light: Mechanistic on compact interfacial and degradation pathways","authors":"Huimin Wen , Xueyao Wang , Xin Zhang , Xinyang Yao , Lihui Huang , Ting Sun , Zhenhui Gao","doi":"10.1016/j.jphotochem.2025.116343","DOIUrl":"10.1016/j.jphotochem.2025.116343","url":null,"abstract":"<div><div>Photocatalysis encounters a major challenge in developing catalysts that are capable of functioning stably and efficiently absorbing visible light. In this study, we designed and synthesized the UiO-66-S-FeS photocatalyst, which featured a type I heterojunction. Its successful synthesis was validated by characterization analyses. The UiO-66-S-FeS catalyst exhibited a “shell-core” structure, with FeS firmly anchored to the surface of UiO-66-SH<sub>2</sub> via Fe-S bonds, creating a robust interface. The interface significantly enhanced the rate of photogenerated carrier transfer and separation during photocatalytic reactions. While retaining the original advantages of active site dispersion and high specific surface area of MOFs, the doping of FeS resulted in good visible light absorption performance. Ultraviolet–visible diffuse reflectance spectroscopy (UV–Vis DRS) revealed that the visible light absorption scope of UiO-66-S-FeS<sub>0.5</sub> was effectively broadened compared to UiO-66-SH<sub>2</sub>. It resulted in a remarkable improvement in tetracycline degradation, achieving a degradation rate of 99.5 % under visible light. Electron spin resonance (ESR) and free radical scavenging experiments identified several reactive species, including ·O<sub>2</sub><sup>−</sup>, h<sup>+</sup>, ·OH and <sup>1</sup>O<sub>2</sub> playing roles in the degradation process. These findings supported the degradation mechanism as a type I heterojunction. This study demonstrated the potential of the UiO-66-S-FeS photocatalyst for effectively removing antibiotic contaminants.</div></div>","PeriodicalId":16782,"journal":{"name":"Journal of Photochemistry and Photobiology A-chemistry","volume":"464 ","pages":"Article 116343"},"PeriodicalIF":4.1,"publicationDate":"2025-02-14","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143429787","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}

引用次数: 0