Journal of Photochemistry and Photobiology A-chemistry最新文献_第2页

Novel benzophenone derivatives photoinitiators based on carbazole group for deep curing and fast 3D printing 基于咔唑基团的新型二苯甲酮衍生物光引发剂，用于深度固化和快速 3D 打印

IF 4.1 3区化学 Q2 CHEMISTRY, PHYSICAL

Journal of Photochemistry and Photobiology A-chemistry

Pub Date : 2024-11-10 DOI: 10.1016/j.jphotochem.2024.116144

Shining Li , Guanhao Ma , Jinqing Qu

With the development of photopolymerization in thick film curing, the design and synthesis of effective photoinitiators are becoming increasingly critical. A series of photoinitiators (4-(dimethylamino)phenyl)(9-ethyl-9H-carbazol-3-yl)methanone (PECM), (4-(dimethylamino)phenyl)(9-phenyl-9H-carbazol-3-yl)methanone (PPCM), (9-allyl-9H-carbazol-3-yl)(4-(dimethylamino)phenyl)methanone (PACM), and (4-(dimethylamino)phenyl)(9-(hex-5-en-1-yl)-9H-carbazol-3-yl)methanone (PHCM) based on carbazole group were synthesized for thick film curing. These photoinitiators exhibited the maximum absorption wavelength red-shifted to 353 nm compared to BP and had high molar absorption coefficients (over 27,000 L·mol⁻¹·cm⁻¹). Under the irradiation of LED, the three-component system composed of photoinitiator, diphenyliodonium hexafluorophosphate, and triethanolamine could initiate the rapid photopolymerization of polyethylene glycol diacrylate (PEGDA 400). Under low intensity LED@405 nm (5 mW/cm²) irradiation, PHCM achieved a final double bond conversion (DC) of 98 % within 20 s, significantly higher than BP (65 %). Under the irradiation of LED@365 nm (5 mW/cm²), PHCM reached 99 % DC within 8 s, while BP reached 97 % within 20 s. This performance was attributed to the fact that the molar absorption coefficients of PHCM at 365 nm (30010 L·mol⁻¹·cm⁻¹) and 405 nm (746 L·mol⁻¹·cm⁻¹) were much higher than those of BP (71 L·mol⁻¹·cm⁻¹, 46 L·mol⁻¹·cm⁻¹). Additionally, curing depth of PHCM reached 8.4 cm after 100 s irradiation under LED@405 nm. PHCM also demonstrated excellent cell compatibility and migration ratio as low as 1.8 %, which was 1/5 of that of BP (9.5 %). Furthermore, PHCM was suitable for 3D printers with 4 s/layer. In addition, the initiation mechanism of the photoinitiator was studied by photodegradation and ESR tests.

随着光聚合技术在厚膜固化领域的发展，设计和合成有效的光引发剂变得越来越重要。一系列光引发剂（4-（二甲基氨基）苯基）（9-乙基-9H-咔唑-3-基）甲酮（PECM）、（4-（二甲基氨基）苯基）（9-苯基-9H-咔唑-3-基）甲酮（PPCM）、合成了基于咔唑基团的 (9-烯丙基-9H-咔唑-3-基)(4-(二甲基氨基)苯基)甲酮 (PACM) 和 (4-(二甲基氨基)苯基)(9-(己-5-烯-1-基)-9H-咔唑-3-基)甲酮 (PHCM)，用于厚膜固化。与 BP 相比，这些光引发剂的最大吸收波长红移至 353 nm，并具有较高的摩尔吸收系数（超过 27,000 L-mol-1-cm-1）。在 LED 的照射下，由光引发剂、二苯碘鎓六氟磷酸盐和三乙醇胺组成的三组分体系可引发聚乙二醇二丙烯酸酯（PEGDA 400）的快速光聚合。在低强度 LED@405 nm（5 mW/cm2）照射下，PHCM 在 20 秒内实现了 98% 的最终双键转化率（DC），显著高于 BP（65%）。在 365 纳米 LED@365 纳米（5 mW/cm2）的照射下，PHCM 在 8 秒内达到了 99% 的双键转化率，而 BP 在 20 秒内达到了 97% 的双键转化率。PHCM 在 365 纳米（30010 L-mol-1-cm-1）和 405 纳米（746 L-mol-1-cm-1）的摩尔吸收系数远高于 BP（71 L-mol-1-cm-1、46 L-mol-1-cm-1）。此外，在 LED@405 纳米波长下照射 100 秒后，PHCM 的固化深度达到 8.4 厘米。PHCM 还表现出优异的细胞相容性，迁移率低至 1.8%，是 BP（9.5%）的 1/5。此外，PHCM 适用于 4 秒/层的 3D 打印机。此外，还通过光降解和 ESR 测试研究了光引发剂的引发机制。

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引用次数: 0

Bright Blue-Light emitting cobalt doped CuS quantum dots: Photophysical studies and selective sensing application of ferric ion 明亮的蓝光发光掺钴 CuS 量子点：光物理研究和铁离子的选择性传感应用

IF 4.1 3区化学 Q2 CHEMISTRY, PHYSICAL

Journal of Photochemistry and Photobiology A-chemistry

Pub Date : 2024-11-09 DOI: 10.1016/j.jphotochem.2024.116137

Mitul Kalita, Mahabul Haque, Amarjyoti Mondal, Atanu Singha Roy

Surface-functionalized quantum dots (QDs) have garnered significant attention in recent years for a variety of applications, including LEDs, photovoltaics, sensing, bioimaging and biomedical domains due to their distinct optical features such as strong photoluminescence behavior, high quantum yields etc. However, formation of nontoxic QDs is very challenging for the researchers because of their lower optical properties as compared to Cd based QDs. The phenomenon of doping in semiconductor QDs is an effective way to achieve high opto-electrical properties in the host QDs. We have presented a low temperature colloidal synthesis of CuS QDs using cobalt (Co²⁺) as a doping agent with an exceptional stability at room temperature for 30 days. The photoluminescence (PL) properties of Co²⁺-doped CuS QDs exhibit a deep-blue emission at 420 nm resulting in excellent optical property with an improvement of photoluminescence quantum yield. Due to remarkable CIE chromaticity coordinates, good CCT values, and high colour purity, the synthesized Co²⁺-doped CuS QDs could be used extensively in LEDs and prove to be useful as blue phosphors. The synthesized Co²⁺-doped CuS QDs also act as a fluorescence probe in the detection of ferric ion (Fe³⁺) with high sensitivity, good selectivity, a low limit of detection (LOD) and limit of quantification (LOQ), of (4.99 ± 0.12) μM and (16.67 ± 0.40) μM, respectively.

近年来，表面功能化量子点（QDs）因其独特的光学特性，如强光致发光行为、高量子产率等，在 LED、光伏、传感、生物成像和生物医学等领域的各种应用中备受关注。然而，与镉基 QDs 相比，无毒 QDs 的光学特性较低，因此对研究人员来说，形成无毒 QDs 非常具有挑战性。半导体 QDs 中的掺杂现象是在宿主 QDs 中实现高光电特性的有效方法。我们介绍了一种以钴（Co2+）为掺杂剂的 CuS QDs 的低温胶体合成方法，该方法在室温下具有 30 天的超强稳定性。掺杂 Co2+ 的 CuS QDs 的光致发光（PL）特性在 420 纳米波长处呈现深蓝色发射，从而提高了光致发光量子产率，实现了优异的光学特性。由于合成的掺 Co2+ 的 CuS QDs 具有出色的 CIE 色度坐标、良好的 CCT 值和高色纯度，因此可广泛应用于 LED 中，并被证明是有用的蓝色荧光粉。合成的掺 Co2+ 的 CuS QDs 还可作为荧光探针检测铁离子 (Fe3+)，其灵敏度高、选择性好、检测限 (LOD) 低、定量限 (LOQ) 低，分别为 (4.99 ± 0.12) μM 和 (16.67 ± 0.40) μM。

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引用次数: 0

Mechanism of glycerol oxidation on bismuth vanadate photoanodes: Influence of tantalum doping 钒酸铋光阳极上的甘油氧化机制：掺杂钽的影响

IF 4.1 3区化学 Q2 CHEMISTRY, PHYSICAL

Journal of Photochemistry and Photobiology A-chemistry

Pub Date : 2024-11-08 DOI: 10.1016/j.jphotochem.2024.116143

Hitoshi Kusama, Kazuhiro Sayama

This study investigated the mechanisms underlying the photoelectrochemical oxidation of glycerol to dihydroxyacetone (DHA) and glyceraldehyde (GLAD) on BiVO₄ and Bi–O–Ta species using density functional theory calculations. The results revealed that for both products and metal-oxides, the first proton-coupled electron-transfer (PCET) step, which forms a carbon-centered radical, served as the rate-limiting step. The formation of DHA from a secondary-carbon-centered radical encountered lower energy barriers compared to the formation of GLAD from a primary-carbon-centered radical, indicating the favorability of the DHA production pathway. The differences between the energy inputs required for DHA and GLAD production were greater on the Bi–O–Ta species compared to the BiVO₄. Furthermore, the production of formic acid (FA) from glycerol via GLAD, involving three H₂O molecules and eight PCET steps, encountered greater energy barriers on Bi–O–Ta species than on BiVO₄. These computational results confirm that the Bi–O–Ta species enhances DHA generation from glycerol while suppressing the production of unfavorable byproducts such as GLAD and FA. Correspondingly, the Ta-doped BiVO₄ photoanode achieves a greater Faradaic efficiency than the BiVO₄ photoanode and approximately 100% selectivity for DHA in acidic media owing to the Bi–O–Ta species formed on the surface.

本研究利用密度泛函理论计算研究了甘油在 BiVO4 和 Bi-O-Ta 物种上光电化学氧化成二羟基丙酮（DHA）和甘油醛（GLAD）的机理。结果表明，对于两种产物和金属氧化物而言，形成碳中心自由基的第一个质子耦合电子转移（PCET）步骤是限速步骤。与一级碳中心自由基形成 GLAD 相比，二级碳中心自由基形成 DHA 所遇到的能量障碍更低，这表明 DHA 的生成途径更为有利。与 BiVO4 相比，Bi-O-Ta 物种生产 DHA 和 GLAD 所需的能量输入差异更大。此外，通过 GLAD 从甘油中生产甲酸（FA）涉及三个 H2O 分子和八个 PCET 步骤，在 Bi-O-Ta 物种上遇到的能量障碍比在 BiVO4 上更大。这些计算结果证实，Bi-O-Ta 物种在抑制 GLAD 和 FA 等不利副产物产生的同时，提高了从甘油中生成 DHA 的能力。相应地，由于表面形成了 Bi-O-Ta 物种，掺杂 Ta 的 BiVO4 光阳极比 BiVO4 光阳极的法拉第效率更高，在酸性介质中对 DHA 的选择性约为 100%。

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引用次数: 0

Antioxidant capacity of edaravone, quercetin, and myricetin involving probabilistic fluctuations using eosin-Y and eosin-B as fluorescent probes in the ORAC assay 在 ORAC 试验中使用曙红-Y 和曙红-B 作为荧光探针，测定依达拉奉、槲皮素和杨梅素涉及概率波动的抗氧化能力

IF 4.1 3区化学 Q2 CHEMISTRY, PHYSICAL

Journal of Photochemistry and Photobiology A-chemistry

Pub Date : 2024-11-08 DOI: 10.1016/j.jphotochem.2024.116142

Miwa Takatsuka , Satoru Goto , Kota Moritake , Yosuke Shimada , Tomohiro Tsuchida

The oxygen radical absorbance capacity (ORAC) assay measures the antioxidant activity of the antioxidants through competitive consumption of peroxyl radicals relative to a fluorescent probe. This study evaluated fluorescein (FLH), eosin Y, and eosin B in ORAC assays using quantum computations. In ORAC-FLH assays, trolox (TRO) and ascorbic acid (ASC) showed fluorescence decay kinetics with a lag time, blocking initial reactions in the quenching cascade. Eosins were more reactive towards peroxyl radicals, making TRO assessment infeasible in ORAC-eosin assays. Quercetin and myricetin exhibited sigmoidal curve drifts proportional to squared and 3/2-ordered incubation times, indicating probabilistic fluorescence decay. Edaravone (EDA) weakly inhibited initial reactions, with accelerated quenching over time. In ORAC-eosin assays, flavonoids and EDA showed indistinguishable behavior due to high eosin reactivity. ORAC-FLH did not significantly assess BHT, though a dose-dependent change in half-life was noted. This study suggests broad applications for ORAC-eosin assays and potential for future comparative research.

氧自由基吸收能力（ORAC）测定法通过过氧自由基相对于荧光探针的竞争性消耗来测量抗氧化剂的抗氧化活性。本研究利用量子计算对 ORAC 试验中的荧光素（FLH）、曙红 Y 和曙红 B 进行了评估。在 ORAC-FLH 试验中，曲洛毒素（TRO）和抗坏血酸（ASC）显示出滞后的荧光衰减动力学，阻断了淬灭级联中的初始反应。曙红对过氧自由基的反应性更强，因此在 ORAC-曙红测定中无法对 TRO 进行评估。槲皮素和杨梅素的曲线漂移与孵育时间的平方和 3/2 排序成正比，表明荧光衰减具有概率性。依达拉奉（EDA）对初始反应有微弱的抑制作用，但随着时间的推移会加速淬灭。在 ORAC-曙红测定中，由于曙红反应活性高，类黄酮和 EDA 的表现难以区分。ORAC-FLH 对 BHT 的评估效果不明显，但半衰期的变化与剂量有关。这项研究表明，ORAC-曙红测定法具有广泛的应用前景和未来比较研究的潜力。

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引用次数: 0

A novel azo-triazolopyridine-based dual naked-eye chemosensor for the selective detection of CN− and Cu2+ ions 基于偶氮-三唑并吡啶的新型裸眼双化学传感器，用于选择性检测 CN- 和 Cu2+ 离子

IF 4.1 3区化学 Q2 CHEMISTRY, PHYSICAL

Journal of Photochemistry and Photobiology A-chemistry

Pub Date : 2024-11-07 DOI: 10.1016/j.jphotochem.2024.116140

Sarah Poormoradkhan Melal, Behzad Khalili, Nosrat O. Mahmoodi, Meysam Pasandideh Nadamani

A new chemosensor incorporating a triazolopyridine and an azo chromophore was synthesized and employed as a colorimetric sensor. Visual investigations for detecting anions and cations revealed that the sensor acts as a highly sensitive and selective chromogenic detector for cyanide (CN⁻) and copper (Cu²⁺) ions. The observable color change from yellow to deep orange for Cu²⁺ and from yellow to purple for CN⁻ allows for detecting these ions without the need for advanced equipment, even with the naked eye. The sensor’s limit of detection (LOD) was determined to be 0.02 μM for CN⁻ ions and 1.13 μM for Cu²⁺ ions. The Job plot indicated that the sensor binds to CN⁻ and Cu²⁺ with a stoichiometric ratio of 1:1 and 2:1, respectively. The ability to accurately and selectively distinguish Cu²⁺ and CN⁻ ions makes this sensor valuable for various analytical applications, including environmental monitoring and chemical analysis. Its capacity to produce noticeable and distinct color changes enables the rapid and straightforward detection of these hazardous ions, making it a practical choice for real-world applications. The quantum yield of A-TAP/Cu²⁺ was 54 % at a λ_max (maximum absorbance) of 450 nm, while that of A-TAP/CN⁻ was 62 % at 538 nm, using a reference sensor with a λ_max of 380 nm.

我们合成了一种包含三唑并吡啶和偶氮发色团的新型化学传感器，并将其用作比色传感器。检测阴离子和阳离子的目测结果表明，该传感器对氰化物（CN-）和铜离子（Cu2+）具有高灵敏度和选择性。Cu2+ 的颜色从黄色变为深橙色，CN- 的颜色从黄色变为紫色，这种可观察到的颜色变化无需先进设备，甚至用肉眼就能检测到这些离子。传感器的检测限（LOD）被确定为 CN- 离子 0.02 μM，Cu2+ 离子 1.13 μM。约伯图表明，传感器与 CN- 和 Cu2+ 的结合比例分别为 1:1 和 2:1。这种传感器能够准确并有选择性地区分 Cu2+ 和 CN- 离子，因此在环境监测和化学分析等各种分析应用中具有重要价值。它能够产生明显而独特的颜色变化，从而能够快速、直接地检测这些有害离子，使其成为实际应用中的一个实用选择。使用 λmax 为 380 nm 的参考传感器，A-TAP/Cu2+ 在 450 nm λmax（最大吸光度）处的量子产率为 54%，而 A-TAP/CN- 在 538 nm 处的量子产率为 62%。

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引用次数: 0

Fluorescent scaffold integrating 2-aryl-1,2,3-triazole and thiazole rings with tuneable optical properties. Fundamental aspects and application prospects 集成 2-芳基-1,2,3-三唑和噻唑环并具有可调光学特性的荧光支架。基础方面和应用前景

IF 4.1 3区化学 Q2 CHEMISTRY, PHYSICAL

Journal of Photochemistry and Photobiology A-chemistry

Pub Date : 2024-11-01 DOI: 10.1016/j.jphotochem.2024.116104

Vitalii A. Krasilnikov , Timur O. Fomin , Maria V. Vargina , Artem S. Minin , Pavel A. Slepukhin , Enrico Benassi , Nataliya P. Belskaya

A fluorescent scaffold was designed and synthesised by the conjugating of the 1,2,3-triazole ring with aryl- or diarylthiazole systems. As a result, two series of thiazole-1,2,3-triazole fluorophores were prepared by the Hantzsch reaction and Suzuki-Miyaura coupling, namely 4-aryl-2-(2-aryl-2H-1,2,3-triazol-4-yl)thiazole (DATTs) and 4,5-diaryl-2-(2-aryl-2H-1,2,3-triazol-4-yl)thiazole (TATTs). Their structures were investigated by XRD and quantum mechanical calculations at DFT level. All the novel compounds were studied under different conditions by UV–vis absorption and fluorescent spectroscopy and TD-DFT calculations. Strong solvato(fluoro)chromism was registered, resulting in a two- or three colour fluorescence depending on solvent polarity, accompanied by an increase in emission intensity when solvent polarity increases. Concentration dependent emissions were found, and DATTs and TATTs exhibited red-shifted absorption and emission compared to the parent triazoles and sensitivity to polar media. Biological tests demonstrated the biocompatibility of the synthesised fluorophores and their low or null toxicity. Multicolour fluorescence of DATTs and TATTs as a function of the excitation wavelength and dye localisation was demonstrated in cell experiments.

通过将 1,2,3-三唑环与芳基或二芳基噻唑系统共轭，设计并合成了一种荧光支架。结果，通过汉茨奇反应和铃木-宫浦偶联制备出了两个系列的噻唑-1,2,3-三唑荧光团，即 4-芳基-2-(2-芳基-2H-1,2,3-三唑-4-基)噻唑（DATTs）和 4,5-二芳基-2-(2-芳基-2H-1,2,3-三唑-4-基)噻唑（TATTs）。通过 XRD 和 DFT 级量子力学计算研究了它们的结构。在不同条件下，通过紫外-可见吸收光谱、荧光光谱和 TD-DFT 计算对所有新型化合物进行了研究。研究发现，该化合物具有很强的溶解（氟）发色性，根据溶剂极性的不同会产生两种或三种颜色的荧光，当溶剂极性增加时，发射强度也会增加。与母体三唑相比，DATTs 和 TATTs 表现出红移吸收和发射，并对极性介质敏感。生物测试表明，合成的荧光团具有生物相容性和低毒性或无毒性。细胞实验表明，DATTs 和 TATTs 的多色荧光是激发波长和染料定位的函数。

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引用次数: 0

Photoelectrodegradation and sensing of pentachlorophenol using In and Mn metalated porphyrins in the presence of TiO2 nanoparticles 在 TiO2 纳米粒子存在下使用 In 和 Mn 金属化卟啉对五氯苯酚进行光电降解和传感

IF 4.1 3区化学 Q2 CHEMISTRY, PHYSICAL

Journal of Photochemistry and Photobiology A-chemistry

Pub Date : 2024-11-01 DOI: 10.1016/j.jphotochem.2024.116118

Mbulelo Jokazi, Sixolile Centane, Philani Mashazi, Tebello Nyokong

This work reports on the study of electrochemical sensing, photodegradation and photoelectrodegradation of pentachlorophenol (PCP). Pentachlorophenol is a toxic compound that is used in the pharmaceutical industries and agriculture. It contaminates water through highly improper disposals and is carcinogenic. Electrochemical sensing was carried out using cyclic voltammetry to detect PCP using indium and manganese metalated porphyrins, TiO₂ nanoparticles and TiO₂-metalloporphyrin composite as catalysts. A conductive indium tin oxide (ITO) was used as a semiconductor. The TiO₂-metalloporphyrin complexes showed the best catalytic activity in both sensing and degradation. Photoelectrodegradation resulted in high efficiency compared to photodegradation and the introduction of H₂O₂ resulted in complete degradation of PCP.

本研究报告介绍了五氯苯酚（PCP）的电化学传感、光降解和光电降解研究。五氯苯酚是一种有毒化合物，主要用于制药业和农业。由于处理不当，五氯苯酚会污染水源，并具有致癌性。使用铟和锰金属化卟啉、TiO2 纳米粒子和 TiO2-金属卟啉复合材料作为催化剂，采用循环伏安法进行电化学传感，检测五氯苯酚。导电铟锡氧化物（ITO）被用作半导体。二氧化钛-金属卟啉复合物在传感和降解方面都表现出最佳的催化活性。与光降解相比，光电降解的效率更高，而引入 H2O2 则可使五氯苯酚完全降解。

引用次数: 0

Three multifunctional difluoroboron fluorescent dyes with five member N-heterocyclic ring for mechanofluorochromic behaviors, the ink-free writing and latent fingerprints imaging 三种具有五个 N-杂环的多功能二氟硼荧光染料，可用于机械氟变色行为、无墨书写和潜在指纹成像

IF 4.1 3区化学 Q2 CHEMISTRY, PHYSICAL

Journal of Photochemistry and Photobiology A-chemistry

Pub Date : 2024-11-01 DOI: 10.1016/j.jphotochem.2024.116125

Chunlin Chen , Jiazhuang Tian , Shan Li , Shulin Gao , Yanhua Yang , Xiangguang Li , Jin Zhang

To further advance the development of multifunctional fluorescent dyes, three difluoroboron compounds (F-1, F-2, and F-3) containing five-membered N-heterocyclic ring moieties that act as the electron-withdrawing units were synthesized. It was observed that compound F-1, which incorporated a 1,2,4-triazole segment, and compound F-3 with 1,2,3-triazole portion exhibited aggregation-induced emission activities suitable for latent fingerprints imaging. In contrast, compound F-2 featuring a pyrazole unit demonstrated an aggregation-caused quenching phenomenon. Additionally, all three compounds displayed mechanofluorochromic behaviors. Specifically, the emission spectra of compound F-1 in the solid state experienced only a slight shift of approximately 5 nm upon grinding, however, compound F-2 underwent a red shift from 475 to 501 nm while compound F-3 shifted from 482 to 507 nm. Furthermore, both compounds F-2 and F-3 could be utilized in ink-free writing applications. Notably, the safety paper prepared using compound F-2 was designed for single-use due to its irreversible mechanofluorochromic behavior, conversely, the safety paper derived from compound F-3 was rewritable owing to its reversible mechanofluorochromic behavior. It provided a foundation for exploration the application of multifunctional difluoroboron compounds with 1,2,3-triazole moiety.

为了进一步推动多功能荧光染料的开发，研究人员合成了三种二氟硼化合物（F-1、F-2 和 F-3），它们含有五元 N-杂环分子作为电子吸收单元。结果表明，含有 1,2,4- 三氮唑部分的化合物 F-1 和含有 1,2,3- 三氮唑部分的化合物 F-3 具有适合潜指纹成像的聚集诱导发射活性。相比之下，含有吡唑单元的化合物 F-2 则表现出聚集引起的淬灭现象。此外，这三种化合物都显示出机械氟变色行为。具体来说，固态化合物 F-1 的发射光谱在研磨时仅发生约 5 纳米的轻微偏移，而化合物 F-2 则发生了从 475 纳米到 501 纳米的红色偏移，化合物 F-3 则从 482 纳米偏移到 507 纳米。此外，化合物 F-2 和 F-3 都可用于无墨书写。值得注意的是，使用化合物 F-2 制备的安全纸因其不可逆的机械氟变色行为而设计为一次性使用，相反，由化合物 F-3 制备的安全纸因其可逆的机械氟变色行为而可重复书写。这为探索具有 1,2,3-三唑分子的多功能二氟硼化合物的应用奠定了基础。

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引用次数: 0

The role of process parameters on photooxidative degradation of 2,4-D herbicide using TiO2 nanoparticles: Kinetic and mechanistic study 使用 TiO2 纳米粒子的过程参数对 2,4-D 除草剂光氧化降解的作用：动力学和机理研究

IF 4.1 3区化学 Q2 CHEMISTRY, PHYSICAL

Journal of Photochemistry and Photobiology A-chemistry

Pub Date : 2024-10-31 DOI: 10.1016/j.jphotochem.2024.116120

Lenka Belháčová , Taťána Supiňková , Darina Smržová , Vlastimil Fíla

This systematic study investigates the effect of a wide range of TiO₂ nanoparticles on the kinetics and mechanism of photocatalytic degradation of the herbicide 2,4-D (2,4-dichlorophenoxyacetic acid). Changes in degradation rate, mineralization, and transformation pathways of 2,4-D correlated with nanoparticle physicochemical properties such as phase composition, size, and total pore volume. Primary intermediates, including hydroxylated chlorophenoxyacetic acids and 2,4-dichlorochlorophenoxy derivatives, were identified and their formation yields linked to the acid-base behaviour of 2,4-D. A comparison with homogeneous UV/H₂O₂-assisted degradation showed similar distribution of hydroxylated aromatic degradation intermediates as with large anatase nanoparticles (70 nm), while smaller particles facilitated pathways leading to the direct 2,4-D mineralization. DFT calculations supported experimental findings, and a scheme of the oxidative degradation of 2,4-D was proposed. Our results demonstrate that monitoring not only pollutant degradation but also overall mineralization is essential for evaluating photocatalysis efficiency and potential for practical applications.

本系统研究探讨了多种 TiO2 纳米粒子对光催化降解除草剂 2,4-D（2,4-二氯苯氧乙酸）的动力学和机理的影响。2,4-D的降解率、矿化度和转化途径的变化与纳米粒子的物理化学特性（如相组成、尺寸和总孔隙度）相关。确定了初级中间产物，包括羟基化的氯苯氧乙酸和 2,4-二氯氯苯氧衍生物，并将它们的形成率与 2,4-D 的酸碱行为联系起来。与均相紫外线/H2O2-辅助降解进行比较后发现，羟基化芳香族降解中间产物的分布与大锐钛型纳米颗粒（70 nm）相似，而较小的颗粒则有利于直接将 2,4-D 矿化。DFT 计算支持了实验结果，并提出了 2,4-D 的氧化降解方案。我们的研究结果表明，不仅要监测污染物降解情况，还要监测整体矿化情况，这对于评估光催化效率和实际应用潜力至关重要。

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引用次数: 0

Insight into solvation-regulated emission: Dissecting the switchable ESIPT/ESPT mechanisms in HNT molecule 洞察溶解调节发射：剖析 HNT 分子中可切换的 ESIPT/ESPT 机制

IF 4.1 3区化学 Q2 CHEMISTRY, PHYSICAL

Journal of Photochemistry and Photobiology A-chemistry

Pub Date : 2024-10-30 DOI: 10.1016/j.jphotochem.2024.116124

Wentian Zhang, Hang Yin, Chunyue Yu, Jie Guo, Ying Shi

As a crucial physical and chemical process, excited-state proton transfer has garnered significant interest among researchers due to its broad applications in photobiology. Recently, Wu et al. synthesized 3-(benzo[d]thiazol-2-yl) naphthalene-2-ol (HNT) molecule that exhibits excited-state intramolecular proton transfer (ESIPT) characteristic in THF while undergoes excited-state intermolecular proton transfer (ESPT) in aqueous solvent, which induce its solvent-regulated emission nature [Dyes and Pigments 182 (2020) 108665]. However, the dynamic interactions between the proton transfer mechanisms and the emission properties of the HNT molecule are yet to be fully elucidated. Specifically, the role of solvation effects in regulating inter- and intramolecular proton transfer, which leads to modifications in fluorescence properties, should be in-depth considered. In the present work, we delved into the ESIPT dynamics of the HNT molecule in aprotic THF, and examined the ESPT in protic aqueous solvent. Our findings indicate that the ESIPT process promotes the intersystem crossing process, which diminishes Keto* emission in THF solvent. Furthermore, the ESPT process within the HNT-water cluster accounts for the observed dual-fluorescence in aqueous solvent. This research illuminates the role of solute–solvent interactions in affecting the ESIPT/ESPT pathways, thereby clarifying the nature of HNT emission and providing an advantageous methodology for engineering novel dyes with customizable fluorescence characteristics.

激发态质子转移作为一种重要的物理和化学过程，由于其在光生物学中的广泛应用而备受研究人员的关注。最近，Wu 等人合成了 3-(苯并[d]噻唑-2-基)萘-2-醇（HNT）分子，该分子在四氢呋喃中表现出激发态分子内质子转移（ESIPT）特征，而在水溶剂中则发生激发态分子间质子转移（ESPT），从而诱导了其溶剂调控发射性质[染料和颜料 182 (2020) 108665]。然而，质子转移机制与 HNT 分子发射特性之间的动态相互作用仍有待全面阐明。具体来说，应深入考虑溶解效应在调节分子间和分子内质子转移中的作用，这将导致荧光特性的改变。在本研究中，我们深入研究了 HNT 分子在非沸腾四氢呋喃中的 ESIPT 动力学，并考察了其在质子水溶液中的 ESPT。我们的研究结果表明，ESIPT 过程促进了系统间的交叉过程，从而减少了 THF 溶剂中的 Keto* 发射。此外，HNT-水簇内的 ESPT 过程也是在水性溶剂中观察到双荧光的原因。这项研究揭示了溶质-溶剂相互作用在影响 ESIPT/ESPT 途径中的作用，从而阐明了 HNT 发射的性质，并为设计具有可定制荧光特性的新型染料提供了有利的方法。

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