Pub Date : 2026-06-01Epub Date: 2026-01-28DOI: 10.1016/j.dyepig.2026.113618
Zece Zhu , Runjing Yang , Ruiqi Mo , Ze-Yu Zhang , Di Tian , Ai-Guo Shen
Triplet-triplet annihilation (TTA) upconversion holds significant potential for enhancing semiconductor photocatalysis by converting low-energy photons into higher-energy emissions. However, the practical application of TTA is often limited by the poor solubility of conventional annihilators, which restricts light absorption and upconversion performance. In this study, a novel annihilator (DPA1) based on 9,10-diphenylanthracene (DPA) was developed by introducing branched alkyl chains, and diphenylmethane was identified as an optimal high-refractive-index solvent. This combination markedly improved the stability of annihilator solutions at high concentrations. Increasing the annihilator concentration in the TTA system effectively suppressed oxygen-induced triplet quenching and back-energy transfer to the sensitizer, resulting in a lower excitation threshold (Ith) and a higher upconversion efficiency (ФUC = 14.3 %), facilitating light energy utilization without deaeration. This optimized upconversion system enabled WO3 to more efficiently utilize visible light for generating hydroxyl radicals. We anticipate that high-concentration annihilator systems will provide bright upconversion luminescence and find broad applications in photocatalysis, photovoltaics, and related fields.
{"title":"High-concentration annihilators for efficient green-to-blue photon upconversion and photocatalytic production of hydroxyl radicals","authors":"Zece Zhu , Runjing Yang , Ruiqi Mo , Ze-Yu Zhang , Di Tian , Ai-Guo Shen","doi":"10.1016/j.dyepig.2026.113618","DOIUrl":"10.1016/j.dyepig.2026.113618","url":null,"abstract":"<div><div>Triplet-triplet annihilation (TTA) upconversion holds significant potential for enhancing semiconductor photocatalysis by converting low-energy photons into higher-energy emissions. However, the practical application of TTA is often limited by the poor solubility of conventional annihilators, which restricts light absorption and upconversion performance. In this study, a novel annihilator (<strong>DPA1</strong>) based on 9,10-diphenylanthracene (<strong>DPA</strong>) was developed by introducing branched alkyl chains, and diphenylmethane was identified as an optimal high-refractive-index solvent. This combination markedly improved the stability of annihilator solutions at high concentrations. Increasing the annihilator concentration in the TTA system effectively suppressed oxygen-induced triplet quenching and back-energy transfer to the sensitizer, resulting in a lower excitation threshold (<strong><em>I</em></strong><sub>th</sub>) and a higher upconversion efficiency (<em>Ф</em><sub>UC</sub> = 14.3 %), facilitating light energy utilization without deaeration. This optimized upconversion system enabled WO<sub>3</sub> to more efficiently utilize visible light for generating hydroxyl radicals. We anticipate that high-concentration annihilator systems will provide bright upconversion luminescence and find broad applications in photocatalysis, photovoltaics, and related fields.</div></div>","PeriodicalId":302,"journal":{"name":"Dyes and Pigments","volume":"249 ","pages":"Article 113618"},"PeriodicalIF":4.2,"publicationDate":"2026-06-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"146090585","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"工程技术","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Pub Date : 2026-06-01Epub Date: 2026-02-03DOI: 10.1016/j.dyepig.2026.113627
Zhiyuan Chen , Tong Li , Jinyu Song , Lai Hu , Songtao Ouyang , Hongjun Zhu , Xiao-Chun Hang , Senqiang Zhu , Rui Liu
Organic light-emitting diodes (OLEDs) are key candidates for next-generation high-efficiency, high-color-purity display and lighting technologies, with multiple-resonance thermally activated delayed fluorescence (MR-TADF) materials as critical emitters. Developing green MR-TADF emitters with high color purity typically requires multi-boron or strongly π-expanded frameworks. In this work, two MR-TADF emitters, CzBNIDID and CzBNIDID-DPA, were developed and synthesized by employing the indolo[3,2-b]indole (IDID) donor unit to enable efficient green emission within a minimal monoboron MR architecture. The IDID unit serves as an effective nitrogen-containing donor and provides substantial conjugation extension, enabling narrowband green emission at 522-525 nm. Its rigid fused skeleton forms a large planar framework that suppresses molecular vibrational coupling, resulting in photoluminescence quantum yields above 90%. Devices based on the two IDID-containing emitters deliver external quantum efficiencies up to 18.8 % with only 17.6% efficiency roll-off at 1000 cd m−2, confirming that effective green MR-TADF performance can be achieved without multi-boron or highly extended MR frameworks. These findings validate the effectiveness of indolo[3,2-b]indole as a robust donor module and provide a promising molecular develop strategy for high-performance green MR-TADF materials.
有机发光二极管（oled）是下一代高效、高色纯度显示和照明技术的关键候选者，多共振热激活延迟荧光（MR-TADF）材料是关键的发射体。开发具有高色纯度的绿色MR-TADF发射器通常需要多硼或强π扩展框架。在这项工作中，利用吲哚[3,2-b]吲哚（IDID）供体单元开发和合成了两个MR- tadf发射器CzBNIDID和CzBNIDID- dpa，从而在最小的单硼MR结构中实现高效的绿色发射。IDID单元作为有效的含氮供体，提供了大量的共轭延伸，实现了522-525 nm的窄带绿色发射。其刚性融合骨架形成一个大的平面框架，抑制分子振动耦合，导致光致发光量子产率在90%以上。基于两个含idd的发射器的器件提供高达18.8%的外部量子效率，在1000 cd m−2时只有17.6%的效率滚降，证实了有效的绿色MR- tadf性能可以在没有多硼或高度扩展的MR框架的情况下实现。这些发现验证了吲哚[3,2-b]吲哚作为一个强大的供体模块的有效性，并为高性能绿色MR-TADF材料的分子开发提供了一个有前途的策略。
{"title":"Indolo[3,2-b]indole-based monoboron multi-resonance TADF materials toward high-efficiency green OLEDs","authors":"Zhiyuan Chen , Tong Li , Jinyu Song , Lai Hu , Songtao Ouyang , Hongjun Zhu , Xiao-Chun Hang , Senqiang Zhu , Rui Liu","doi":"10.1016/j.dyepig.2026.113627","DOIUrl":"10.1016/j.dyepig.2026.113627","url":null,"abstract":"<div><div>Organic light-emitting diodes (OLEDs) are key candidates for next-generation high-efficiency, high-color-purity display and lighting technologies, with multiple-resonance thermally activated delayed fluorescence (MR-TADF) materials as critical emitters. Developing green MR-TADF emitters with high color purity typically requires multi-boron or strongly π-expanded frameworks. In this work, two MR-TADF emitters, <strong>CzBNIDID</strong> and <strong>CzBNIDID-DPA</strong>, were developed and synthesized by employing the indolo[3,2-b]indole (IDID) donor unit to enable efficient green emission within a minimal monoboron MR architecture. The IDID unit serves as an effective nitrogen-containing donor and provides substantial conjugation extension, enabling narrowband green emission at 522-525 nm. Its rigid fused skeleton forms a large planar framework that suppresses molecular vibrational coupling, resulting in photoluminescence quantum yields above 90%. Devices based on the two IDID-containing emitters deliver external quantum efficiencies up to 18.8 % with only 17.6% efficiency roll-off at 1000 cd m<sup>−2</sup>, confirming that effective green MR-TADF performance can be achieved without multi-boron or highly extended MR frameworks. These findings validate the effectiveness of indolo[3,2-b]indole as a robust donor module and provide a promising molecular develop strategy for high-performance green MR-TADF materials.</div></div>","PeriodicalId":302,"journal":{"name":"Dyes and Pigments","volume":"249 ","pages":"Article 113627"},"PeriodicalIF":4.2,"publicationDate":"2026-06-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"146184781","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"工程技术","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Aromatic polyamides (aramids) featuring dual triarylamine cores in the repeating unit were synthesized through phosphorylation polyamidation using 4,4′-oxydibenzoic acid and three bis(triarylamine)-diamine monomers, each with varying aromatic π-bridges, specifically 1,4-phenylene, naphthalene-2,6-diyl, and pyrene-1,6-diyl groups. These aramids demonstrated excellent solubility in polar organic solvents, enabling the formation of flexible and robust films via solution casting. They demonstrated significant thermal stability, characterized by moderate glass transition temperatures (236–262 °C), negligible weight loss below 400 °C, and high char yields (exceeding 60 % at 800 °C in nitrogen). The polymer films displayed reversible redox processes and pronounced color changes during cyclic voltammetry scanning within the range of 0–1.2 V. The structural effects of the aromatic π-bridges between the triarylamine cores on both the oxidation potential and electrochromic stability of the aramids were investigated. Notably, for aramids with greater separation between the triarylamine centers, the oxidation onset potential increased, while electrochromic stability decreased.
{"title":"Effects of π-bridges on the electrochemical and electrochromic properties of bis(triarylamine)-based aramids","authors":"Sheng-Huei Hsiao , Yaw-Terng Chern , Qun Zhang , Meng-Dong Lee , Nien-Chen Tsai","doi":"10.1016/j.dyepig.2026.113585","DOIUrl":"10.1016/j.dyepig.2026.113585","url":null,"abstract":"<div><div>Aromatic polyamides (aramids) featuring dual triarylamine cores in the repeating unit were synthesized through phosphorylation polyamidation using 4,4′-oxydibenzoic acid and three bis(triarylamine)-diamine monomers, each with varying aromatic π-bridges, specifically 1,4-phenylene, naphthalene-2,6-diyl, and pyrene-1,6-diyl groups. These aramids demonstrated excellent solubility in polar organic solvents, enabling the formation of flexible and robust films via solution casting. They demonstrated significant thermal stability, characterized by moderate glass transition temperatures (236–262 °C), negligible weight loss below 400 °C, and high char yields (exceeding 60 % at 800 °C in nitrogen). The polymer films displayed reversible redox processes and pronounced color changes during cyclic voltammetry scanning within the range of 0–1.2 V. The structural effects of the aromatic π-bridges between the triarylamine cores on both the oxidation potential and electrochromic stability of the aramids were investigated. Notably, for aramids with greater separation between the triarylamine centers, the oxidation onset potential increased, while electrochromic stability decreased.</div></div>","PeriodicalId":302,"journal":{"name":"Dyes and Pigments","volume":"249 ","pages":"Article 113585"},"PeriodicalIF":4.2,"publicationDate":"2026-06-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"146036634","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"工程技术","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Pub Date : 2026-06-01Epub Date: 2026-01-21DOI: 10.1016/j.dyepig.2026.113590
Paula Nabais , Mara Espírito Santo , Mila Crippa , Natércia Teixeira , Dominique Cardon
For millennia, organic dyes have been used in artworks such as textiles and have great artistic and historic value. They may provide clues to the understanding of the technology behind an artwork's production. The characterization of natural organic colourants in artworks is still a challenge to this day, and of the natural dyes used in cultural heritage, yellows are some of the most difficult to identify.
This paper explores the potential of combining molecular fluorescence in the visible range with high-performance liquid chromatography coupled with diode-array detection, to disclose historical dye formulations.
By analysing historically accurate reconstructions following recipes from two 18th c. French master dyers, Antoine Janot and Paul Gout, it was possible to demonstrate that molecular fluorescence is highly sensitive to the presence of specific dye ingredients and different use of recipes. Luteolin (Lut) and Luteolin 7-O-glucoside (Lut-7-O-glc) were identified as the main compounds, with the first being extracted in higher amounts, especially in Janot's variations. The analytical data demonstrated that molecular fluorescence is very sensitive to recipe differences: the presence of tartar correlated with a higher Lut presence, and the use of lime induced a slight shift in the emission maxima, even without affecting the spectral shape due to the exhaustion of molecules in the dye bath. Moreover, our findings revealed technological insights, showing that Paul Gout's optimized recipes achieved comparable yellow tonality to Janot's using a lower percentage of weld. This will provide key knowledge on the technological processes for dyeing with weld from these 18th c. French masters, while creating a molecular fluorescence database for the analysis of artworks.
几千年来，有机染料一直用于纺织品等艺术品，具有很高的艺术和历史价值。它们可能为理解艺术品生产背后的技术提供线索。时至今日，艺术作品中天然有机色素的特征仍然是一个挑战，在文化遗产中使用的天然染料中，黄色是最难识别的。本文探讨了将可见范围内的分子荧光与高效液相色谱和二极管阵列检测相结合，揭示历史染料配方的潜力。通过分析两位18世纪法国染色大师Antoine Janot和Paul Gout的配方，历史上准确的重建有可能证明分子荧光对特定染料成分的存在和不同配方的使用高度敏感。木犀草素（Lut）和木犀草素7- o -葡糖苷（Lut-7- o -glc）是主要的化合物，其中木犀草素的含量较高，尤其是在雅诺氏变种中。分析数据表明，分子荧光对配方差异非常敏感：酒石的存在与较高的Lut存在相关，石灰的使用诱导了发射最大值的轻微变化，即使没有由于染料浴中分子耗尽而影响光谱形状。此外，我们的研究结果揭示了技术见解，表明Paul Gout的优化配方使用较低的焊缝百分比实现了与Janot相当的黄色色调。这将提供这些18世纪法国大师的焊接染色技术过程的关键知识，同时创建一个用于艺术品分析的分子荧光数据库。
{"title":"Disclosing the dyeing formulations of weld yellows from 18th-century recipe books with molecular fluorescence","authors":"Paula Nabais , Mara Espírito Santo , Mila Crippa , Natércia Teixeira , Dominique Cardon","doi":"10.1016/j.dyepig.2026.113590","DOIUrl":"10.1016/j.dyepig.2026.113590","url":null,"abstract":"<div><div>For millennia, organic dyes have been used in artworks such as textiles and have great artistic and historic value. They may provide clues to the understanding of the technology behind an artwork's production. The characterization of natural organic colourants in artworks is still a challenge to this day, and of the natural dyes used in cultural heritage, yellows are some of the most difficult to identify.</div><div>This paper explores the potential of combining molecular fluorescence in the visible range with high-performance liquid chromatography coupled with diode-array detection, to disclose historical dye formulations.</div><div>By analysing historically accurate reconstructions following recipes from two 18th c. French master dyers, Antoine Janot and Paul Gout, it was possible to demonstrate that molecular fluorescence is highly sensitive to the presence of specific dye ingredients and different use of recipes. Luteolin (Lut) and Luteolin 7-<em>O</em>-glucoside (Lut-7-<em>O</em>-glc) were identified as the main compounds, with the first being extracted in higher amounts, especially in Janot's variations. The analytical data demonstrated that molecular fluorescence is very sensitive to recipe differences: the presence of tartar correlated with a higher Lut presence, and the use of lime induced a slight shift in the emission maxima, even without affecting the spectral shape due to the exhaustion of molecules in the dye bath. Moreover, our findings revealed technological insights, showing that Paul Gout's optimized recipes achieved comparable yellow tonality to Janot's using a lower percentage of weld. This will provide key knowledge on the technological processes for dyeing with weld from these 18th c. French masters, while creating a molecular fluorescence database for the analysis of artworks.</div></div>","PeriodicalId":302,"journal":{"name":"Dyes and Pigments","volume":"249 ","pages":"Article 113590"},"PeriodicalIF":4.2,"publicationDate":"2026-06-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"146036636","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"工程技术","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Aquilegia buergeriana var. oxysepala and A. flabellata var. pumila are two commonly found Aquilegia species in Japan. To clarify the chemical differences underlying the sepal color difference between the two species, we investigated the pigments in their flowers. A total of seven previously undescribed compounds were isolated from the flowers of A. buergeriana var. oxysepala and A. flabellata var. pumila. One previously undescribed anthocyanin, delphinidin 3-O-(3″-malonylglucopyranoside), together with three known delphinidin glucosides, was isolated and identified from A. buergeriana var. oxysepala, while six previously undescribed compounds were isolated and identified from A. flabellata var. pumila. These included four delphinidin glycosides, one flavonol glycoside, and one C-glycosyl flavone; specifically, delphinidin 3-O-glucopyranoside-7-O-(6″-E-caffeoylglucopyranoside), delphinidin 3-O-(6″-E-caffeoylglucopyranoside)-7-O-(6‴-E-caffeoylglucopyranoside), delphinidin 3-O-(3″,6″-E-dicaffeoylglucopyranoside)-7-O-(6‴-E-caffeoylglucopyranoside), delphinidin 3-O-[3″-O-(1⁗-E-caffeoylglucopyranosyl)-(6→3)-malonyl-(6″-malonylglucopyranoside)-7-O-(6‴-E-caffeoylglucopyranoside), quercetin 3-O-glucopyranoside-7-O-[6''-(4‴-O-glucopyranosyl-E-p-coumaroyl)-glucopyranoside], and luteolin 6-C-[6''-(4‴-O-glucopyranosyl-E-p-coumaroyl)-glucopyranoside]. Seven known phenolics were also found in the flowers of A. flabellata var. pumila.
The pH of the sepals and petals of both species ranged from 5.6 to 5.8. In vitro sepal color reconstruction experiments showed that the sepal colors of A. buergeriana var. oxysepala and A. flabellata var. pumila could be attributed to their respective major anthocyanins. The violet coloration of A. flabellata var. pumila sepals is primarily due to intramolecular copigmentation rather than intermolecular effects. The main structural difference between these anthocyanins is that those of A. flabellata var. pumila possess a 6-caffeoylglucoside moiety at the 7-position, whereas those of A. buergeriana var. oxysepala do not. Our findings suggest that 7-O-glycosylation and acylation of delphinidin may play an important role in the formation of blue hue in the flower.
黄貂鱼是日本常见的两种黄貂鱼。为了弄清这两种植物萼片颜色差异背后的化学差异，我们研究了它们花中的色素。共分离到7个以前未见过的化合物，这些化合物分别来自布氏花和黄斑花。分离鉴定了一种先前未被描述的花青素，即飞燕苷3- o -（3″-丙二酰葡萄糖吡喃苷）和三种已知的飞燕苷糖苷类化合物，并从黄翅飞燕中分离鉴定了六种先前未被描述的化合物。其中包括四种飞燕苷苷、一种黄酮醇苷和一种c -糖基黄酮；具体来说，是delphi苷3- o -glucopyranoside-7- o -(6″- e- caffeoylglucopyranoside)， delphi苷3- o -(6″- e- caffeoylglucopyranoside)-7- o -(6″- e- caffeoylglucopyranoside)， delphi苷3- o -(3″，6″- e- dicaffeoylglucopyranoside)-7- o -(6″- e- caffeoylglucopyranoside)， delphi苷3- o -[3″- o -(1⁗- e- caffeoylglucopyranoside)-(6 -″- e- caffeoylglucopyranoside)-(6 -″- e- caffeoylglucopyranoside)]，槲皮素3- o -glucopyranoside-7- o -[6”-(4 - o -glucopyranoside- e- p-coumaroyl)-glucopyranoside]，木犀草素6- c -[6′-(4′- o - glucopyranoyl - e -p-coumaroyl)- glucopyrano苷]。此外，还在黄柳花中发现了7种已知的酚类物质。两种植物萼片和花瓣的pH值均在5.6 ~ 5.8之间。离体萼片颜色重建实验表明，布氏蜂属和黄斑蜂属的萼片颜色可能与它们各自的主要花青素有关。黄翅草萼片的紫色主要是由于分子内的共色素作用，而不是分子间的作用。这两种花青素在结构上的主要区别是，黄叶菊变种花青素在7位上含有6-咖啡基糖苷，而黄叶菊变种花青素在7位上没有。我们的研究结果表明，飞燕草苷的7- o糖基化和酰化可能在花的蓝色色调形成中起重要作用。
{"title":"Acylated delphinidin glycosides from red-purple sepals of Aquilegia buergeriana var. oxysepala and violet sepals of A. flabellata var. pumila (Ranunculaceae)","authors":"Qi Qin , Kohtaro Sugahara , Takahisa Nakane , Kazushige Honda , Fumi Tatsuzawa , Tsukasa Iwashina , Takayuki Mizuno","doi":"10.1016/j.dyepig.2026.113567","DOIUrl":"10.1016/j.dyepig.2026.113567","url":null,"abstract":"<div><div><em>Aquilegia buergeriana</em> var. <em>oxysepala</em> and <em>A. flabellata</em> var. <em>pumila</em> are two commonly found <em>Aquilegia</em> species in Japan. To clarify the chemical differences underlying the sepal color difference between the two species, we investigated the pigments in their flowers. A total of seven previously undescribed compounds were isolated from the flowers of <em>A. buergeriana</em> var. <em>oxysepala</em> and <em>A. flabellata</em> var. <em>pumila</em>. One previously undescribed anthocyanin, delphinidin 3-<em>O</em>-(3″-malonylglucopyranoside), together with three known delphinidin glucosides, was isolated and identified from <em>A. buergeriana</em> var. <em>oxysepala</em>, while six previously undescribed compounds were isolated and identified from <em>A. flabellata</em> var. <em>pumila</em>. These included four delphinidin glycosides, one flavonol glycoside, and one <em>C</em>-glycosyl flavone; specifically, delphinidin 3-<em>O</em>-glucopyranoside-7-<em>O</em>-(6″-<em>E</em>-caffeoylglucopyranoside), delphinidin 3-<em>O</em>-(6″-<em>E</em>-caffeoylglucopyranoside)-7-<em>O</em>-(6‴-<em>E</em>-caffeoylglucopyranoside), delphinidin 3-<em>O</em>-(3″,6″-<em>E</em>-dicaffeoylglucopyranoside)-7-<em>O</em>-(6‴-<em>E</em>-caffeoylglucopyranoside), delphinidin 3-<em>O</em>-[3″-<em>O</em>-(1⁗-<em>E</em>-caffeoylglucopyranosyl)-(6→3)-malonyl-(6″-malonylglucopyranoside)-7-<em>O</em>-(6‴-<em>E</em>-caffeoylglucopyranoside), quercetin 3-<em>O</em>-glucopyranoside-7-<em>O</em>-[6''-(4‴-<em>O</em>-glucopyranosyl-<em>E</em>-<em>p</em>-coumaroyl)-glucopyranoside], and luteolin 6-<em>C</em>-[6''-(4‴-<em>O</em>-glucopyranosyl-<em>E</em>-<em>p</em>-coumaroyl)-glucopyranoside]. Seven known phenolics were also found in the flowers of <em>A. flabellata</em> var. <em>pumila</em>.</div><div>The pH of the sepals and petals of both species ranged from 5.6 to 5.8. <em>In vitro</em> sepal color reconstruction experiments showed that the sepal colors of <em>A. buergeriana</em> var. <em>oxysepala</em> and <em>A. flabellata</em> var. <em>pumila</em> could be attributed to their respective major anthocyanins. The violet coloration of <em>A. flabellata</em> var. <em>pumila</em> sepals is primarily due to intramolecular copigmentation rather than intermolecular effects. The main structural difference between these anthocyanins is that those of <em>A. flabellata</em> var. <em>pumila</em> possess a 6-caffeoylglucoside moiety at the 7-position, whereas those of <em>A. buergeriana</em> var. <em>oxysepala</em> do not. Our findings suggest that 7-<em>O</em>-glycosylation and acylation of delphinidin may play an important role in the formation of blue hue in the flower.</div></div>","PeriodicalId":302,"journal":{"name":"Dyes and Pigments","volume":"249 ","pages":"Article 113567"},"PeriodicalIF":4.2,"publicationDate":"2026-06-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"146036581","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"工程技术","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Pub Date : 2026-06-01Epub Date: 2026-01-20DOI: 10.1016/j.dyepig.2026.113586
Roy Merkezoğlu , Hızır Ali Malkoç , Mustafa Özyürek
Fluorescence-based probes and sensors have emerged as indispensable tools for the detection of alkaline phosphatase (ALP), a clinically significant enzyme, owing to their high sensitivity, real-time imaging capabilities, and superior spatial resolution. This review examines fluorescence-based ALP detection techniques published between 2020 and 2025 and divides them into three main categories, which are small-molecule fluorogenic probes, nanomaterial-based fluorescent sensors and nucleic acid-assisted hybrid systems. In this context, particular attention is given to the structural evolution of various fluorophore scaffolds and the engineering of molecular dye platforms designed to modulate specific photophysics for enzyme-responsive signaling. By utilizing cutting-edge design components like near-infrared and ratiometric fluorophores, nanoparticle-based signal amplifiers, and deoxyribonucleic acid/ribonucleic acid (DNA/RNA)-mediated amplification circuits (including aptamer and clustered regularly interspaced short palindromic repeats (CRISPR)-driven mechanisms), researchers have improved analytical performance across these platforms. A wide range of applications, such as clinical diagnostics (ultrasensitive serum assays), live-cell and in vivo imaging of enzyme activity, environmental monitoring, and high-throughput screening. These advances have enabled applications ranging from ultrasensitive serum assays to live-cell imaging and portable readouts. This review highlights the increasing significance of fluorescence-based ALP detection in analytical chemistry and biomedicine by showcasing both state-of-the-art probe design and practical deployment. It also explores how current developments are laying the groundwork for next-generation ALP sensors with even higher sensitivity, specificity, and versatility. In addition to summarizing recent reports, we benchmark the 2020–2025 literature against pre-2020 ALP sensing paradigms to delineate genuine step-changes and to highlight persistent limitations that remain unresolved. Lastly, it discusses the opportunities and challenges that still need to be overcome before these ALP sensing technologies can be used in clinical and field settings.
{"title":"Fluorescence-based strategies for alkaline phosphatase detection: A comprehensive review","authors":"Roy Merkezoğlu , Hızır Ali Malkoç , Mustafa Özyürek","doi":"10.1016/j.dyepig.2026.113586","DOIUrl":"10.1016/j.dyepig.2026.113586","url":null,"abstract":"<div><div>Fluorescence-based probes and sensors have emerged as indispensable tools for the detection of alkaline phosphatase (ALP), a clinically significant enzyme, owing to their high sensitivity, real-time imaging capabilities, and superior spatial resolution. This review examines fluorescence-based ALP detection techniques published between 2020 and 2025 and divides them into three main categories, which are small-molecule fluorogenic probes, nanomaterial-based fluorescent sensors and nucleic acid-assisted hybrid systems. In this context, particular attention is given to the structural evolution of various fluorophore scaffolds and the engineering of molecular dye platforms designed to modulate specific photophysics for enzyme-responsive signaling. By utilizing cutting-edge design components like near-infrared and ratiometric fluorophores, nanoparticle-based signal amplifiers, and deoxyribonucleic acid/ribonucleic acid (DNA/RNA)-mediated amplification circuits (including aptamer and clustered regularly interspaced short palindromic repeats (CRISPR)-driven mechanisms), researchers have improved analytical performance across these platforms. A wide range of applications, such as clinical diagnostics (ultrasensitive serum assays), live-cell and in vivo imaging of enzyme activity, environmental monitoring, and high-throughput screening. These advances have enabled applications ranging from ultrasensitive serum assays to live-cell imaging and portable readouts. This review highlights the increasing significance of fluorescence-based ALP detection in analytical chemistry and biomedicine by showcasing both state-of-the-art probe design and practical deployment. It also explores how current developments are laying the groundwork for next-generation ALP sensors with even higher sensitivity, specificity, and versatility. In addition to summarizing recent reports, we benchmark the 2020–2025 literature against pre-2020 ALP sensing paradigms to delineate genuine step-changes and to highlight persistent limitations that remain unresolved. Lastly, it discusses the opportunities and challenges that still need to be overcome before these ALP sensing technologies can be used in clinical and field settings.</div></div>","PeriodicalId":302,"journal":{"name":"Dyes and Pigments","volume":"249 ","pages":"Article 113586"},"PeriodicalIF":4.2,"publicationDate":"2026-06-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"146036582","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"工程技术","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Pub Date : 2026-06-01Epub Date: 2026-02-03DOI: 10.1016/j.dyepig.2026.113630
Shen Zhang, Zhuo Wang
In consideration of the potential threat, the establishment of efficient approach for fluazinam determination is necessary. Based on the superior property of carbon dots and biomass, sulfur doped biomass-based carbon dots (SBCDs) were constructed using a simple hydrothermal approach, in which peanuts were applied as carbon sources with the addition of methionine. The well-dispersed SBCDs displayed optimal emission wavelength of 435 nm under the excitation wavelength of 364 nm. Owing to the detection principle of fluorescence quenching through static quenching and inner filter effects, the SBCDs were used to detect fluazinam with a broad linear range of 0-100 μM and a detection limit of 0.026 μM. Additionally, the SBCDs also exhibited temperature sensing with a wide linear range of 15-95 °C. Moreover, the as-prepared SBCDs were effectively used for the determination of fluazinam in tap water and orange juice samples. The SBCDs displayed tremendous potential for the sensing of fluazinam and temperature.
{"title":"Peanut-derived carbon dots as a fluorescence probe for the determination of fluazinam and temperature","authors":"Shen Zhang, Zhuo Wang","doi":"10.1016/j.dyepig.2026.113630","DOIUrl":"10.1016/j.dyepig.2026.113630","url":null,"abstract":"<div><div>In consideration of the potential threat, the establishment of efficient approach for fluazinam determination is necessary. Based on the superior property of carbon dots and biomass, sulfur doped biomass-based carbon dots (SBCDs) were constructed using a simple hydrothermal approach, in which peanuts were applied as carbon sources with the addition of methionine. The well-dispersed SBCDs displayed optimal emission wavelength of 435 nm under the excitation wavelength of 364 nm. Owing to the detection principle of fluorescence quenching through static quenching and inner filter effects, the SBCDs were used to detect fluazinam with a broad linear range of 0-100 μM and a detection limit of 0.026 μM. Additionally, the SBCDs also exhibited temperature sensing with a wide linear range of 15-95 °C. Moreover, the as-prepared SBCDs were effectively used for the determination of fluazinam in tap water and orange juice samples. The SBCDs displayed tremendous potential for the sensing of fluazinam and temperature.</div></div>","PeriodicalId":302,"journal":{"name":"Dyes and Pigments","volume":"249 ","pages":"Article 113630"},"PeriodicalIF":4.2,"publicationDate":"2026-06-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"146184782","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"工程技术","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Pub Date : 2026-06-01Epub Date: 2026-01-30DOI: 10.1016/j.dyepig.2026.113611
Leshi Li , Haowen Deng , Zixuan Zhang, Zhuping Chen, Jingjing He, Qiannan Wang, Zepeng Wang, Zhen-Qiang Yu, Yue Wu
Materials that can emit circularly polarized luminescence (CPL) are attracting considerable interest because of their unique chiroptical properties and broad range of applications. Most reported CPL-active materials, however, have low luminescence dissymmetry factors (|glᵤm|), limited quantum efficiency as well as poor stability and processability. Here, a copolymerization strategy, involving an achiral luminescent dye (a tetraphenylethylene (TPE) derivative) as the emitter and chiral cholesterol (Chol) moieties to induce helicity, was proposed to prepare polymer, poly-TPE-Chol. Thin film of poly-TPE-Chol shows highly dissymmetric and emissive CPL with a high |glᵤm| of 1.11 × 10−2 and a photoluminescence quantum yield (QY) of 28.6%, beyond those of TPE-Chol monomer. This is attributed to promoted chiral supramolecular ordering and increased molecular confinement for suppressing non-radiative decay towards TPE units in poly-TPE-Chol, respectively. This strategy, proven to be general, paves the way for designing non-doped CPL polymers with high |glum| values and QY.
{"title":"Cholesteric copolymerization strategy endows achiral fluorophore with bright circularly polarized luminescence","authors":"Leshi Li , Haowen Deng , Zixuan Zhang, Zhuping Chen, Jingjing He, Qiannan Wang, Zepeng Wang, Zhen-Qiang Yu, Yue Wu","doi":"10.1016/j.dyepig.2026.113611","DOIUrl":"10.1016/j.dyepig.2026.113611","url":null,"abstract":"<div><div>Materials that can emit circularly polarized luminescence (CPL) are attracting considerable interest because of their unique chiroptical properties and broad range of applications. Most reported CPL-active materials, however, have low luminescence dissymmetry factors (|<em>g</em><sub>l</sub>ᵤ<sub>m</sub>|), limited quantum efficiency as well as poor stability and processability. Here, a copolymerization strategy, involving an achiral luminescent dye (a tetraphenylethylene (TPE) derivative) as the emitter and chiral cholesterol (Chol) moieties to induce helicity, was proposed to prepare polymer, poly-TPE-Chol. Thin film of poly-TPE-Chol shows highly dissymmetric and emissive CPL with a high |<em>g</em><sub>l</sub>ᵤ<sub>m</sub>| of 1.11 × 10<sup>−2</sup> and a photoluminescence quantum yield (QY) of 28.6%, beyond those of TPE-Chol monomer. This is attributed to promoted chiral supramolecular ordering and increased molecular confinement for suppressing non-radiative decay towards TPE units in poly-TPE-Chol, respectively. This strategy, proven to be general, paves the way for designing non-doped CPL polymers with high |<em>g</em><sub>lum</sub>| values and QY.</div></div>","PeriodicalId":302,"journal":{"name":"Dyes and Pigments","volume":"249 ","pages":"Article 113611"},"PeriodicalIF":4.2,"publicationDate":"2026-06-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"146184780","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"工程技术","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Since prehistoric times, humans have used dye-producing plants to color textiles, artworks, and ritual objects. Yellow-yielding species have been especially important due to their availability and the chemical stability of many of their flavonoid-based colorants. Among them, Rhamnus species (buckthorns) are notable for producing yellow to greenish hues from their flavonoid-rich berries. These long-standing practices inform modern research on natural colorants, phytochemistry, and sustainable textile science.
In this context, this study investigates the chemical and chromatic evolution of cotton fabrics dyed with Rhamnus cathartica (European buckthorn) berries when subjected to accelerated light ageing. Fabrics were exposed to xenon-lamp irradiation equivalent to 3, 30, and 300 years of museum-type light. Color fading was assessed by CIELAB colorimetry, and dye degradation was analyzed using LC-DAD and untargeted LC-MS-based metabolomics. Colorimetric data showed rapid fading, fabrics appearing even whiter than undyed samples after the 300-year equivalent exposure. LC-DAD analysis revealed a drastic decline of most coloring compounds, including flavonoids and anthraquinones, which became undetectable in the most aged samples, highlighting the limited sensitivity of LC-DAD for heavily degraded textiles. In contrast, LC-MS metabolomics enabled the detection and putative annotation of 25 dye molecules, mainly flavonoid glycosides and anthraquinones. Molecular networking highlighted distinct structural families, and surprisingly many dye-related compounds remained detectable even in fully bleached fabrics.
These results demonstrated that LC-MS-based metabolomics can constitute a powerful tool for identifying residual dyes in historical textiles, supporting conservation and reconstruction of ancient dyeing practices.
{"title":"When true colors still shine through: LC-MS-based metabolomics study of fabrics dyed with European buckthorn (Rhamnus cathartica) berries after accelerated light ageing","authors":"Marine Chambaud , Lindsay Mas-Normand , Céline Joliot , Carole Mathe , Olivier Dangles , Gérald Culioli","doi":"10.1016/j.dyepig.2026.113625","DOIUrl":"10.1016/j.dyepig.2026.113625","url":null,"abstract":"<div><div>Since prehistoric times, humans have used dye-producing plants to color textiles, artworks, and ritual objects. Yellow-yielding species have been especially important due to their availability and the chemical stability of many of their flavonoid-based colorants. Among them, <em>Rhamnus</em> species (buckthorns) are notable for producing yellow to greenish hues from their flavonoid-rich berries. These long-standing practices inform modern research on natural colorants, phytochemistry, and sustainable textile science.</div><div>In this context, this study investigates the chemical and chromatic evolution of cotton fabrics dyed with <em>Rhamnus cathartica</em> (European buckthorn) berries when subjected to accelerated light ageing. Fabrics were exposed to xenon-lamp irradiation equivalent to 3, 30, and 300 years of museum-type light. Color fading was assessed by CIELAB colorimetry, and dye degradation was analyzed using LC-DAD and untargeted LC-MS-based metabolomics. Colorimetric data showed rapid fading, fabrics appearing even whiter than undyed samples after the 300-year equivalent exposure. LC-DAD analysis revealed a drastic decline of most coloring compounds, including flavonoids and anthraquinones, which became undetectable in the most aged samples, highlighting the limited sensitivity of LC-DAD for heavily degraded textiles. In contrast, LC-MS metabolomics enabled the detection and putative annotation of 25 dye molecules, mainly flavonoid glycosides and anthraquinones. Molecular networking highlighted distinct structural families, and surprisingly many dye-related compounds remained detectable even in fully bleached fabrics.</div><div>These results demonstrated that LC-MS-based metabolomics can constitute a powerful tool for identifying residual dyes in historical textiles, supporting conservation and reconstruction of ancient dyeing practices.</div></div>","PeriodicalId":302,"journal":{"name":"Dyes and Pigments","volume":"249 ","pages":"Article 113625"},"PeriodicalIF":4.2,"publicationDate":"2026-06-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"146184784","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"工程技术","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Pub Date : 2026-06-01Epub Date: 2026-02-05DOI: 10.1016/j.dyepig.2026.113632
Zengrong Li , Xuelong Huang , Xiaoyan Li , Zihong Chen , Chu Liu , Xinru Chen , Yongjun Deng , Yuchen Pan , Tao Jia , Zhixiong Cao
Most organic small-molecule photoacoustic (PA) contrast agents exhibit absorption in the NIR-I window (700–900 nm), limiting their utility in deep-tissue imaging due to insufficient signal-to-noise ratio (SNR) and penetration depth. To address this, we repurpose the A-DA′D-A-type molecule Y-QC4F—featuring difluorinated quinoidal acceptors—for NIR-II (1000–1700 nm) PA imaging. The synergistic integration of quinoidal character and fluorination narrows the optical bandgap and extends π-conjugation, redshifting the thin-film absorption maximum to 1052 nm—closely aligned with the commonly used 1064 nm laser excitation wavelength. Upon nanoformulation with DSPE-mPEG2000, Y-QC4F@NPs display strong NIR-II absorption in aqueous media, a high photothermal conversion efficiency (49.9%), and robust photostability. In vivo, intravenous administration yields a 51.4-fold PA signal enhancement in mouse ear vasculature (resolving vessels down to 40 μm) and a 173.2-fold enhancement in cerebral vasculature (60 μm resolution), demonstrating clear blood–brain barrier penetration. Combined with minimal cytotoxicity, negligible hemolysis, and no observable histological damage, this work establishes the synergy between quinoidal architecture and strategic fluorination as a rational molecular design strategy for high-performance A-DA′D-A-type small-molecule NIR-II photoacoustic contrast agents.
大多数有机小分子光声（PA）造影剂在NIR-I窗口（700-900 nm）表现出吸收，由于信噪比（SNR）和穿透深度不足，限制了它们在深部组织成像中的应用。为了解决这个问题，我们重新设计了A-DA ' d - a型分子y - qc4f -具有二氟化quinoidal受体-用于NIR-II (1000-1700 nm) PA成像。quinoidal特性和氟化的协同集成缩小了光学带隙，扩展了π共轭，使薄膜吸收最大值红移至1052 nm，与常用的1064 nm激光激发波长紧密对准。在DSPE-mPEG2000纳米配方后，Y-QC4F@NPs在水介质中表现出较强的NIR-II吸收，较高的光热转换效率（49.9%）和良好的光稳定性。在体内，静脉给药可使小鼠耳部血管的PA信号增强51.4倍（分辨率为40 μm），脑血管的PA信号增强173.2倍（分辨率为60 μm），显示出清晰的血脑屏障穿透。结合最小的细胞毒性，可忽略的溶血，没有观察到的组织学损伤，这项工作建立了quinoidal结构和策略氟化之间的协同作用，作为高性能a - da ' d - a型小分子NIR-II光声造影剂的合理分子设计策略。
{"title":"A fluorinated quinoidal A-DA′D-A small molecule enables high-performance NIR-II photoacoustic imaging","authors":"Zengrong Li , Xuelong Huang , Xiaoyan Li , Zihong Chen , Chu Liu , Xinru Chen , Yongjun Deng , Yuchen Pan , Tao Jia , Zhixiong Cao","doi":"10.1016/j.dyepig.2026.113632","DOIUrl":"10.1016/j.dyepig.2026.113632","url":null,"abstract":"<div><div>Most organic small-molecule photoacoustic (PA) contrast agents exhibit absorption in the NIR-I window (700–900 nm), limiting their utility in deep-tissue imaging due to insufficient signal-to-noise ratio (SNR) and penetration depth. To address this, we repurpose the A-DA′D-A-type molecule Y-QC4F—featuring difluorinated quinoidal acceptors—for NIR-II (1000–1700 nm) PA imaging. The synergistic integration of quinoidal character and fluorination narrows the optical bandgap and extends π-conjugation, redshifting the thin-film absorption maximum to 1052 nm—closely aligned with the commonly used 1064 nm laser excitation wavelength. Upon nanoformulation with DSPE-mPEG<sub>2000</sub>, Y-QC4F@NPs display strong NIR-II absorption in aqueous media, a high photothermal conversion efficiency (49.9%), and robust photostability. <em>In vivo</em>, intravenous administration yields a 51.4-fold PA signal enhancement in mouse ear vasculature (resolving vessels down to 40 μm) and a 173.2-fold enhancement in cerebral vasculature (60 μm resolution), demonstrating clear blood–brain barrier penetration. Combined with minimal cytotoxicity, negligible hemolysis, and no observable histological damage, this work establishes the synergy between quinoidal architecture and strategic fluorination as a rational molecular design strategy for high-performance A-DA′D-A-type small-molecule NIR-II photoacoustic contrast agents.</div></div>","PeriodicalId":302,"journal":{"name":"Dyes and Pigments","volume":"249 ","pages":"Article 113632"},"PeriodicalIF":4.2,"publicationDate":"2026-06-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"146184786","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"工程技术","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
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