pH balance is a prerequisite for maintaining cell function optimally and performs an important role in diverse physiological activities. Even subtle changes in cellular pH can influence many cell behaviors. More specifically, for mitochondria, its unique functions under physiological conditions depend largely on its pH values. Therefore, an effective analytical method needs to be developed to detect the alteration of intracellular pH values, especial in mitochondria. In this work, a ratiometric pH fluorescent probe (DPM) based on fluorescence resonance energy transfer (FRET) mechanism was developed by constructing coumarin and hemicyanine fluorophore. DPM could respond to pH changes by the FRET-off and FRET-on process depending on the cyclization and ring-opening reaction. DPM exhibited high energy transfer efficiency (89.1 %) and responded to pH ranges of 6.0–8.0 rapidly and selectively (pKa value of 7.6 in solution and 7.0 in cells). Moreover, DPM exhibited nearly non-toxicity to living cells and excellent photostability. DPM showed great pH-responsive feature in cells and achieved detection of mitochondrial acidification. The present work not only provided a new structure for pH fluorescence probe and simple synthetic method for the FRET-based probe but also found that the probe could target mitochondria in living cells.
{"title":"A ratiometric fluorescent probe based on FRET mechanism for pH and its cell imaging","authors":"Zhen-Ming Yue , Shu-Mei Zhai , Bing-Yu Wei , Bao-Xiang Zhao , Zhao-Min Lin","doi":"10.1016/j.dyepig.2024.112544","DOIUrl":"10.1016/j.dyepig.2024.112544","url":null,"abstract":"<div><div>pH balance is a prerequisite for maintaining cell function optimally and performs an important role in diverse physiological activities. Even subtle changes in cellular pH can influence many cell behaviors. More specifically, for mitochondria, its unique functions under physiological conditions depend largely on its pH values. Therefore, an effective analytical method needs to be developed to detect the alteration of intracellular pH values, especial in mitochondria. In this work, a ratiometric pH fluorescent probe (<strong>DPM</strong>) based on fluorescence resonance energy transfer (FRET) mechanism was developed by constructing coumarin and hemicyanine fluorophore. <strong>DPM</strong> could respond to pH changes by the FRET-off and FRET-on process depending on the cyclization and ring-opening reaction. <strong>DPM</strong> exhibited high energy transfer efficiency (89.1 %) and responded to pH ranges of 6.0–8.0 rapidly and selectively (pKa value of 7.6 in solution and 7.0 in cells). Moreover, <strong>DPM</strong> exhibited nearly non-toxicity to living cells and excellent photostability. <strong>DPM</strong> showed great pH-responsive feature in cells and achieved detection of mitochondrial acidification. The present work not only provided a new structure for pH fluorescence probe and simple synthetic method for the FRET-based probe but also found that the probe could target mitochondria in living cells.</div></div>","PeriodicalId":302,"journal":{"name":"Dyes and Pigments","volume":"233 ","pages":"Article 112544"},"PeriodicalIF":4.1,"publicationDate":"2024-11-15","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142656675","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}
Smart windows can regulate indoor lighting and heat intensity by isolating external light and heat, thereby achieving the goal of saving building energy consumption. However, traditional smart windows require additional power consumption to adjust color changes and thus regulate transmittance, and can only achieve relatively single control of light intensity and heat. Developing smart windows with dynamic photothermal modulation remains challenging. This paper reports two novel benzothiadiazole extended viologen derivatives DBTBB and DBTBH. The carboxymethylcellulose sodium hydrogel-state electrochromic devices based on DBTBB and DBTBH showed good electrochromic performance including a low operating voltage, a rapid response time, a high optical contrast, excellent cycling stability, and a large coloration efficiency. A dynamic photothermal modulation electrochromic smart window self-powered by a small commercial solar panel was constructed using the electrochromic hydrogel based on DBTBB, which could sense the changes in external irradiating light intensity and dynamically adjust the indoor light and heat without additional consumption of electricity, and the adjusting capability increased with the increase of irradiating light intensity. In addition, the application in smart color changing sunglasses self-powered by a solar panel was also investigated, the electrochromic sunglasses showed dynamic transmittance modulation in response to irradiating light intensities with good cycling stability, a gradual change in purple color from light to dark was observed as the irradiating light intensity increased from 105 → 225→415 → 650→920 lux. Moreover, both text and a colored logo were clearly displayed under different irradiating light intensities. This provides new methods for electrochromic applications in commercial settings and improving human quality of life, thereby creating new possibilities in the increasingly intelligent world.
{"title":"Dynamic optical and thermal modulation of electrochromic smart windows and sunglasses based on benzothiadiazole-extended viologen derivatives","authors":"Yu-Zhen Li, Zhi-hao Cui, Dong-yun Jiang, Pu-yang Tang, Cheng-bin Gong, Qian Tang","doi":"10.1016/j.dyepig.2024.112543","DOIUrl":"10.1016/j.dyepig.2024.112543","url":null,"abstract":"<div><div>Smart windows can regulate indoor lighting and heat intensity by isolating external light and heat, thereby achieving the goal of saving building energy consumption. However, traditional smart windows require additional power consumption to adjust color changes and thus regulate transmittance, and can only achieve relatively single control of light intensity and heat. Developing smart windows with dynamic photothermal modulation remains challenging. This paper reports two novel benzothiadiazole extended viologen derivatives DBTBB and DBTBH. The carboxymethylcellulose sodium hydrogel-state electrochromic devices based on DBTBB and DBTBH showed good electrochromic performance including a low operating voltage, a rapid response time, a high optical contrast, excellent cycling stability, and a large coloration efficiency. A dynamic photothermal modulation electrochromic smart window self-powered by a small commercial solar panel was constructed using the electrochromic hydrogel based on DBTBB, which could sense the changes in external irradiating light intensity and dynamically adjust the indoor light and heat without additional consumption of electricity, and the adjusting capability increased with the increase of irradiating light intensity. In addition, the application in smart color changing sunglasses self-powered by a solar panel was also investigated, the electrochromic sunglasses showed dynamic transmittance modulation in response to irradiating light intensities with good cycling stability, a gradual change in purple color from light to dark was observed as the irradiating light intensity increased from 105 → 225→415 → 650→920 lux. Moreover, both text and a colored logo were clearly displayed under different irradiating light intensities. This provides new methods for electrochromic applications in commercial settings and improving human quality of life, thereby creating new possibilities in the increasingly intelligent world.</div></div>","PeriodicalId":302,"journal":{"name":"Dyes and Pigments","volume":"233 ","pages":"Article 112543"},"PeriodicalIF":4.1,"publicationDate":"2024-11-15","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142656680","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 : 2024-11-13DOI: 10.1016/j.dyepig.2024.112539
Andrei S. Starikov , Alexey V. Borodachev , Pavel A. Tarakanov , Nikita A. Slesarenko , Sergey V. Simonov , Anton O. Simakov , Olga I. Istakova , Olga A. Goncharova , Dmitry V. Konev , Victor E. Pushkarev
The first covalently linked dimer has been prepared for cyclazine systems by regioselective oxidative homocoupling of 1,2-dicarbomethoxy-3-phenylcycl[3.2.2]azine. The regioselectivity of this reaction at 4-position, having been confirmed by X-ray diffraction analysis and NMR spectroscopy, has been also reliably predicted within the model of average local ionization energy on the molecular surface of the starting monomer at the BP86/def2-TZVP level of theory. Due to the planar π-π interaction of the cycl[3.2.2]azine subunits, the dimer is a green fluorophore (λem = 527 nm, toluene), characterized by a bathochromic shift of the main bands in the UV–vis and fluorescence spectra relative to the monomer by 41 and 71 nm, respectively. Furthermore, the dimer demonstrates an increased fluorescence quantum yield relative to the monomer (55 % vs. 35 % in toluene), and according to the data of X-ray diffraction analysis, DFT calculations and variable temperature 1D and 2D 1H NMR spectroscopy, is characterized by hindered rotation of the S1-state-involved cycl[3.2.2]azine cores along the C4–C4′ bond axis. Such prerequisites determine good application potential of the 4-4′ coupled cycl[3.2.2]azine derivatives as turn-on fluorescent, i.e. fluorogenic probes for advanced bioimaging in living systems. Finally, unlike the monomer, the dimer shows reversibility of both one- and two-electron reduction and oxidation processes, and therefore can become the basis of both n- and p-type semiconductors.
通过 1,2-二碳甲氧基-3-苯基环[3.2.2]氮的区域选择性氧化同偶联反应，制备出了环嗪系统的第一个共价连接二聚体。该反应在 4 位的区域选择性已通过 X 射线衍射分析和核磁共振光谱得到证实，并在 BP86/def2-TZVP 理论水平上，根据起始单体分子表面的平均局部电离能模型进行了可靠的预测。由于环[3.2.2]氮亚基的平面 π-π 相互作用，二聚体是一种绿色荧光体（λem = 527 nm，甲苯），其特征是紫外可见光谱和荧光光谱中的主带相对于单体分别发生了 41 nm 和 71 nm 的浴色偏移。根据 X 射线衍射分析、DFT 计算和变温一维和二维 1H NMR 光谱分析的数据，二聚体的特征是 S1 状态参与的环[3.2.2]氮核沿 C4-C4′ 键轴受阻旋转。这些先决条件决定了 4-4′ 偶联环[3.2.2]吖嗪衍生物具有很好的应用潜力，可作为开启型荧光即荧光探针，用于活体系统中的高级生物成像。最后，与单体不同，二聚体在单电子和双电子还原和氧化过程中都表现出可逆性，因此可以成为 n 型和 p 型半导体的基础。
{"title":"First oxidative coupling of cyclazine heterocycle via regioselective dimerization of 1,2-dicarbomethoxy-3-phenylcycl[3.2.2]azine: Synthesis, theoretical aspects and physicochemical studies","authors":"Andrei S. Starikov , Alexey V. Borodachev , Pavel A. Tarakanov , Nikita A. Slesarenko , Sergey V. Simonov , Anton O. Simakov , Olga I. Istakova , Olga A. Goncharova , Dmitry V. Konev , Victor E. Pushkarev","doi":"10.1016/j.dyepig.2024.112539","DOIUrl":"10.1016/j.dyepig.2024.112539","url":null,"abstract":"<div><div>The first covalently linked dimer has been prepared for cyclazine systems by regioselective oxidative homocoupling of 1,2-dicarbomethoxy-3-phenylcycl[3.2.2]azine. The regioselectivity of this reaction at 4-position, having been confirmed by X-ray diffraction analysis and NMR spectroscopy, has been also reliably predicted within the model of average local ionization energy on the molecular surface of the starting monomer at the BP86/def2-TZVP level of theory. Due to the planar π-π interaction of the cycl[3.2.2]azine subunits, the dimer is a green fluorophore (λ<sub>em</sub> = 527 nm, toluene), characterized by a bathochromic shift of the main bands in the UV–vis and fluorescence spectra relative to the monomer by 41 and 71 nm, respectively. Furthermore, the dimer demonstrates an increased fluorescence quantum yield relative to the monomer (55 % <em>vs.</em> 35 % in toluene), and according to the data of X-ray diffraction analysis, DFT calculations and variable temperature 1D and 2D <sup>1</sup>H NMR spectroscopy, is characterized by hindered rotation of the S<sub>1</sub>-state-involved cycl[3.2.2]azine cores along the C4–C4′ bond axis. Such prerequisites determine good application potential of the 4-4′ coupled cycl[3.2.2]azine derivatives as turn-on fluorescent, i.e. fluorogenic probes for advanced bioimaging in living systems. Finally, unlike the monomer, the dimer shows reversibility of both one- and two-electron reduction and oxidation processes, and therefore can become the basis of both n- and p-type semiconductors.</div></div>","PeriodicalId":302,"journal":{"name":"Dyes and Pigments","volume":"233 ","pages":"Article 112539"},"PeriodicalIF":4.1,"publicationDate":"2024-11-13","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142656678","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 : 2024-11-13DOI: 10.1016/j.dyepig.2024.112541
Sergei A. Chernenko , Anton L. Shatsauskas , Yuri V. Shatalin , Victoria S. Shubina , Margarita I. Kobyakova , Tatyana Yu Zheleznova , Anastasia S. Kostyuchenko , Alexander S. Fisyuk
A series of previously unknown 1-alkylamino-3H-naphtho[1,2,3-de]quinoline-2,7-diones, 1-alkylamino-6-nitro-3H-naphtho[1,2,3-de]quinoline-2,7-diones, and 1-alkylamino-6-amino-3H-naphtho[1,2,3-de]quinoline-2,7-diones was obtained by nucleophilic substitution of the tosyl group of 1-tosyl-3H-naphtho[1,2,3-de]quinoline-2,7-dione with aliphatic amines. Among the synthesized compounds, fluorophores emitting light from the blue-green to orange-red region of the visible spectrum with fluorescence quantum yields up to 0.39 were found. Some of the synthesized compounds showed phototoxic effects on human breast carcinoma cell line BT474. It was shown that 3-butyl-1-(butylamino)-6-nitronaphthoquinolinedione stains exclusively lipid droplets, has a large Stokes shift and can be used for visualization of these organelles.
{"title":"1-Alkylamino-3H-naphtho[1,2,3-de]quinoline-2,7-diones. Visualization of lipid droplets in living cells","authors":"Sergei A. Chernenko , Anton L. Shatsauskas , Yuri V. Shatalin , Victoria S. Shubina , Margarita I. Kobyakova , Tatyana Yu Zheleznova , Anastasia S. Kostyuchenko , Alexander S. Fisyuk","doi":"10.1016/j.dyepig.2024.112541","DOIUrl":"10.1016/j.dyepig.2024.112541","url":null,"abstract":"<div><div>A series of previously unknown 1-alkylamino-3<em>H</em>-naphtho[1,2,3-<em>de</em>]quinoline-2,7-diones, 1-alkylamino-6-nitro-3<em>H</em>-naphtho[1,2,3-<em>de</em>]quinoline-2,7-diones, and 1-alkylamino-6-amino-3<em>H</em>-naphtho[1,2,3-<em>de</em>]quinoline-2,7-diones was obtained by nucleophilic substitution of the tosyl group of 1-tosyl-3<em>H</em>-naphtho[1,2,3-<em>de</em>]quinoline-2,7-dione with aliphatic amines. Among the synthesized compounds, fluorophores emitting light from the blue-green to orange-red region of the visible spectrum with fluorescence quantum yields up to 0.39 were found. Some of the synthesized compounds showed phototoxic effects on human breast carcinoma cell line BT474. It was shown that 3-butyl-1-(butylamino)-6-nitronaphthoquinolinedione stains exclusively lipid droplets, has a large Stokes shift and can be used for visualization of these organelles.</div></div>","PeriodicalId":302,"journal":{"name":"Dyes and Pigments","volume":"233 ","pages":"Article 112541"},"PeriodicalIF":4.1,"publicationDate":"2024-11-13","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142656679","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 : 2024-11-12DOI: 10.1016/j.dyepig.2024.112535
Flávio Figueira , Andreia S.F. Farinha , Adriano Santana , Johannes S. Vrouwenvelder , Augusto C. Tomé , Dmitry Chernyshov , Filipe A. Almeida Paz , José A.S. Cavaleiro , João P.C. Tomé
The synthesis and spectroscopic studies of four sensors for fluoride chromogenic sensing are described. The new compounds were prepared by the Knoevenagel condensation of diformyl-substituted bipyrrolic and dipyrrolic synthons ([2,2′-bipyrrole]-5,5′-dicarbaldehyde and dipyrromethane-1,9-dicarbaldehyde moieties) with malononitrile or indane-1,3-dione. They strongly absorb in the visible region and significant color changes occur in the presence of fluoride anions. Acetate and dihydrogenphosphate anions also induce observable colorimetric changes, albeit to a lesser extent. These changes, which are visible to the unaided eye, are associated with NH-bonding interactions that are unique to each anion. Non-linear regression analysis of the ground- and excited-state changes revealed anion recognition in a 2:1 stoichiometry (Host:Guest), where the electronegative character of the substituents (malononitrile or indane-1,3-dione residues) controls the sensitivity of the binding. The proposed systems all feature exceptional anion receptors that display an impressive chromogenic response through NH-bonding. Among these, compound 3 stands out with exceptionally high affinity constants of up to 7.39x10⁹ M⁻2, as well as an extremely low limit of detection at 92 ppm. NMR spectroscopy and mass spectrometry confirmed the structures of the synthesized compounds, with increased complexity in the NMR spectra due to the presence of malononitrile and indane-1,3-dione moieties. These findings highlight the potential of incorporating highly conjugated push-pull chromophores into bipyrrolic and dipyrrolic synthons for improved fluoride sensing performance in terms of both binding and signaling.
{"title":"Colorimetric fluoride ion sensors based on dipyrrolic and bipyrrolic compounds: Synthesis and anion recognition","authors":"Flávio Figueira , Andreia S.F. Farinha , Adriano Santana , Johannes S. Vrouwenvelder , Augusto C. Tomé , Dmitry Chernyshov , Filipe A. Almeida Paz , José A.S. Cavaleiro , João P.C. Tomé","doi":"10.1016/j.dyepig.2024.112535","DOIUrl":"10.1016/j.dyepig.2024.112535","url":null,"abstract":"<div><div>The synthesis and spectroscopic studies of four sensors for fluoride chromogenic sensing are described. The new compounds were prepared by the Knoevenagel condensation of diformyl-substituted bipyrrolic and dipyrrolic synthons ([2,2′-bipyrrole]-5,5′-dicarbaldehyde and dipyrromethane-1,9-dicarbaldehyde moieties) with malononitrile or indane-1,3-dione. They strongly absorb in the visible region and significant color changes occur in the presence of fluoride anions. Acetate and dihydrogenphosphate anions also induce observable colorimetric changes, albeit to a lesser extent. These changes, which are visible to the unaided eye, are associated with NH-bonding interactions that are unique to each anion. Non-linear regression analysis of the ground- and excited-state changes revealed anion recognition in a 2:1 stoichiometry (Host:Guest), where the electronegative character of the substituents (malononitrile or indane-1,3-dione residues) controls the sensitivity of the binding. The proposed systems all feature exceptional anion receptors that display an impressive chromogenic response through NH-bonding. Among these, compound 3 stands out with exceptionally high affinity constants of up to 7.39x10⁹ M⁻<sup>2</sup>, as well as an extremely low limit of detection at 92 ppm. NMR spectroscopy and mass spectrometry confirmed the structures of the synthesized compounds, with increased complexity in the NMR spectra due to the presence of malononitrile and indane-1,3-dione moieties. These findings highlight the potential of incorporating highly conjugated push-pull chromophores into bipyrrolic and dipyrrolic synthons for improved fluoride sensing performance in terms of both binding and signaling.</div></div>","PeriodicalId":302,"journal":{"name":"Dyes and Pigments","volume":"233 ","pages":"Article 112535"},"PeriodicalIF":4.1,"publicationDate":"2024-11-12","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142656676","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"工程技术","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"OA","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Pub Date : 2024-11-12DOI: 10.1016/j.dyepig.2024.112540
Mohamed R. Elmorsy , Safa A. Badawy , Hagar S. Elmetwaly , Esraa H. Elrewiny , Fatma M. Eshra , Ahmed E. Soliman , Kholoud E. Salem , Ehab Abdel-Latif , M. M. Elkholy
This study presents a significant advancement in tandem dye-sensitized solar cells (T-DSSCs) through the development of two carbazole-phenothiazine hybrid sensitizers, AEFH-1 and AEFH-2. AEFH-2, featuring a 4-carboxylcyanoacetamide acceptor group, thus achieving a remarkable power conversion efficiency (PCE) of 11.70 %, surpassing AEFH-1 (10.21 %) and the standard N719 dye (7.60 %). The superior performance of AEFH-2 is attributed to its optimized molecular design, which enhances the charge separation and electron injection efficiency. The incident photon-to-current efficiency (IPCE) of AEFH-2 reached 91.54 %, which was significantly higher than that of N719 (77.0 %) because of its strong electron-withdrawing groups and multiple anchoring functionalities, which improved TiO2 binding and charge transfer. Furthermore, an innovative double-sided parallel tandem DSSC (PT-DSSC) architecture was developed by integrating (N719 (top) and AEFH-2 (bottom)), resulting in a PCE of 12.85 %. This configuration exhibited exceptional photovoltaic parameters, including a Voc of 0.900 V, Jsc of 21.01 mA/cm2, and a fill factor of 67.95 %. The high IPCE of 97.50 % in the tandem setup was attributed to the complementary absorption profiles of N719 and AEFH-2, coupled with the light-trapping effect of the double-sided structure, enabling superior light harvesting and charge separation. Stability analysis further confirmed the durability of the tandem PT-DSSC, with performance maintained over 1000 h of continuous illumination, thus emphasizing its practical applicability. These findings underscore the potential of molecular engineering and architectural innovation to significantly enhance the efficiency and scalability of DSSCs, paving the way for high-performance, long-lasting solar energy devices.
{"title":"Carbazole-phenothiazine sensitizers boost tandem DSSC efficiency to 12.85 %","authors":"Mohamed R. Elmorsy , Safa A. Badawy , Hagar S. Elmetwaly , Esraa H. Elrewiny , Fatma M. Eshra , Ahmed E. Soliman , Kholoud E. Salem , Ehab Abdel-Latif , M. M. Elkholy","doi":"10.1016/j.dyepig.2024.112540","DOIUrl":"10.1016/j.dyepig.2024.112540","url":null,"abstract":"<div><div>This study presents a significant advancement in tandem dye-sensitized solar cells (T-DSSCs) through the development of two carbazole-phenothiazine hybrid sensitizers, <strong>AEFH-1</strong> and <strong>AEFH-2. AEFH-2</strong>, featuring a 4-carboxylcyanoacetamide acceptor group, thus achieving a remarkable power conversion efficiency (<em>PCE</em>) of 11.70 %, surpassing <strong>AEFH-1</strong> (10.21 %) and the standard <strong>N719</strong> dye (7.60 %). The superior performance of <strong>AEFH-2</strong> is attributed to its optimized molecular design, which enhances the charge separation and electron injection efficiency. The incident photon-to-current efficiency (<em>IPCE</em>) of <strong>AEFH-2</strong> reached 91.54 %, which was significantly higher than that of <strong>N719</strong> (77.0 %) because of its strong electron-withdrawing groups and multiple anchoring functionalities, which improved TiO<sub>2</sub> binding and charge transfer. Furthermore, an innovative double-sided parallel tandem DSSC (PT-DSSC) architecture was developed by integrating (<strong>N719 (top) and AEFH-2 (bottom)),</strong> resulting in a <em>PCE</em> of 12.85 %. This configuration exhibited exceptional photovoltaic parameters, including a <em>Voc</em> of 0.900 V, <em>Jsc</em> of 21.01 mA/cm<sup>2</sup>, and a fill factor of 67.95 %. The high <em>IPCE</em> of 97.50 % in the tandem setup was attributed to the complementary absorption profiles of <strong>N719</strong> and <strong>AEFH-2,</strong> coupled with the light-trapping effect of the double-sided structure, enabling superior light harvesting and charge separation. Stability analysis further confirmed the durability of the tandem PT-DSSC, with performance maintained over 1000 h of continuous illumination, thus emphasizing its practical applicability. These findings underscore the potential of molecular engineering and architectural innovation to significantly enhance the efficiency and scalability of DSSCs, paving the way for high-performance, long-lasting solar energy devices.</div></div>","PeriodicalId":302,"journal":{"name":"Dyes and Pigments","volume":"233 ","pages":"Article 112540"},"PeriodicalIF":4.1,"publicationDate":"2024-11-12","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142656677","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 : 2024-11-12DOI: 10.1016/j.dyepig.2024.112537
Hasrat Ali, Johan E. van Lier
We report on the synthesis and spectral properties of BODIPY 1,3-diyne dimers and 1,1-diynyl-1-alkene trimers, prepared via the Pd-catalyzed homocoupling reaction of a series of gem-dibromovinyl BODIPY (1,1-dibromo-1-alkene 4,4-difluoro-5-aryl-4-bora-3a,4a-diaza-s-indacene) dyes. The dimer and trimer moieties are connected through the ethynyl bond, attached at p-meso-phenyl or β-positions of the pyrrole ring, directly or through the phenyl spacer ring at the β-position. The assigned molecular structures of the products were confirmed using MS, 1H, 13C, 9F NMR and 11B NMR spectroscopic techniques. The absorption, fluorescence and solvatochromic properties were investigated in different solvents. The absorption maxima of unsubstituted pyrrole derivatives are bathochromic shifted as compared to the tetramethyl pyrrole substituted analogs. The highest absorption maxima were obtained when unsubstituted pyrrole 1,1-diynyl-1-alkene trimers featured a phenyl ring at the β-position. Dimers do fluoresce while trimers are void of fluorescence properties.
{"title":"Palladium catalyzed homocoupling reactions of gem-dibromo BODIPYs: Formation of dimer and trimer products","authors":"Hasrat Ali, Johan E. van Lier","doi":"10.1016/j.dyepig.2024.112537","DOIUrl":"10.1016/j.dyepig.2024.112537","url":null,"abstract":"<div><div>We report on the synthesis and spectral properties of BODIPY 1,3-diyne dimers and 1,1-diynyl-1-alkene trimers, prepared <em>via</em> the Pd-catalyzed homocoupling reaction of a series of <em>gem</em>-dibromovinyl BODIPY (1,1-dibromo-1-alkene 4,4-difluoro-5-aryl-4-bora-3a,4a-diaza-<em>s</em>-indacene) dyes. The dimer and trimer moieties are connected through the ethynyl bond, attached at <em>p</em>-<em>meso</em>-phenyl or β-positions of the pyrrole ring, directly or through the phenyl spacer ring at the β-position. The assigned molecular structures of the products were confirmed using MS, <sup>1</sup>H, <sup>13</sup>C, <sup>9</sup>F NMR and <sup>11</sup>B NMR spectroscopic techniques. The absorption, fluorescence and solvatochromic properties were investigated in different solvents. The absorption maxima of unsubstituted pyrrole derivatives are bathochromic shifted as compared to the tetramethyl pyrrole substituted analogs. The highest absorption maxima were obtained when unsubstituted pyrrole 1,1-diynyl-1-alkene trimers featured a phenyl ring at the β-position. Dimers do fluoresce while trimers are void of fluorescence properties.</div></div>","PeriodicalId":302,"journal":{"name":"Dyes and Pigments","volume":"233 ","pages":"Article 112537"},"PeriodicalIF":4.1,"publicationDate":"2024-11-12","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142656352","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 : 2024-11-10DOI: 10.1016/j.dyepig.2024.112538
Anastasia I. Ershova, Ilzia I. Khakimova, Mikhail Yu. Ievlev, Oleg V. Ershov
A method of preparation of new representatives of donor-acceptor stilbazoles based on pyridine-2-thione containing a cyano group and a trifluoromethyl moiety in the acceptor part of the molecule was developed. The synthesized stilbazoles exhibited pronounced fluorescence, with quantum yields up to about 15 % significantly improved compared to traditional thioxonicotinonitriles, which typically lack such properties. The emission turned out to be strongly dependent on the tautomeric equlibrium in the solution that was studied using both computational methods and comprehensive spectroscopic analysis. Solvato(fluoro)chromism and the influence of the substituent on the spectral characteristics of the compounds were also investigated. It was established that the emission maximum could be tuned from 418 to 630 nm covering almost the entire visible spectrum. The design of stilbazoles enhanced their photophysical properties making them suitable candidates for environmental monitoring or biological sensing. As a result a new chemosensor was developed demonstrating high selectivity for the detection of micromolar concentration of mercury(II) ions (LoD 1.34 μM) and submicromolar concentration of cadmium(II) ions (LoD 0.875 μM) in aqueous media.
{"title":"2-Thiopyridone-based stilbazoles: Synthesis, photo-physical properties and sensing of Hg(II) and Cd(II) ions","authors":"Anastasia I. Ershova, Ilzia I. Khakimova, Mikhail Yu. Ievlev, Oleg V. Ershov","doi":"10.1016/j.dyepig.2024.112538","DOIUrl":"10.1016/j.dyepig.2024.112538","url":null,"abstract":"<div><div>A method of preparation of new representatives of donor-acceptor stilbazoles based on pyridine-2-thione containing a cyano group and a trifluoromethyl moiety in the acceptor part of the molecule was developed. The synthesized stilbazoles exhibited pronounced fluorescence, with quantum yields up to about 15 % significantly improved compared to traditional thioxonicotinonitriles, which typically lack such properties. The emission turned out to be strongly dependent on the tautomeric equlibrium in the solution that was studied using both computational methods and comprehensive spectroscopic analysis. Solvato(fluoro)chromism and the influence of the substituent on the spectral characteristics of the compounds were also investigated. It was established that the emission maximum could be tuned from 418 to 630 nm covering almost the entire visible spectrum. The design of stilbazoles enhanced their photophysical properties making them suitable candidates for environmental monitoring or biological sensing. As a result a new chemosensor was developed demonstrating high selectivity for the detection of micromolar concentration of mercury(II) ions (LoD 1.34 μM) and submicromolar concentration of cadmium(II) ions (LoD 0.875 μM) in aqueous media.</div></div>","PeriodicalId":302,"journal":{"name":"Dyes and Pigments","volume":"233 ","pages":"Article 112538"},"PeriodicalIF":4.1,"publicationDate":"2024-11-10","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142656353","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 : 2024-11-07DOI: 10.1016/j.dyepig.2024.112528
Yun-Hao Yang , Wei-Long Cui , Mao-Hua Wang, Jian-Yong Wang
Viscosity is an important parameter of the cell microenvironment and is closely related to the occurrence of many diseases in vivo. Lipid droplets, as organelles that store and metabolize lipids, play a crucial role in various physiological processes related to cell metabolism. Monitoring cell viscosity and lipid droplets status is of great significance in studying cell function and disease pathogenesis. In this study, a series of novel fluorescent dyes were successfully synthesized by using malononitrile derivatives as fluorophores and modified by different substituents. The photophysical data of these dyes were summarized and the effects of different substituents on the optical properties of the dyes were studied. In addition, these dyes showed significant fluorescence enhancement effects in high-viscosity environments. Based on this, we further developed a novel viscosity-sensitive fluorescent probe DCN-LD that can be used for lipid droplets imaging. DCN-LD not only showed high viscosity sensitivity and good fluorescence stability but also exhibited AIE properties, large Stokes shifts (151 nm), and was capable of labeling intracellular lipid droplets. Finally, DCN-LD was successfully applied to monitor the changes in intracellular lipid droplets and changes in intracellular viscosity.
{"title":"Synthesis of fluorescent dyes based on the electron-withdrawing core of malononitrile and construction of viscosity-sensitive AIE probe with large Stokes shift for lipid droplets imaging","authors":"Yun-Hao Yang , Wei-Long Cui , Mao-Hua Wang, Jian-Yong Wang","doi":"10.1016/j.dyepig.2024.112528","DOIUrl":"10.1016/j.dyepig.2024.112528","url":null,"abstract":"<div><div>Viscosity is an important parameter of the cell microenvironment and is closely related to the occurrence of many diseases in vivo. Lipid droplets, as organelles that store and metabolize lipids, play a crucial role in various physiological processes related to cell metabolism. Monitoring cell viscosity and lipid droplets status is of great significance in studying cell function and disease pathogenesis. In this study, a series of novel fluorescent dyes were successfully synthesized by using malononitrile derivatives as fluorophores and modified by different substituents. The photophysical data of these dyes were summarized and the effects of different substituents on the optical properties of the dyes were studied. In addition, these dyes showed significant fluorescence enhancement effects in high-viscosity environments. Based on this, we further developed a novel viscosity-sensitive fluorescent probe <strong>DCN-LD</strong> that can be used for lipid droplets imaging. <strong>DCN-LD</strong> not only showed high viscosity sensitivity and good fluorescence stability but also exhibited <strong>AIE</strong> properties, large Stokes shifts (151 nm), and was capable of labeling intracellular lipid droplets. Finally, <strong>DCN-LD</strong> was successfully applied to monitor the changes in intracellular lipid droplets and changes in intracellular viscosity.</div></div>","PeriodicalId":302,"journal":{"name":"Dyes and Pigments","volume":"233 ","pages":"Article 112528"},"PeriodicalIF":4.1,"publicationDate":"2024-11-07","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142656351","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 : 2024-11-06DOI: 10.1016/j.dyepig.2024.112529
Yu Guan, Weize Wu, Jing Su, Liping Zhang
Rhodamine B (RhB) is a widely utilized xanthene dye known for its strong fluorescence, high quantum yield, bright color, and versatility in various applications. However, RhB type dyes face significant limitations due to their susceptibility to photodegradation. Herein, four RhB amine derivatives (RhB-1, RhB-2, RhB-3, and RhB-4) were synthesized to improve the light resistance through functionalization of the 4′ position of the carboxyphenyl ring with acrylamide, butylamine, octylamine, and cyclohexanamine, respectively. The mechanism of improving light resistance was analyzed. The results show that the derivatives demonstrated significantly enhanced light resistance compared to RhB, with the ability to form supramolecular structures including dimers and aggregates that protect against UV degradation. Light resistance for RhB-1 was significantly improved with increasing concentration as the photodegradation efficacy drops from 84.8 % (1.5 × 10−5 mol/L) to 10 % (2.0 × 10−4 mol/L), due to the dominant changes from monomers to J-dimers to H-aggregates. When incorporated into three-component thermochromic systems, the derivatives not only improved the light resistance with double duration of UV irradiation but also expanded the range of color change temperatures. This work advances the development of RhB derivatives with superior optical properties and durability, enhancing its applicability in environments requiring prolonged exposure to light.
{"title":"Synthesis of rhodamine B amine derivatives with improved light resistance and its application in thermochromic materials","authors":"Yu Guan, Weize Wu, Jing Su, Liping Zhang","doi":"10.1016/j.dyepig.2024.112529","DOIUrl":"10.1016/j.dyepig.2024.112529","url":null,"abstract":"<div><div>Rhodamine B (RhB) is a widely utilized xanthene dye known for its strong fluorescence, high quantum yield, bright color, and versatility in various applications. However, RhB type dyes face significant limitations due to their susceptibility to photodegradation. Herein, four RhB amine derivatives (RhB-1, RhB-2, RhB-3, and RhB-4) were synthesized to improve the light resistance through functionalization of the 4′ position of the carboxyphenyl ring with acrylamide, butylamine, octylamine, and cyclohexanamine, respectively. The mechanism of improving light resistance was analyzed. The results show that the derivatives demonstrated significantly enhanced light resistance compared to RhB, with the ability to form supramolecular structures including dimers and aggregates that protect against UV degradation. Light resistance for RhB-1 was significantly improved with increasing concentration as the photodegradation efficacy drops from 84.8 % (1.5 × 10<sup>−5</sup> mol/L) to 10 % (2.0 × 10<sup>−4</sup> mol/L), due to the dominant changes from monomers to J-dimers to H-aggregates. When incorporated into three-component thermochromic systems, the derivatives not only improved the light resistance with double duration of UV irradiation but also expanded the range of color change temperatures. This work advances the development of RhB derivatives with superior optical properties and durability, enhancing its applicability in environments requiring prolonged exposure to light.</div></div>","PeriodicalId":302,"journal":{"name":"Dyes and Pigments","volume":"233 ","pages":"Article 112529"},"PeriodicalIF":4.1,"publicationDate":"2024-11-06","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142656387","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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