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Halogenated dibenzoylmethane Eu3+ complexes as spectroscopic markers: a pioneering photobleaching strategy for counterfeit applications and controlling luminescence efficiency† 卤化二苯甲酰甲烷Eu3+配合物作为光谱标记物:用于伪造应用和控制发光效率的开创性光漂白策略
IF 6 2区 材料科学
Materials Chemistry Frontiers Pub Date : 2025-01-08 DOI: 10.1039/D4QM00933A
Alisia V. Tsorieva, Vladislav M. Korshunov, Mikhail T. Metlin, Tatiana S. Vlasova, Victoria E. Gontcharenko, Daria A. Metlina, Victor O. Kompanets, Sergey V. Chekalin and Ilya V. Taydakov
{"title":"Halogenated dibenzoylmethane Eu3+ complexes as spectroscopic markers: a pioneering photobleaching strategy for counterfeit applications and controlling luminescence efficiency†","authors":"Alisia V. Tsorieva, Vladislav M. Korshunov, Mikhail T. Metlin, Tatiana S. Vlasova, Victoria E. Gontcharenko, Daria A. Metlina, Victor O. Kompanets, Sergey V. Chekalin and Ilya V. Taydakov","doi":"10.1039/D4QM00933A","DOIUrl":"https://doi.org/10.1039/D4QM00933A","url":null,"abstract":"<p >A novel method for identifying counterfeit goods based on the difference between photobleaching rates of spectroscopic marker components is proposed. Controlled photobleaching of the dye is achieved <em>via</em> introduction of halogens (I, Cl, Br, and F) into the aromatic moiety of the dibenzoylmethane (DBM) ligand in coordination compounds of Eu<small><sup>3+</sup></small>. A spectroscopic marker model that consists of two coordination compounds with different halogens is developed. These compounds exhibit indistinguishable luminescence spectra and emission intensities at low irradiation power. However, exceeding the threshold irradiation power results in rapid photobleaching of the marker fragment derived from the complex with the highest charge number of halogen atoms. This approach introduces new possibilities for quality control of goods that require storage in light-protected environments. The results obtained during the research have both practical and fundamental significance. For the first time, it is established that the halogenation of the DBM ligand leads to the intersystem crossing process termination. Energy of electronic excitation transfers from the singlet excited state to the ion through a charge transfer state instead of the triplet excited state. Such energy transfer pathways sensitize luminescence of Eu<small><sup>3+</sup></small> more effectively, resulting in an increase in quantum yield up to 64% upon the introduction of chlorine atoms.</p>","PeriodicalId":86,"journal":{"name":"Materials Chemistry Frontiers","volume":" 5","pages":" 809-817"},"PeriodicalIF":6.0,"publicationDate":"2025-01-08","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143480825","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"材料科学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
引用次数: 0
Excited-state intramolecular proton transfer derivatives as self-absorption free luminophores for luminescent solar concentrators† 分子内激发态质子转移衍生物作为自吸收自由发光基团用于发光太阳能聚光器†
IF 6 2区 材料科学
Materials Chemistry Frontiers Pub Date : 2025-01-08 DOI: 10.1039/D4QM00874J
Phatsathorn Chonlateeroj, Suangsiri Arunlimsawat, Pattarapapa Janthakit, Rattanasiri Wannapakdee, Wijitra Waengdongbung, Taweesak Sudyoadsuk, Pisist Kumnorkaew and Vinich Promarak
{"title":"Excited-state intramolecular proton transfer derivatives as self-absorption free luminophores for luminescent solar concentrators†","authors":"Phatsathorn Chonlateeroj, Suangsiri Arunlimsawat, Pattarapapa Janthakit, Rattanasiri Wannapakdee, Wijitra Waengdongbung, Taweesak Sudyoadsuk, Pisist Kumnorkaew and Vinich Promarak","doi":"10.1039/D4QM00874J","DOIUrl":"https://doi.org/10.1039/D4QM00874J","url":null,"abstract":"<p >Luminescent solar concentrators (LSCs) have garnered considerable attention for their potential to enhance solar energy harvesting in photovoltaic (PV) systems. However, self-absorption often hinders their efficiency, caused by the overlap between the absorption and emission spectra. Herein, we design, synthesize, and study a series of novel excited-state intramolecular proton transfer (ESIPT) dyes as a new class of self-absorption-free luminophores for efficient transparent LSC-PV devices. <strong>HBTM</strong>, <strong>HBTPM</strong>, and <strong>HBTBP</strong> dyes comprise 2-(benzo[<em>d</em>]thiazol-2-yl)phenol as an electron-donating ESIPT unit functionalized with different π–acceptor moieties of ((3-hexylthiophen-2-yl)methylene)malononitrile, (4-(3-hexylthiophen-2-yl)benzylidene)malononitrile, and (4-(3-hexylthiophen-2-yl)phenyl)(phenyl)methanone, respectively. Theoretical and photophysical analyses confirm the ESIPT nature of these dyes. They show absorption in the UV-blue region and orange-red emissions with large Stokes shifts (4388–10269 cm<small><sup>−1</sup></small>) and decent fluorescence quantum yields (28–47%). Their LSC samples are well prepared by dispersion in a transparent polymethyl methacrylate (PMMA) matrix. The LSC slabs possess good photophysical properties of the dyes with minimal overlap integrals (OI*) of 0.28–1.56% and edge emission efficiencies (<em>η</em><small><sub>edge</sub></small>) of 47–57%. Photovoltaic performance assessments reveal power conversion efficiencies (PCE) of 0.46% to 0.68% with external photon efficiencies (<em>η</em><small><sub>ext</sub></small>) of 7.69% for <strong>HBTM</strong>, 6.91% for <strong>HBTPM</strong>, and 2.98% for <strong>HBTBP</strong>. Particularly, <strong>HBTBP</strong>-based LSC exhibits excellent transparency (AVT = 93%; CRI = 97) suitable for window applications. This work represents a significant step toward reducing self-absorption in LSCs while improving photovoltaic performance, paving the way for scalable solar concentrator technologies based on organic materials.</p>","PeriodicalId":86,"journal":{"name":"Materials Chemistry Frontiers","volume":" 4","pages":" 695-709"},"PeriodicalIF":6.0,"publicationDate":"2025-01-08","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143379720","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"材料科学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
引用次数: 0
Improving stability and efficiency of PTAA-based inverted perovskite solar cells through a guest strategy† 通过客体策略提高ptaa基倒置钙钛矿太阳能电池的稳定性和效率
IF 6 2区 材料科学
Materials Chemistry Frontiers Pub Date : 2025-01-08 DOI: 10.1039/D4QM00917G
Jieying Cao, Xinxing Yin, Lei Lu, Jiaxing Song, Lin Hu, Yingzhi Jin, Zhen Su, Zaifang Li and Jiefeng Hai
{"title":"Improving stability and efficiency of PTAA-based inverted perovskite solar cells through a guest strategy†","authors":"Jieying Cao, Xinxing Yin, Lei Lu, Jiaxing Song, Lin Hu, Yingzhi Jin, Zhen Su, Zaifang Li and Jiefeng Hai","doi":"10.1039/D4QM00917G","DOIUrl":"https://doi.org/10.1039/D4QM00917G","url":null,"abstract":"<p >Although poly[bis(4-phenyl) (2,4,6-trimethylphenyl)amine] (PTAA) has been extensively investigated as a hole transport material, its performance regarding stability and efficiency still encounters challenges. In this study, through the introduction of a novel guest molecule BQ-BO, the energy level configuration, hole transport, and interface passivation of PTAA have been significantly enhanced. The large conjugated electron-deficient core and methoxy-substituted triphenylamine arm structure of BQ-BO not only optimize the HOMO energy level but also enhance the hole mobility and conductivity, attaining a photoelectric conversion efficiency of 21.81%. It also exhibited outstanding thermal stability, maintaining an initial efficiency of 90% after 1000 hours of continuous heating at 85 °C, in contrast to a pure PTAA-based device whose efficiency dropped to 70% after 400 hours.</p>","PeriodicalId":86,"journal":{"name":"Materials Chemistry Frontiers","volume":" 4","pages":" 658-665"},"PeriodicalIF":6.0,"publicationDate":"2025-01-08","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143379716","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"材料科学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
引用次数: 0
Silicoaluminophosphate-seeded Al-pair-enriched low-silica CHA zeolites for enhanced Sr2+ capture† 硅-磷酸铝种子富集al -对低硅CHA沸石增强Sr2+捕获†
IF 6 2区 材料科学
Materials Chemistry Frontiers Pub Date : 2025-01-06 DOI: 10.1039/D4QM01030B
Yufei Wang, Haopeng Su, Shuang Liu, Junyao Pan, Haoyang Zhang, Xue Ding, Yuxin Yan, Keyan Jin, Binyu Wang and Wenfu Yan
{"title":"Silicoaluminophosphate-seeded Al-pair-enriched low-silica CHA zeolites for enhanced Sr2+ capture†","authors":"Yufei Wang, Haopeng Su, Shuang Liu, Junyao Pan, Haoyang Zhang, Xue Ding, Yuxin Yan, Keyan Jin, Binyu Wang and Wenfu Yan","doi":"10.1039/D4QM01030B","DOIUrl":"https://doi.org/10.1039/D4QM01030B","url":null,"abstract":"<p >Radioactive strontium-90 (<small><sup>90</sup></small>Sr<small><sup>2+</sup></small>) in wastewater poses a significant threat to both the environment and living organisms. Conventional treatment strategies, such as ion-exchange resins followed by cement solidification, can still carry the risk of leakage under certain conditions. Low-silica zeolites have demonstrated strong cation sorption capabilities, with <strong>CHA</strong> zeolites showing particular promise for nuclear wastewater treatment. However, synthesizing low-silica <strong>CHA</strong> zeolites with Si/Al ratios around 2 typically requires fluorides or complex crystallization processes. In this study, we present a one-step, fluoride-free synthesis method for low-silica <strong>CHA</strong> zeolites using the silicoaluminophosphate (SAPO) zeolite SAPO-35 as the seed. The SAPO-seeded synthesis method enhances the formation of Al-pairs within the <strong>CHA</strong> framework by releasing partially connected Si and Al species from the SAPO seed. This significantly improves the zeolite's capability to capture the divalent Sr<small><sup>2+</sup></small>. The resulting zeolite exhibits a 10% higher Sr<small><sup>2+</sup></small> sorption capacity per ion-exchange site compared to <strong>CHA</strong> zeolites synthesized without the SAPO seed. The synthesized zeolite exhibits exceptional Sr<small><sup>2+</sup></small> removal efficiency across dosages of 1/50–1/500 g mL<small><sup>−1</sup></small> and the pH range of 3–12. At temperatures of 25 °C, 60 °C, and 80 °C, the sorption capacities reach 112 mg g<small><sup>−1</sup></small>, 144 mg g<small><sup>−1</sup></small>, and 186 mg g<small><sup>−1</sup></small>, respectively. This work highlights the potential of SAPO-seeded synthesis as a practical and scalable approach for producing Al-pair-enriched, low-silica <strong>CHA</strong> zeolites, indicating the high effectiveness for removing <small><sup>90</sup></small>Sr<small><sup>2+</sup></small> from nuclear wastewater and offering a promising solution for radioactive wastewater management.</p>","PeriodicalId":86,"journal":{"name":"Materials Chemistry Frontiers","volume":" 4","pages":" 666-675"},"PeriodicalIF":6.0,"publicationDate":"2025-01-06","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143379717","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"材料科学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
引用次数: 0
High-performance MOF-based electromagnetic wave absorption materials: design and performance optimization 高性能mof基电磁波吸收材料:设计与性能优化
IF 6 2区 材料科学
Materials Chemistry Frontiers Pub Date : 2025-01-06 DOI: 10.1039/D4QM01054J
Xiao-Xuan Fan, Zhan-Zhan Wang, Xin-Ci Zhang, Lin Li and Mao-Sheng Cao
{"title":"High-performance MOF-based electromagnetic wave absorption materials: design and performance optimization","authors":"Xiao-Xuan Fan, Zhan-Zhan Wang, Xin-Ci Zhang, Lin Li and Mao-Sheng Cao","doi":"10.1039/D4QM01054J","DOIUrl":"https://doi.org/10.1039/D4QM01054J","url":null,"abstract":"<p >In recent years, the issue of increasing electromagnetic pollution has posed significant challenges for researchers in the field of electromagnetic dissipation, highlighting the urgent need for effective solutions. Metal–organic frameworks (MOFs) have garnered considerable attention due to their compositional designability, large specific surface area, and tunable chemical structure, making them highly desirable precursors for electromagnetic wave absorption materials (EMWAMs). MOF-based EMWAMs exhibit remarkable performance advantages, such as lightweight properties, high loss capability, and a wide effective absorption bandwidth. These advantages are primarily attributed to their excellent impedance matching and multiple attenuation mechanisms. This paper provides a concise discussion on the relationship between the mechanisms and microstructure of EMWAMs. The research progress of MOF-based EMWAMs in recent years is reviewed, including the classification of MOF and MOF composite precursors, design principles and preparation methods. Finally, the problems, challenges and future opportunities of MOF-based EMWAMs are presented. We aim for this review to offer new insights into the design and fabrication of MOF-based EMWAMs, thereby enhancing both the fundamental understanding and practical application of these materials.</p>","PeriodicalId":86,"journal":{"name":"Materials Chemistry Frontiers","volume":" 3","pages":" 403-417"},"PeriodicalIF":6.0,"publicationDate":"2025-01-06","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143107448","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"材料科学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
引用次数: 0
Dual role of lone pair electron and rattling vibration in Zintl phase BaCaPb thermoelectric material† Zintl相BaCaPb热电材料中孤对电子和咔嗒振动的双重作用
IF 6 2区 材料科学
Materials Chemistry Frontiers Pub Date : 2025-01-06 DOI: 10.1039/D4QM00972J
Shuwei Tang, Pengfei Zhang, Da Wan, Xiaodong Li, Peng Ai, Zhiwei Zhang, Wanrong Guo, Shulin Bai and Xiuling Qi
{"title":"Dual role of lone pair electron and rattling vibration in Zintl phase BaCaPb thermoelectric material†","authors":"Shuwei Tang, Pengfei Zhang, Da Wan, Xiaodong Li, Peng Ai, Zhiwei Zhang, Wanrong Guo, Shulin Bai and Xiuling Qi","doi":"10.1039/D4QM00972J","DOIUrl":"https://doi.org/10.1039/D4QM00972J","url":null,"abstract":"<p >The crystal structure, phonon dispersion curves, electronic transport parameters, and thermoelectric (TE) properties of the Zintl phase BaCaPb compound are investigated by first-principles calculations in combination with a two-channel model. The regular residuals analysis demonstrates the crucial role of four-phonon scattering behavior in evaluating the thermal transport properties of the BaCaPb compound on account of the noticeable optical–optical gap. The origin of the rattling vibration behaviour is investigated by the quantitative analysis of chemical bond. The diffusion-like phonons are predominantly influenced by the rattling vibration of the Ba atom in the BaCaPb compound. Moreover, the dual role of the lone electrons in Pb and the rattling vibration of the Ba atom contributes to the ultralow lattice thermal conductivity (1.46 W m<small><sup>−1</sup></small> K<small><sup>−1</sup></small>@ 300 K) in the BaCaPb compound. In addition, the TE properties of the BaCaPb compound are evaluated in consideration of multiple carrier scatterings, and optimal figures of merit (<em>ZT</em>s) of 1.7 and 1.0 are achieved for the <em>n</em>-type and <em>p</em>-type BaCaPb compounds at 600 K. The present work not only reveals the excellent TE properties of the Zintl phase BaCaPb compound through an in-depth study of their thermal and electronic transport properties, but also adopts a two-channel model for the theoretical design of high-efficiency TE materials.</p>","PeriodicalId":86,"journal":{"name":"Materials Chemistry Frontiers","volume":" 4","pages":" 592-607"},"PeriodicalIF":6.0,"publicationDate":"2025-01-06","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143379675","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"材料科学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
引用次数: 0
Bifunctional CuNi-x nano-alloys for electrocatalytic nitrate reduction and HPAM oxidation coupling reactions† 用于电催化硝酸还原和HPAM氧化偶联反应的双功能cu -x纳米合金
IF 6 2区 材料科学
Materials Chemistry Frontiers Pub Date : 2025-01-06 DOI: 10.1039/D4QM00962B
Lijie Qi, Yu Fu, Borui Ji, Bauyrzhan Sarsenbekuly, Wanli Kang, Hongbin Yang and Shujun Liu
{"title":"Bifunctional CuNi-x nano-alloys for electrocatalytic nitrate reduction and HPAM oxidation coupling reactions†","authors":"Lijie Qi, Yu Fu, Borui Ji, Bauyrzhan Sarsenbekuly, Wanli Kang, Hongbin Yang and Shujun Liu","doi":"10.1039/D4QM00962B","DOIUrl":"https://doi.org/10.1039/D4QM00962B","url":null,"abstract":"<p >Electrochemical synthesis of ammonia (NH<small><sub>3</sub></small>) through cathodic nitrate reduction presents an effective alternative to the Haber–Bosch process, enabling efficient ammonia production without significant environmental pollution. The electrocatalytic degradation strategy is an efficient and environmentally friendly tool for the treatment of oily wastewater containing partially hydrolized polyacrylamide (HPAM). Thus, coupling cathodic nitrate reduction with anodic HPAM oxidation can further enhance ammonia synthesis efficiency and HPAM degradation efficiency. Here, we reported an N-doped carbon nanotube loaded with CuNi-<em>x</em> (<em>x</em> = 0.5, 1, 2) as an electrocatalyst for cathodic nitrate reduction coupled with anodic HPAM oxidative degradation. Notably, the CuNi-1 variant achieved the highest ammonia yield of 4962.76 ± 40.22 μg h<small><sup>−1</sup></small> mg<small><sub>cat</sub></small><small><sup>−1</sup></small> and a faradaic efficiency of 85.91 ± 0.42%. Furthermore, the oxidative degradation rate of HPAM reached a maximum of 81.91 ± 0.36% within 2 h. Anodic HPAM oxidation not only promotes cathodic nitrate reduction but also enables the acquisition of valuable anodic products. Using <em>in situ</em> ATR-SEIRAS, <em>in situ</em> DEMS, and DFT calculations, we thoroughly analyzed reaction intermediates and the critical role of the CuNi bimetallic system in electrocatalytic nitrate reduction. The coupled reaction system was established to achieve both efficient ammonia synthesis and HPAM degradation.</p>","PeriodicalId":86,"journal":{"name":"Materials Chemistry Frontiers","volume":" 4","pages":" 638-647"},"PeriodicalIF":6.0,"publicationDate":"2025-01-06","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143379714","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"材料科学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
引用次数: 0
Organelle-targeting activity-based hemicyanine derivatives for enhanced and selective type-I photodynamic therapy under hypoxia conditions† 基于细胞器靶向活性的半菁氨酸衍生物在缺氧条件下增强和选择性i型光动力治疗
IF 6 2区 材料科学
Materials Chemistry Frontiers Pub Date : 2024-12-31 DOI: 10.1039/D4QM00744A
Musa Dirak, Ayca Saymaz, Alperen Acari, Yunus Akkoc, Haluk Samet Kocak, Cansu M. Yenici, Devrim Gozuacik, Hande Gunduz and Safacan Kolemen
{"title":"Organelle-targeting activity-based hemicyanine derivatives for enhanced and selective type-I photodynamic therapy under hypoxia conditions†","authors":"Musa Dirak, Ayca Saymaz, Alperen Acari, Yunus Akkoc, Haluk Samet Kocak, Cansu M. Yenici, Devrim Gozuacik, Hande Gunduz and Safacan Kolemen","doi":"10.1039/D4QM00744A","DOIUrl":"https://doi.org/10.1039/D4QM00744A","url":null,"abstract":"<p >Type-I photosensitizers (PSs) have attracted great attention in recent years as they minimally rely on the tissue oxygen (<small><sup>3</sup></small>O<small><sub>2</sub></small>) to generate highly cytotoxic reactive oxygen species (ROS) in the scope of photodynamic therapy (PDT). Thus, they hold great promise for effective treatment of hypoxic cancer cells, which is a challenging task for type-II PSs. However, compared to conventional type-II PSs, the number of cancer cell selective type-I PSs is quite low. Thus, there is still a need for type-I PSs that can induce photocytotoxicity only in cancer cells without causing damage to normal tissues even under light irradiation. Additionally, targeting PSs to specific organelles has lately appeared to be a promising approach to improve the therapeutic outcome of PDT. Although a few examples of organelle-targeted type-I PS cores have emerged recently, activity-based and organelle-targeted type-I PSs have remained scarce. In this study, we report two organelle-targeted and hydrogen sulfide (H<small><sub>2</sub></small>S) responsive type-I PSs (<strong>HEHM</strong> and <strong>HEH</strong>) based on a highly modular and easily accessible heavy atom decorated hemicyanine core. <strong>HEHM</strong> localizes to mitochondria due to its cationic structure, whereas <strong>HEH</strong> targets endoplasmic reticulum (ER) as it bears an ER-targeting sulfonamide moiety, and it marks the first example of an activity-based and ER-targeted type-I PS based on a hemicyanine core. Both PSs can be selectively activated in neuroblastoma cells (SH-SY5Y) upon reacting with high levels of endogenous H<small><sub>2</sub></small>S and induce similar photocytotoxicity through a type-I PDT mechanism under both normoxic (20% O<small><sub>2</sub></small>) and hypoxic (1% O<small><sub>2</sub></small>) conditions. <strong>HEHM</strong> is shown to cause PDT-induced mitochondria stress, while <strong>HEH</strong> triggers ER stress upon LED irradiation (640 nm, 66.7 mW cm<small><sup>−2</sup></small>). Additionally, <strong>HEH</strong> is shown to induce immunogenic cell death (ICD) followed by PDT action. In contrast, negligible ROS generation and cell death are observed in normal cells, which is a critical and challenging task for any type of therapeutic modality. They also allow fluorescence imaging of cancer cells due to their emissive nature, suggesting that they function as phototheranostic agents. This study introduces a rational approach to develop new generation activity-based and organelle-targeted type-I PDT agents towards effective and selective treatment of hypoxic tumors.</p>","PeriodicalId":86,"journal":{"name":"Materials Chemistry Frontiers","volume":" 4","pages":" 648-657"},"PeriodicalIF":6.0,"publicationDate":"2024-12-31","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143379715","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"材料科学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
引用次数: 0
Guanidinium-appended γ-cyclodextrin: efficient fullerene solubiliser for enhanced photodynamic therapy† 胍-附加γ-环糊精:增强光动力治疗的高效富勒烯增溶剂
IF 6 2区 材料科学
Materials Chemistry Frontiers Pub Date : 2024-12-31 DOI: 10.1039/D4QM00875H
Mervyn Ho Kong Man, Henry Chak Man Yau and Kou Okuro
{"title":"Guanidinium-appended γ-cyclodextrin: efficient fullerene solubiliser for enhanced photodynamic therapy†","authors":"Mervyn Ho Kong Man, Henry Chak Man Yau and Kou Okuro","doi":"10.1039/D4QM00875H","DOIUrl":"https://doi.org/10.1039/D4QM00875H","url":null,"abstract":"<p >Efficient solubilisation of fullerenes in aqueous media is crucial for their photodynamic therapy (PDT) applications. We demonstrated the efficacy of guanidinium-appended γ-cyclodextrin (CD<small><sup>Gu</sup></small>) as a novel solubiliser for C<small><sub>60</sub></small> and C<small><sub>70</sub></small> fullerenes, achieving exceptionally high aqueous concentrations of 3.1 mM and 0.37 mM, respectively, through simple mechanical mixing in the presence of Na<small><sup>+</sup></small> ions. The resulting complexes, CD<small><sup>Gu</sup></small>⊃C<small><sub>60</sub></small> and CD<small><sup>Gu</sup></small>⊃C<small><sub>70</sub></small>, enabled efficient fullerene transfer to cell membranes, a critical factor for PDT efficacy. Notably, CD<small><sup>Gu</sup></small>⊃C<small><sub>70</sub></small> exhibited excellent singlet oxygen (<small><sup>1</sup></small>0<small><sub>2</sub></small>) generation (quantum yield <em>Φ</em><small><sub>Δ</sub></small> = 0.77 at 630 nm) and induced &gt;90% cell death with only 5 min of white light exposure <em>in vitro</em>. This research highlights the importance of molecular dispersion in enhancing fullerenes’ photosensitising activity and membrane transfer, potentially advancing fullerene-based PDT approaches.</p>","PeriodicalId":86,"journal":{"name":"Materials Chemistry Frontiers","volume":" 5","pages":" 793-799"},"PeriodicalIF":6.0,"publicationDate":"2024-12-31","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143480864","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"材料科学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
引用次数: 0
Design and electrospinning synthesis of red luminescent-highly anisotropic conductive Janus nanobelt hydrogel array films† 红色发光-高各向异性导电Janus纳米带水凝胶阵列膜的设计与静电纺丝合成
IF 6 2区 材料科学
Materials Chemistry Frontiers Pub Date : 2024-12-23 DOI: 10.1039/D4QM00852A
Haina Qi, Huazhi Huang, Yaolin Hu, Ning Li, Liu Yang, Xuejian Zhang, Yongtao Li, Hongkai Zhao, Dan Li and Xiangting Dong
{"title":"Design and electrospinning synthesis of red luminescent-highly anisotropic conductive Janus nanobelt hydrogel array films†","authors":"Haina Qi, Huazhi Huang, Yaolin Hu, Ning Li, Liu Yang, Xuejian Zhang, Yongtao Li, Hongkai Zhao, Dan Li and Xiangting Dong","doi":"10.1039/D4QM00852A","DOIUrl":"https://doi.org/10.1039/D4QM00852A","url":null,"abstract":"<p >The preparation of anisotropic conducting hydrogels with high anisotropic conductivity using simple methods is a major challenge. Herein we present a new strategy for significantly enhancing the degree of anisotropic conductivity of hydrogel materials. Highly oriented Janus nanobelts are used as the building block to avoid undesirable interactions between conducting and insulating materials, resulting in highly conductive hydrogel materials. As a case study, in this paper, anisotropic conductive-luminescent bifunctional Janus nanobelt hydrogel array films (denoted as JAHFs) are prepared by parallel electrospinning and gelation, utilizing highly oriented Janus nanobelts, <em>i.e.</em> [Eu(TTA)<small><sub>3</sub></small>(TPPO)<small><sub>2</sub></small>/gelatin (GE)]//[carbon black (CB)/GE] Janus nanobelts, as building blocks. The high degree of integration between the highly oriented array film and the anisotropic conductive-luminescent materials endows the hydrogel material with high anisotropic conductivity and multifunctionality. The anisotropic conductivity of JAHFs is as high as 1.52 × 10<small><sup>5</sup></small> when the mass ratio of CB/GE is 7%, which achieves a significant increase in anisotropic conductivity through a simple preparation method. JAHFs have a distinct red luminescence at 616 nm. The tunability of luminescence and conductive anisotropy is demonstrated by adjusting the contents of Eu(TTA)<small><sub>3</sub></small>(TPPO)<small><sub>2</sub></small> and CB. The tensile strength and the elongation at break of JAHFs along the parallel direction of Janus nanobelts are 0.61 MPa and 80.75%. The good mechanical properties of JAHFs provide a guarantee for the assembly of strain sensors. JAHFs exhibited rapid responses under various tensile strains and temperatures, and the assembled strain sensors are utilized to detect human joint motion with good stability and sensitivity. This method is also applicable to the preparation of other multifunctional anisotropic conducting hydrogel materials. This study contributes new approaches and technical support for enhancing the anisotropic conductivity of hydrogel materials and sets the groundwork for developing other multifunctional conductive hydrogel materials.</p>","PeriodicalId":86,"journal":{"name":"Materials Chemistry Frontiers","volume":" 4","pages":" 710-724"},"PeriodicalIF":6.0,"publicationDate":"2024-12-23","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143379677","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"材料科学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
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