Journal of Photochemistry and Photobiology A-chemistry最新文献_第3页

Elucidating the effect of positional isomerism on the emission properties of high-performance Luminogens 阐明了位置异构对高性能发光材料发射性能的影响

IF 4.7 3区化学 Q2 CHEMISTRY, PHYSICAL

Journal of Photochemistry and Photobiology A-chemistry

Pub Date : 2025-12-27 DOI: 10.1016/j.jphotochem.2025.117015

Xianchao Du , Qianyun Liu , Xiang Liu , Datai Liu , Dongqin Bi , He Lei , Xinfeng Cheng , Dongfang Qiu , Maosen Yuan

The development of organic fluorescent materials with high quantum yields in the aggregated state has emerged as a vital research hotspot. Positional isomerism (regioisomerism), an effective strategy for modulating molecular properties, plays a key role in the design of organic fluorescent materials. Herein, four regioisomeric derivatives (FO-1, FO-2, FO-3, and FO-4) with triphenylamine units at different fluorenone positions were synthesized to investigate the effect of regioisomerism on their optical properties. All fluorenone derivatives exhibited aggregation-induced emission and strong solid-state luminescence. FO-3 exhibited a higher fluorescence quantum yield in the aggregated state than FO-1 and FO-2. In contrast, FO-4 displayed the weakest emission. Optical measurements, single-crystal structure analyses, and theoretical calculations confirmed that regioisomerism significantly influenced charge distribution and molecular packing, leading to variations in intermolecular and intramolecular interactions. Consequently, the four fluorenone derivatives exhibited distinct luminescent properties. Upon doping into light-emitting devices, FO-1, FO-2, FO-3, and FO-4 exhibited strong aggregated emission, high stability, and current-controllable brightness. This study provides a valuable theoretical basis for developing high-performance organic fluorescent materials and investigating the effect of regioisomerism on their photophysical properties.

在聚合态下开发高量子产率的有机荧光材料已成为一个重要的研究热点。位置异构（区域异构）是调节分子性质的一种有效策略，在有机荧光材料的设计中起着关键作用。本文合成了四种具有不同氟酮位置三苯胺单元的区域异构体衍生物（FO-1、FO-2、FO-3和FO-4），研究了区域异构体对其光学性质的影响。所有芴酮衍生物均表现出聚集致发光和强固态发光。聚合态FO-3的荧光量子产率高于FO-1和FO-2。而FO-4的辐射最弱。光学测量、单晶结构分析和理论计算证实，区域异构现象显著影响电荷分布和分子堆积，导致分子间和分子内相互作用的变化。因此，四种芴酮衍生物表现出不同的发光性质。在发光器件中掺杂后，FO-1、FO-2、FO-3和FO-4表现出强聚集发光、高稳定性和电流可控亮度。该研究为开发高性能有机荧光材料以及研究区域异构对其光物理性质的影响提供了有价值的理论依据。

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引用次数: 0

Synergistic promotion of visible-light-driven photocatalytic Cr(VI) reduction by lattice distortion and sulfur vacancies in in-doped CdS nanoparticles under simulated complex ionic environments 在模拟复杂离子环境下，晶格畸变和硫空位对掺杂CdS纳米颗粒可见光催化Cr（VI）还原的协同促进作用

IF 4.7 3区化学 Q2 CHEMISTRY, PHYSICAL

Journal of Photochemistry and Photobiology A-chemistry

Pub Date : 2025-12-25 DOI: 10.1016/j.jphotochem.2025.117017

Chang Feng , Yuhong Lin , Yadong Zheng , Zhuoyuan Chen , Jiangping Jing , Li Ma , Jian Hou

Lattice regulation and defect engineering are proven effective strategies to enhance the photocatalytic performance of semiconductor photocatalysts, and have thus garnered extensive research attention in the field of photocatalysis. Therefore, the design of photocatalysts with the synergistic effects of lattice distortion and defect states has emerged as a research priority. In this work, an indium (in)-doped cadmium sulfide (InCdS) photocatalyst was fabricated via a facile water bath method. The lattice distortion and sulfur (S) vacancy induced by in doping, and the photocatalytic Cr(VI) reduction performance of InCdS were systematically investigated. The results demonstrated that in doping not only triggered lattice distortion in CdS but also significantly elevated its S vacancy concentration. Meanwhile, the introduction of in³⁺ selectively suppressed the growth of the CdS (200) crystal plane, which induced the morphological transformation of CdS from nanosheets to uniform spherical nanoclusters and remarkably enhanced its specific surface area. The synergistic effect of lattice distortion and S vacancies significantly promotes the separation efficiency of photogenerated carriers in InCdS, thereby enhancing its photocatalytic performance for Cr(VI) reduction. Specifically, 5 %InCdS achieves complete reduction of 30 mg⋅L⁻¹ Cr(VI) within merely 25 min under visible light irradiation, and its reaction rate constant is 15.26 times that of pure CdS. More importantly, 5 %InCdS exhibits excellent stability during the photocatalytic Cr(VI) reduction process. Further mechanistic analysis reveals that photogenerated electrons serve as the dominant active species responsible for the photocatalytic Cr(VI) reduction reaction. This work provides a theoretical basis for the development and design of high-efficiency photocatalysts via simple synthesis strategies that induce lattice distortion and S vacancies, thereby offering new insights into their practical application in the treatment of Cr-containing wastewater

晶格调控和缺陷工程是提高半导体光催化剂光催化性能的有效策略，因此在光催化领域得到了广泛的研究关注。因此，设计具有晶格畸变和缺陷态协同效应的光催化剂已成为研究的重点。本研究采用易溶水浴法制备了一种掺铟硫化镉（InCdS）光催化剂。系统地研究了掺杂引起的晶格畸变和硫空位，以及光催化还原Cr（VI）的性能。结果表明，掺杂不仅引发了CdS的晶格畸变，而且显著提高了CdS的S空位浓度。同时，in3+的引入选择性地抑制了CdS（200）晶面的生长，诱导CdS从纳米片到均匀球形纳米团簇的形态转变，并显著提高了其比表面积。晶格畸变和S空位的协同作用显著提高了incd中光生载流子的分离效率，从而增强了其光催化还原Cr（VI）的性能。其中，5% InCdS在可见光照射下仅25 min即可完全还原30 mg⋅L−1 Cr(VI)，其反应速率常数是纯CdS的15.26倍。更重要的是，5%的InCdS在光催化Cr（VI）还原过程中表现出优异的稳定性。进一步的机理分析表明，光生电子是光催化Cr（VI）还原反应的主要活性物质。这项工作为通过诱导晶格畸变和S空位的简单合成策略开发和设计高效光催化剂提供了理论基础，从而为其在含铬废水处理中的实际应用提供了新的见解

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引用次数: 0

Tailoring TiO2 photocatalysis via interfacial charge transfer complexes with substituted salicylic acids: A combined theoretical and spectroscopic study 通过取代水杨酸的界面电荷转移配合物剪裁TiO2光催化：理论和光谱的结合研究

IF 4.7 3区化学 Q2 CHEMISTRY, PHYSICAL

Journal of Photochemistry and Photobiology A-chemistry

Pub Date : 2025-12-25 DOI: 10.1016/j.jphotochem.2025.117018

Miriama Malček Šimunková , Dana Dvoranová , Karol Lušpai , Zuzana Dyrčíková , Izabela Lukačovič Vajová , Miljana Dukić , Vesna Lazić , Dušan Sredojević , Jovan M. Nedeljković

The modification of titanium dioxide (TiO₂), taking advantage of the interfacial charge transfer (ICT) complex formation, represents a novel and effective strategy for bandgap engineering, leading to the formation of visible-light-responsive materials. In this study, TiO₂-based ICT complexes were prepared using salicylic acid (SA) and its derivatives, substituted at the position 5 (–F, –SO₃H, –NH₂). Absorption of modified samples is red-shifted compared to pristine TiO₂, as predicted by the density functional theory (DFT) calculations using cluster models in which ligands form bidentate binuclear complexes with surface Ti atoms. Low-temperature solid-state electron paramagnetic resonance (EPR) studies demonstrated that LED@405 nm excitation of TiO₂-based ICT complexes leads to generation of charge carriers more effectively than LED@365 nm excitation. In addition, photoinduced charge-carrier generation upon LED@405 nm was comparable to LED@365 nm exposure with notable variations in photocatalytic mechanisms, depending on the functional group. An electron-donating group enhanced the photoreduction capacity. On the other side, the presence of electron-withdrawing substituents slightly improved the oxidation activity. Overall, the ICT complex with SA displayed the better photocatalytic activity compared to those with substituted SA. The results show that substitution of SA at the position 5– does not significantly enhance the overall photocatalytic performance of the investigated ICT complexes; however, it influences the underlying photocatalytic pathway, shifting the balance between photoreduction and photooxidation processes. These findings emphasize the potential of ICT complexes to optimize TiO₂ properties for specific light-driven applications.

利用界面电荷转移（ICT）络合物的形成，对二氧化钛（TiO2）进行改性，代表了一种新的有效的带隙工程策略，从而形成可见光响应材料。在本研究中，利用水杨酸（SA）及其衍生物在5位（-F, -SO3H, -NH2）取代制备了基于tio2的ICT配合物。与原始TiO2相比，修饰样品的吸收红移，正如密度泛函理论（DFT）使用簇模型预测的那样，配体与表面Ti原子形成双齿双核配合物。低温固态电子顺磁共振（EPR）研究表明，LED@405 nm激发tio2基ICT配合物比LED@365 nm激发更有效地产生载流子。此外，在LED@405 nm处产生的光诱导电荷载流子与LED@365 nm暴露相当，光催化机制因官能团的不同而有显著差异。一个给电子基团增强了光还原能力。另一方面，吸电子取代基的存在略微提高了氧化活性。总的来说，与取代SA的ICT配合物相比，SA的光催化活性更好。结果表明，在5 -位置取代SA并没有显著提高所研究的ICT配合物的整体光催化性能；然而，它会影响潜在的光催化途径，改变光还原和光氧化过程之间的平衡。这些发现强调了ICT配合物优化TiO2性能的潜力，以用于特定的光驱动应用。

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引用次数: 0

Polymeric fluorescent probes for the detection and removal of 4-nitrophenol 用于检测和去除4-硝基苯酚的聚合荧光探针

IF 4.7 3区化学 Q2 CHEMISTRY, PHYSICAL

Journal of Photochemistry and Photobiology A-chemistry

Pub Date : 2025-12-24 DOI: 10.1016/j.jphotochem.2025.117008

Fan Fan , Jiao He , Junyu Chen , Xinjian Cheng

4-Nitrophenol (4-NP) poses a threat to the environment and human health. Developing a method to efficiently detect and separate 4-NP is of great significance. In this work, boron-dipyrromethane (BODIPY) phosphor was first prepared. Then, a small molecule fluorescent probe (BD-Ac) with an acetylene group was prepared through a Schiff base formation reaction. At the same time, the reversible addition-fragmentation chain transfer (RAFT) reagents (CTA-1, CTA-2) were prepared and polymerized with ethyl 2- (hydroxymethyl) acrylate and tert-butyl vinylcarbamate to obtain three non-fluorescent macromolecules P-01, P-02, and P-03 containing amino groups (−NH₂). The three polymers P-01, P-02, and P-03 were combined with the small molecule fluorescent probe (BD-Ac) through the alkyne-amine click reaction to obtain three fluorescent macromolecules P-1, P-2, and P-3. Meanwhile, through gel permeation chromatography (GPC) testing, it was confirmed that they have a good narrow distribution, with PDI values reaching 1.08, 1.05, and 1.06 respectively. Due to the existence of excited-state proton transfer (ESPT), 4-NP can quench the fluorescence of three fluorescent macromolecules. Limit of detection (LOD) reached 2.8 × 10⁻⁷ mol/L, 3.4 × 10⁻⁷ mol/L, and 4.8 × 10⁻⁷ mol/L respectively. Not only can it identify 4-NP, but it can also achieve efficient separation of 4-NP. The separation efficiencies are 67.9 %, 68.9 %, and 60.3 % respectively. The as-prepared polymeric fluorescence probes might find application in the analytical and environmental sciences.

4-硝基苯酚（4-NP）对环境和人类健康构成威胁。开发一种有效检测和分离4-NP的方法具有重要意义。本文首次制备了硼-二吡咯甲烷（BODIPY）荧光粉。然后，通过席夫碱形成反应制备了带有乙炔基团的小分子荧光探针（BD-Ac）。同时，制备了可逆加成-断裂链转移（RAFT）试剂（CTA-1、CTA-2），并与2-（羟甲基）丙烯酸乙酯和乙烯氨基甲酸叔丁酯进行聚合，得到了三个含氨基（−NH2）的非荧光大分子P-01、P-02和P-03。将三种聚合物P-01、P-02和P-03与小分子荧光探针（BD-Ac）通过炔胺咔嗒反应结合，得到三种荧光大分子P-1、P-2和P-3。同时，通过凝胶渗透色谱（GPC）检测，证实它们具有良好的窄分布，PDI值分别达到1.08、1.05和1.06。由于激发态质子转移（ESPT）的存在，4-NP可以猝灭三种荧光大分子的荧光。检出限（LOD）分别为2.8 × 10−7 mol/L、3.4 × 10−7 mol/L和4.8 × 10−7 mol/L。它不仅可以识别4-NP，而且可以实现4-NP的高效分离。分离效率分别为67.9%、68.9%和60.3%。所制备的聚合物荧光探针在分析科学和环境科学中具有广泛的应用前景。

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引用次数: 0

Terminal branch twisting induced molecular distortion: A strategy for advanced NIR-II photothermal/photodynamic therapy 末端分支扭曲诱导的分子畸变：一种先进的NIR-II光热/光动力治疗策略

IF 4.7 3区化学 Q2 CHEMISTRY, PHYSICAL

Journal of Photochemistry and Photobiology A-chemistry

Pub Date : 2025-12-24 DOI: 10.1016/j.jphotochem.2025.116999

Xiaoye Chen , Yu Cheng , Ding Tan, Yan Sun, Yu Gao , Haijun Chen

Photothermal therapy (PTT) and photodynamic therapy (PDT) represent promising strategies for tumor treatment, as their synergistic effects significantly enhance cancer therapeutic efficacy. In this study, we synthesized compound 111 with second near-infrared region (NIR-II) absorption using terminal branch twisting strategy. Compared to the lead compound 55, 111 exhibits greater distortion with the dihedral angle between the two planes containing the side chains increasing from 31.9° to 48.3°. This structural difference facilitated intersystem crossing, thereby enhancing both photothermal conversion efficiency and singlet oxygen production. Furthermore, the introduction of polyethylene glycol (PEG) branches improves the water solubility and biocompatibility, expanding its potential for in vivo applications. Compared to lead compound, 111 exhibited excellent tumor ablation in vitro and in vivo models. This work provides an important theoretical and practical basis for the development of a new generation of synergistic therapeutic platforms in the NIR-II region.

光热疗法（PTT）和光动力疗法（PDT）具有协同作用，可显著提高肿瘤的治疗效果，是一种很有前景的肿瘤治疗策略。在本研究中，我们采用末端分支扭转策略合成了具有第二近红外吸收的化合物111。与先导化合物55相比，111表现出更大的畸变，包含侧链的两个平面之间的二面角从31.9°增加到48.3°。这种结构差异促进了系统间的交叉，从而提高了光热转换效率和单线态氧气产量。此外，聚乙二醇（PEG）分支的引入改善了水溶性和生物相容性，扩大了其在体内应用的潜力。与先导化合物相比，111在体外和体内模型中均表现出良好的肿瘤消融效果。这项工作为开发新一代NIR-II区域的协同治疗平台提供了重要的理论和实践基础。

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引用次数: 0

Structurally stable S-scheme engineering of In2S3/ZnSe heterostructure for boosting dual-functional photocatalysis of H2O2 production in pure water and 2-mercaptobenzothiazole removal In2S3/ZnSe异质结构促进纯水产H2O2和去除2-巯基苯并噻唑双功能光催化的结构稳定s方案工程

IF 4.7 3区化学 Q2 CHEMISTRY, PHYSICAL

Journal of Photochemistry and Photobiology A-chemistry

Pub Date : 2025-12-24 DOI: 10.1016/j.jphotochem.2025.117016

Andre Lennox Olayemi Macauley , Jie Jiang , Ziyu Feng , Nan Sun , Yongjian Sun , Wenli Zhang , Yinhua Jiang , Yan Liu , Jianming Zhang , Haiqing Xu

The design of effective S-scheme heterojunction photocatalytic systems for producing H₂O₂ and degrading organic contaminants is the promising concepts towards sustainable development. However, the S-scheme photocatalyst system still poses significant challenges in the dynamic process and internal mechanism of interfacial charge transfer. In this paper, a novel S-scheme In₂S₃/ZnSe (ISZS) heterojunction was constructed by loading ZnSe nanoparticles on In₂S₃ nanosheets to form the tight interface contact through an in-situ solvothermal method, which exhibited superior bifunctional photocatalytic performances for H₂O₂ production and the degradation of 2-mercaptobenzothiazole (MBT). Especially, the optimal sample 10ISZS achieved an H₂O₂ generation rate of 1304.25 μmol g⁻¹ h⁻¹ without oxygen bubbling or any sacrificial agent under visible light, which was 4.36 and 2.59 times more superior to those of pure In₂S₃ and ZnSe. Furthermore, 10ISZS demonstrated a high MBT removal efficiency of 94.3 % within 40 min, and these bifunctional performances also surpassed some reported heterostructures. The exceptional bifunctional photocatalytic performance of ISZS could be attributed to its close interface contact, matched band position and S-scheme charge transfer mechanism, which facilitated efficient charge separation and preserved strong redox capability to enhance the generation and utilization efficiency of superoxide radicals (•O₂⁻) and electrons (e⁻). This work provides insights into the importance of heterojunction engineering in boosting the bifunctional photocatalytic efficiency of S-scheme ZnSe-based photocatalytic systems for efficient and sustainable applications.

设计有效的s型异质结光催化系统产生H2O2和降解有机污染物是可持续发展的有前途的概念。然而，s型光催化剂体系在界面电荷转移的动力学过程和内部机理方面仍面临重大挑战。本文采用原位溶剂热法，将ZnSe纳米颗粒负载在In2S3纳米片上，形成紧密的界面接触，构建了一种新型的S-scheme In2S3/ZnSe （ISZS）异质结，该异质结在H2O2生成和2-巯基苯并噻唑（MBT）降解方面表现出优异的双功能光催化性能。最优样品10ISZS在无氧鼓泡和任何牺牲剂的情况下，H2O2的生成速率为1304.25 μmol g−1 h−1，分别是纯In2S3和ZnSe的4.36和2.59倍。此外，10ISZS在40 min内表现出高达94.3%的MBT去除效率，并且这些双功能性能也超过了一些报道的异质结构。ISZS具有优异的双功能光催化性能，主要归因于其紧密的界面接触、匹配的能带位置和S-scheme电荷转移机制，有利于有效的电荷分离，并保持了较强的氧化还原能力，从而提高了超氧自由基（•O2−）和电子（e−）的生成和利用效率。这项工作提供了异质结工程在提高S-scheme znse基光催化系统的双功能光催化效率方面的重要性，以实现高效和可持续的应用。

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引用次数: 0

Harnessing light for antimicrobial action: light-driven inactivation of Gram-positive bacteria by boronic acid-based zinc(II) phthalocyanines 利用光进行抗菌作用：以硼酸为基础的锌（II）酞菁对革兰氏阳性细菌的光驱动失活

IF 4.7 3区化学 Q2 CHEMISTRY, PHYSICAL

Journal of Photochemistry and Photobiology A-chemistry

Pub Date : 2025-12-23 DOI: 10.1016/j.jphotochem.2025.117007

Daiane N. Maronde , José E. Rodríguez-Borges , Adelaide Almeida , Leandro M.O. Lourenço

Photodynamic inactivation (PDI) has emerged as an efficient approach to combat resistant pathogens, particularly Gram-positive bacteria such as Staphylococcus aureus. In this study, we report the synthesis, characterization, and antimicrobial evaluation of three novel zinc(II) phthalocyanines (Pcs) functionalized with 4-mercaptophenylboronic acid units (tetra-substituted ZnPc 1, octa-substituted ZnPc 2, and octa-substituted fluorinated ZnPc 3). Their PDI performance was investigated against S. aureus at two concentrations (5.0 and 10.0 μM) under white light irradiation at 100 mW cm⁻² (up to 60 min; total light dose 360 J cm⁻²), both in the absence and presence of potassium iodide (KI). The ZnPc 1 demonstrated potent activity against S. aureus, reducing bacterial counts by approximately 4 log units at 5 μM and nearly 7 log units at 10 μM after 60 min of light irradiation. Remarkably, upon addition of KI, inactivation of S. aureus to the detection limit of the method was achieved within 30 min at both concentrations. The ZnPc 2 exhibited the most potent effect, leading to inactivation to the detection limit of the method within only 15 min with KI at both concentrations, and without KI at 30 min (10 μM) or 45 min (5 μM). The ZnPc 3 required KI to achieve bacterial inactivation, with reductions observed after 60 min at 5 and 10 μM. These results demonstrate that structural modification with functional units strongly influences the antimicrobial efficacy of ZnPcs 1–3, with the ZnPc 2 emerging as the most promising drug. The synergistic role of KI further highlights the potential of these boronic acid-functionalized phthalocyanines as efficient photosensitizers for photodynamic therapy against Gram-positive pathogens.

光动力失活（PDI）已成为对抗耐药病原体，特别是革兰氏阳性细菌如金黄色葡萄球菌的有效方法。在这项研究中，我们报道了三种新型的4-巯基苯硼酸功能化的锌（II）酞菁（Pcs）的合成、表征和抗菌评价（四取代ZnPc 1，八取代ZnPc 2和八取代氟化ZnPc 3）。在100 mW cm - 2的白光照射下（持续60 min，总光剂量360 J cm - 2），在没有和存在碘化钾（KI）的情况下，研究了两种浓度（5.0和10.0 μM）下对金黄色葡萄球菌的PDI性能。ZnPc 1对金黄色葡萄球菌具有较强的抑制活性，在光照60 min后，在光照5 μM时减少约4个对数单位，在光照10 μM时减少近7个对数单位。值得注意的是，在加入KI后，在两种浓度下，金黄色葡萄球菌的失活均在30分钟内达到该方法的检测限。ZnPc 2表现出最强的失活效果，在两种浓度的KI作用下，仅在15 min内即可达到该方法的检出限，而在没有KI作用的情况下，在30 min （10 μM）或45 min （5 μM）下即可达到该方法的失活限。ZnPc 3需要KI才能实现细菌灭活，在5 μM和10 μM下60分钟后观察到细菌的减少。这些结果表明，功能单元的结构修饰强烈影响znpc1 - 3的抗菌效果，其中znpc2是最有希望的药物。KI的协同作用进一步强调了这些硼酸功能化酞菁作为有效光敏剂的潜力，可用于针对革兰氏阳性病原体的光动力治疗。

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引用次数: 0

A carbohydrazide-based Schiff base derivative for colorimetric and fluorometric detection of Cu2+, Co2+, and OH− ions: Validation through DFT, test strips, cellular imaging, and real water analysis 一种基于碳酰肼的希夫碱衍生物，用于比色和荧光检测Cu2+， Co2+和OH -离子：通过DFT，试纸，细胞成像和实际水分析验证

IF 4.7 3区化学 Q2 CHEMISTRY, PHYSICAL

Journal of Photochemistry and Photobiology A-chemistry

Pub Date : 2025-12-23 DOI: 10.1016/j.jphotochem.2025.117013

Sanket Kadam , Muthaiah Shellaiah , Wen-Tai Li , Purav Badani , Kamlesh Awasthi , Nobuhiro Ohta , Ganesh Chaturbhuj

Advancing a one-pot Schiff base probe for multi-analyte detection is still in demand. Herein, a carbohydrazide and 8-hydroxyjulolidine-9-carboxaldehyde-derived Schiff base probe, namely CHSP1, is reported as a sensor for copper (Cu²⁺), cobalt (Co²⁺), and hydroxide (OH⁻) in dimethyl sulfoxide (DMSO). Relevant to distinct ultraviolet (UV)-Visible peaks, the CHSP1 shows strong photoluminescence (PL) quenching at 505 nm for Cu²⁺/Co²⁺, and a distinct PL Turn-On signal at 430 nm for OH⁻. For Cu²⁺/Co²⁺ and OH⁻, the optimal operating pH values are established as 6–8 and 6–10. From Job's plots, the stoichiometries of CHSP1 + Cu²⁺, CHSP1 + Co²⁺, and CHSP1 + OH- are determined to be 1:1, 1:1, and 1:2, respectively, as supported by mass data. Linear PL responses of CHSP1 to Cu²⁺, Co²⁺, and OH⁻ are documented as 0.1–90 μM, 0.1–90 μM, and 0.1–500 μM with the appraised detection limits (LODs) of 469 nM (nM = 10⁻⁹ M), 349 nM, and 81.5 nM, respectively. The association constant (K_a) values of CHSP1 to Cu²⁺, Co²⁺, and OH⁻ ions are determined to be 7.175 × 10⁴ M⁻¹, 1.428 × 10⁵ M^-1, and 8.822 × 10⁵ M⁻² respectively. The binding mode and mechanism have been validated through extensive UV/PL, ¹H NMR titrations, Time-Resolved Photoluminescence (TRPL), and density functional theory (DFT) investigations. Test strip analysis, cellular imaging, and 18 data points from real-water analysis validate the sensing applications, which could advance similar designs in the future.

推进一罐希夫碱探针的多分析物检测仍然是有需求的。本文报道了一种碳肼和8-羟基julolidin -9-羧醛衍生的希夫碱探针CHSP1，作为二甲基亚砜（DMSO）中铜（Cu2+）、钴（Co2+）和氢氧化物（OH−）的传感器。CHSP1具有明显的紫外可见峰，Cu2+/Co2+在505 nm处表现出强烈的光致发光（PL）猝灭，OH−在430 nm处表现出明显的PL开启信号。Cu2+/Co2+和OH−的最佳操作pH值分别为6-8和6-10。根据Job的图，CHSP1 + Cu2+、CHSP1 + Co2+和CHSP1 + OH-的化学计量量分别为1:1、1:1和1:2，并得到了大量数据的支持。CHSP1对Cu2+、Co2+和OH -的线性PL响应范围分别为0.1 ~ 90 μM、0.1 ~ 90 μM和0.1 ~ 500 μM，鉴定检出限（lod）分别为469 nM （nM = 10 ~ 9 M）、349 nM和81.5 nM。CHSP1与Cu2+、Co2+和OH -离子的缔合常数Ka值分别为7.175 × 104 M-1、1.428 × 105 M-1和8.822 × 105 M- 2。结合模式和机制已通过广泛的UV/PL， 1H NMR滴定，时间分辨光致发光（TRPL）和密度泛函理论（DFT）研究得到验证。测试条分析、细胞成像和来自真实水分析的18个数据点验证了传感应用，这可以推动未来类似的设计。

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引用次数: 0

Boosting photocatalytic hydrogen evolution with a S-scheme MgIn2S4/ZnIn2S4 heterojunction s型MgIn2S4/ZnIn2S4异质结促进光催化析氢

IF 4.7 3区化学 Q2 CHEMISTRY, PHYSICAL

Journal of Photochemistry and Photobiology A-chemistry

Pub Date : 2025-12-23 DOI: 10.1016/j.jphotochem.2025.117006

Yafei Zhang , Xiuxiu Tian , Wenfeng Xu , Hongqing Ma , Weina Mu , Chun Chang

Solar-driven water splitting for the generation of renewable hydrogen is a highly promising method to tackle the critical issues of environmental contamination and rising worldwide energy needs. Consequently, the development of highly efficient, stable photocatalysts with suppressed electron-hole recombination is of paramount importance. Herein, a S-scheme heterojunction composed of MgIn₂S₄ and ZnIn₂S₄ was constructed. At a 30 wt% loading, the composite catalyst exhibited a hydrogen evolution rate of 759 μmol·g⁻¹·h⁻¹ under simulated sunlight, which is 1.75 and 54.22 times higher than those of pure ZnIn₂S₄ and MgIn₂S₄, respectively. This enhancement is attributed to directed electron transfer and enhanced separation of photo-induced electron-hole pairs, resulting in significantly enhanced hydrogen production performance and excellent stability. These findings offer both theoretical and experimental insights for the rational design of advanced multinary sulfide photocatalysts.

太阳能驱动的水分解生产可再生氢是一种非常有前途的方法，可以解决环境污染和全球能源需求不断增长的关键问题。因此，开发高效、稳定、抑制电子-空穴复合的光催化剂是至关重要的。在此基础上，构建了由MgIn2S4和ZnIn2S4组成的S-scheme异质结。负载为30 wt%时，复合催化剂在模拟日光下的析氢速率为759 μmol·g−1·h−1，分别是纯ZnIn2S4和MgIn2S4的1.75和54.22倍。这种增强归因于定向电子转移和光致电子空穴对分离的增强，从而显著提高了产氢性能和优异的稳定性。这些发现为合理设计先进的多硫化物光催化剂提供了理论和实验见解。

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引用次数: 0

Can azulene-embedded nanographenes achieve efficient anti-Kasha fluorescence? Insights from non-adiabatic dynamics 嵌入azulene的纳米石墨烯能否实现高效的抗卡沙荧光？非绝热动力学的见解

IF 4.7 3区化学 Q2 CHEMISTRY, PHYSICAL

Journal of Photochemistry and Photobiology A-chemistry

Pub Date : 2025-12-23 DOI: 10.1016/j.jphotochem.2025.117012

Nikita A. Shekhovtsov, Mark B. Bushuev

The design of materials on the base of azulene-embedded benzenoid nanographenes and polycyclic aromatic hydrocarbons (PAHs) has garnered a steadily growing interest in the recent decade due to their unique electronic properties originating from the azulene core. While a huge success has been achieved in applying these PAHs in optoelectronic devices due to narrow HOMO-LUMO gap and near-infrared absorption, the potential for exploiting another azulene's intrinsic feature – anti-Kasha emission - remains unrealized. In this work, we employ non-adiabatic dynamics to study the excited state relaxation for two representative examples of azulene-embedded PAHs featuring azulene-naphthalene and azulene-phenyl cores, Az₂Nap₂ and Az₂Ph₂, and reveal the ultrafast decay of the S₂ state for both compounds in the picosecond range. According to the analysis of the vibronic coupling constants and normal modes associated with them, three key factors drive such rapid excited state relaxation: i) symmetry reduction from C_2v (azulene) to C₂ (PAHs); ii) the intrinsic vibrational activity of the azulene core, which remains active upon embedding it into PAH and iii) the vibrational activity of groups which bridge or fuse azulene units into a single PAH molecule. These findings challenge the well-known assumption that enhanced rigidity in azulene-embedded PAHs impedes non-radiative decay pathways and favors anti-Kasha emission, thus highlighting fundamental limitations for designing such materials. We establish that the strategic design of PAHs with maximized S₂–S₁ energy gaps must supersede the pursuit of structural rigidification as the paramount strategy for achieving efficient anti-Kasha emission.

由于其独特的电子特性源自于azulene核心，基于azulene嵌入的苯纳米石墨烯和多环芳烃（PAHs）的材料设计在最近十年中获得了稳步增长的兴趣。虽然这些多环芳烃在光电子器件中的应用取得了巨大的成功，但由于其窄小的HOMO-LUMO间隙和近红外吸收，利用另一种azulene的固有特性-抗kasha发射的潜力仍未实现。在这项工作中，我们采用非绝热动力学研究了两个具有代表性的Az2Nap2和Az2Ph2的az2萘和Az2Ph2的激发态弛豫，并揭示了这两种化合物的S2态在皮秒范围内的超快衰减。根据与之相关的振动耦合常数和正模的分析，有三个关键因素驱动这种快速激发态弛缓：1)从C2v （azulene）对称性还原为C2 (PAHs)；ii) azulene核心的固有振动活性，它在嵌入多环芳烃后仍保持活性；iii)桥接或融合azulene单元成单个多环芳烃分子的基团的振动活性。这些发现挑战了众所周知的假设，即azulene嵌入的多环芳烃的增强刚性阻碍了非辐射衰变途径并有利于反卡沙发射，从而突出了设计此类材料的基本局限性。我们建立了具有最大S2-S1能量间隙的多环芳烃战略设计必须取代追求结构刚性作为实现有效抗卡沙排放的首要策略。

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引用次数: 0