Lingyu Kong, Manfen Zhao, Xiaofei Zhu, Jianfei Liu, Di Zhang, Yong Ye
The hydroxyl radical (·OH), widely recognized as the most potent free radical, plays a crucial role in numerous physiological and pathological pathways due to its strong oxidizability. Ferroptosis, as a novel mode of cell death, is initiated by the accumulation of iron-dependent lipid peroxidation. Among them, ·OH as the original reactive oxygen species (ROSs) is mass-produced due to Fenton reaction in vivo and closely related to cancer treatment. Besides, endoplasmic reticulum (ER) as a membrane-rich structure organelle, is a crucial organelle in all eukaryotes where excessive expression of ROSs, including ·OH can trigger ER stress which was reported that was closely related to ferroptosis. So developing a new probe for their interrelationship research is important. In this paper, we constructed a 1,8-naphthalimide-based ER-targeted fluorescence probe named M-1 to monitor ·OH variation in vitro and vivo. What's more, we achieved the monitor of ·OH during ER stress and ferroptosis processes in cancer cells, and further explored the important role of ER stress and ferroptosis processes in SF (sorafenib) involved cancer cells.
{"title":"A novel ·OH-monitor ER-targeted probe to expose the function of Sorafenib.","authors":"Lingyu Kong, Manfen Zhao, Xiaofei Zhu, Jianfei Liu, Di Zhang, Yong Ye","doi":"10.1002/asia.202400980","DOIUrl":"https://doi.org/10.1002/asia.202400980","url":null,"abstract":"<p><p>The hydroxyl radical (·OH), widely recognized as the most potent free radical, plays a crucial role in numerous physiological and pathological pathways due to its strong oxidizability. Ferroptosis, as a novel mode of cell death, is initiated by the accumulation of iron-dependent lipid peroxidation. Among them, ·OH as the original reactive oxygen species (ROSs) is mass-produced due to Fenton reaction in vivo and closely related to cancer treatment. Besides, endoplasmic reticulum (ER) as a membrane-rich structure organelle, is a crucial organelle in all eukaryotes where excessive expression of ROSs, including ·OH can trigger ER stress which was reported that was closely related to ferroptosis. So developing a new probe for their interrelationship research is important. In this paper, we constructed a 1,8-naphthalimide-based ER-targeted fluorescence probe named M-1 to monitor ·OH variation in vitro and vivo. What's more, we achieved the monitor of ·OH during ER stress and ferroptosis processes in cancer cells, and further explored the important role of ER stress and ferroptosis processes in SF (sorafenib) involved cancer cells.</p>","PeriodicalId":145,"journal":{"name":"Chemistry - An Asian Journal","volume":null,"pages":null},"PeriodicalIF":3.5,"publicationDate":"2024-09-24","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142306768","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Hydrogen-bonded organic frameworks (HOFs) are crystalline materials assembled by intermolecular hydrogen-bonding interactions, and their hydrogen-bonding structures are effective pathways for proton transport. Herein, we synthesize iHOF-45 using 4,4'-diaminodiphenylmethane and 1,3,6,8-pyrenetetrasulfonicacid sodium salt with 2D hydrogen-bonding networks. The introduction of ionic bond based on the weak hydrogen-bonding force was employed to enhance the stability of ionic HOFs (iHOFs). Thermal analyses demonstrated that iHOF-45 exhibited excellent thermal stability up to 332 °C. The proton conductivity of iHOF-45 was evaluated, demonstrating a notable increase with rising temperature and RH. At 100 °C and 98% RH, the conductivity reached 5.25 × 10-3 S cm-1. The activation energy (Ea) of iHOF-45 was calculated to be 0.281 eV for 98% RH, and the proton conduction was attributed to the Grotthuss mechanism, whereby the protons were transported in 2D hydrogen-bonding networks. Moreover, iHOF-45 was doped into SPEEK to prepare composite membranes, the proton conductivity of the 15%-iHOF-45/SPEEK membrane reached 9.52 × 10-2 S cm-1 at 80 °C and 98% RH, representing a 45.1% increase over that of the SPEEK. This suggests that doping enhances the proton conductivity of SPEEK and providing a reference for the development of high proton conductivity materials.
{"title":"High proton conductivity of sulfonate-amine ionic HOFs and enhancement of SPEEK composite membranes.","authors":"Dan Yang, Xu-Yong Chen, Li-Hui Cao","doi":"10.1002/asia.202400870","DOIUrl":"https://doi.org/10.1002/asia.202400870","url":null,"abstract":"<p><p>Hydrogen-bonded organic frameworks (HOFs) are crystalline materials assembled by intermolecular hydrogen-bonding interactions, and their hydrogen-bonding structures are effective pathways for proton transport. Herein, we synthesize iHOF-45 using 4,4'-diaminodiphenylmethane and 1,3,6,8-pyrenetetrasulfonicacid sodium salt with 2D hydrogen-bonding networks. The introduction of ionic bond based on the weak hydrogen-bonding force was employed to enhance the stability of ionic HOFs (iHOFs). Thermal analyses demonstrated that iHOF-45 exhibited excellent thermal stability up to 332 °C. The proton conductivity of iHOF-45 was evaluated, demonstrating a notable increase with rising temperature and RH. At 100 °C and 98% RH, the conductivity reached 5.25 × 10-3 S cm-1. The activation energy (Ea) of iHOF-45 was calculated to be 0.281 eV for 98% RH, and the proton conduction was attributed to the Grotthuss mechanism, whereby the protons were transported in 2D hydrogen-bonding networks. Moreover, iHOF-45 was doped into SPEEK to prepare composite membranes, the proton conductivity of the 15%-iHOF-45/SPEEK membrane reached 9.52 × 10-2 S cm-1 at 80 °C and 98% RH, representing a 45.1% increase over that of the SPEEK. This suggests that doping enhances the proton conductivity of SPEEK and providing a reference for the development of high proton conductivity materials.</p>","PeriodicalId":145,"journal":{"name":"Chemistry - An Asian Journal","volume":null,"pages":null},"PeriodicalIF":3.5,"publicationDate":"2024-09-24","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142306769","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Pavel Aleksandrovich Panchenko, Anastasija V Efremenko, Anna S Polyakova, Alexey V Feofanov, Maria A Ustimova, Yuri V Fedorov, Olga A Fedorova
Styrylpyridinium dye bearing azadithia-15-crown-5 ether receptor group SP and 4-alkoxy-1,8-naphthalimide fluorophore were linked using copper-catalyzed azide-alkyne cycloaddition click reaction to afford dyad compound NI-SP. Chemosensor NI-SP exhibited selective ratiometric fluorescent response to the presence of Hg2+ in aqueous solution due to the interplay between resonance energy transfer (RET) and intramolecular charge transfer (ICT) processes occurred upon excitation. The observed switching of the ratio of emission intensities in the blue and red channels R was higher than in the case of monochromophoric styrylpyridine derivative SP showing ratiometric response based on ICT mechanism only. Biological studies revealed that NI-SP penetrates into human lung adenocarcinoma A549 cells and accumulates in cytoplasm and lysosomes. When cells were pre-incubated with mercury (II) perchlorate, the ratio R was increased 2.6 times, which enables detection of intracellular Hg2+ ions and their quantitative analysis in the 0.7 - 6.0 μM concentration range.
{"title":"Application of RET Approach for Ratiometric Response Enhancement of ICT Fluorescent Hg2+ Probe Based on Crown-containing Styrylpyridinium Dye.","authors":"Pavel Aleksandrovich Panchenko, Anastasija V Efremenko, Anna S Polyakova, Alexey V Feofanov, Maria A Ustimova, Yuri V Fedorov, Olga A Fedorova","doi":"10.1002/asia.202400777","DOIUrl":"https://doi.org/10.1002/asia.202400777","url":null,"abstract":"<p><p>Styrylpyridinium dye bearing azadithia-15-crown-5 ether receptor group SP and 4-alkoxy-1,8-naphthalimide fluorophore were linked using copper-catalyzed azide-alkyne cycloaddition click reaction to afford dyad compound NI-SP. Chemosensor NI-SP exhibited selective ratiometric fluorescent response to the presence of Hg2+ in aqueous solution due to the interplay between resonance energy transfer (RET) and intramolecular charge transfer (ICT) processes occurred upon excitation. The observed switching of the ratio of emission intensities in the blue and red channels R was higher than in the case of monochromophoric styrylpyridine derivative SP showing ratiometric response based on ICT mechanism only. Biological studies revealed that NI-SP penetrates into human lung adenocarcinoma A549 cells and accumulates in cytoplasm and lysosomes. When cells were pre-incubated with mercury (II) perchlorate, the ratio R was increased 2.6 times, which enables detection of intracellular Hg2+ ions and their quantitative analysis in the 0.7 - 6.0 μM concentration range.</p>","PeriodicalId":145,"journal":{"name":"Chemistry - An Asian Journal","volume":null,"pages":null},"PeriodicalIF":3.5,"publicationDate":"2024-09-23","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142277547","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
In this study, we have developed a Chitin(Ch)-Poly(dioxanone)(PDO) gel system, which can be potentially used for tissue engineering. Hydrogel has been widely used in biomedical applications for its tuneable properties and biocompatibility. Chitin (Ch) is a natural biopolymer used for its ability to mimic the natural extracellular matrix due to N-acetyl glucosamine structural units. Poly (dioxanone) (PDO) is an FDA-approved synthetic biopolymer known for its mechanical properties, good biocompatibility, and poor inflammatory response. Based on this, we have developed Ch-PDO composite gel using simple regeneration chemistry and characterized it using FT-IR and SEM. The developed composite gel showed improved gel strength, good swelling ability,and controlled degradation behaviour. It also showed good injectability with shear thinning properties and hemocompatibility. Further, the biocompatibility and cell adhesion studies of the prepared gels were studied using dental follicle stem cells (DFSCs). The prepared Ch-PDO gel was biocompatible and showed DFSCs cell attachment. Osteogenic mineralization and RUNX2 expression of the prepared Ch and Ch-PDO gel was studied and Ch-PDO gel showed an enhanced mineralization and RUNX2 expression. Therefore, the developed chitin-PDO gel could be potentially used for bone tissue engineering.
{"title":"Synthesis, Characterization and Osteogenic Properties of Chitin-Polydioxanone Composite Gel.","authors":"Kavipriya Murugaiyan, Arthi Chandramouli, Jayakumar Rangasamy","doi":"10.1002/asia.202401024","DOIUrl":"https://doi.org/10.1002/asia.202401024","url":null,"abstract":"<p><p>In this study, we have developed a Chitin(Ch)-Poly(dioxanone)(PDO) gel system, which can be potentially used for tissue engineering. Hydrogel has been widely used in biomedical applications for its tuneable properties and biocompatibility. Chitin (Ch) is a natural biopolymer used for its ability to mimic the natural extracellular matrix due to N-acetyl glucosamine structural units. Poly (dioxanone) (PDO) is an FDA-approved synthetic biopolymer known for its mechanical properties, good biocompatibility, and poor inflammatory response. Based on this, we have developed Ch-PDO composite gel using simple regeneration chemistry and characterized it using FT-IR and SEM. The developed composite gel showed improved gel strength, good swelling ability,and controlled degradation behaviour. It also showed good injectability with shear thinning properties and hemocompatibility. Further, the biocompatibility and cell adhesion studies of the prepared gels were studied using dental follicle stem cells (DFSCs). The prepared Ch-PDO gel was biocompatible and showed DFSCs cell attachment. Osteogenic mineralization and RUNX2 expression of the prepared Ch and Ch-PDO gel was studied and Ch-PDO gel showed an enhanced mineralization and RUNX2 expression. Therefore, the developed chitin-PDO gel could be potentially used for bone tissue engineering.</p>","PeriodicalId":145,"journal":{"name":"Chemistry - An Asian Journal","volume":null,"pages":null},"PeriodicalIF":3.5,"publicationDate":"2024-09-23","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142306770","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
In this study, two novel tetra-substituted manganese (III) phthalocyanines bearing 9H-Carbazol-2-yloxy groups on peripheral or non-peripheral positions were prepared and used for modification of reduced graphene oxide by applying a simple one-step electrodeposition technique for the first time. The manganese (III) phthalocyanines (1 and 2) were electropolymerized and graphene oxide was electrochemically converted into reduced graphene oxide simultaneously. Subsequently, an rGO-MnPc hybrid structure was formed directly on the NiF electrode (substrate) via layer-by-layer assembly. Additionally, the effect of substituent position on the charge storage capacity of the prepared hybrid capacitive candidates was investigated. The fabricated hybrid electrodes exhibited remarkable electrochemical performance due to the combination of manganese (III) phthalocyanines and reduced graphene oxide. The NiF/rGO2-2 electrode exhibited the highest specific capacitance (512.4 F g-1) at 0.5 A g-1 and the remained specific capacitance was obtained 88.1% after 5000 consecutive charge-discharge cycles. An asymmetric supercapacitor (ASC) was constructed from rGO2-2 as the positive electrode and rGO as the negative electrode with a working potential of 1.5 V. The as-prepared device delivered a specific energy of 17.4 Wh kg-1 at 350 W kg-1. Hence, manganese (III) phthalocyanine-reduced graphene oxide electrodes can be considered outstanding materials for energy storage applications in the future.
{"title":"Electrodeposition of Manganese (III) Phthalocyanine/ Reduced Graphene Oxide for Asymmetric Supercapacitor Devices.","authors":"Hacer Yasemin Yenilmez, Nazlı Farajzadeh Öztürk, Özlem Budak, Özlem İpsiz Öney, Atıf Koca, Zehra Altuntaş Bayir","doi":"10.1002/asia.202400938","DOIUrl":"https://doi.org/10.1002/asia.202400938","url":null,"abstract":"<p><p>In this study, two novel tetra-substituted manganese (III) phthalocyanines bearing 9H-Carbazol-2-yloxy groups on peripheral or non-peripheral positions were prepared and used for modification of reduced graphene oxide by applying a simple one-step electrodeposition technique for the first time. The manganese (III) phthalocyanines (1 and 2) were electropolymerized and graphene oxide was electrochemically converted into reduced graphene oxide simultaneously. Subsequently, an rGO-MnPc hybrid structure was formed directly on the NiF electrode (substrate) via layer-by-layer assembly. Additionally, the effect of substituent position on the charge storage capacity of the prepared hybrid capacitive candidates was investigated. The fabricated hybrid electrodes exhibited remarkable electrochemical performance due to the combination of manganese (III) phthalocyanines and reduced graphene oxide. The NiF/rGO2-2 electrode exhibited the highest specific capacitance (512.4 F g-1) at 0.5 A g-1 and the remained specific capacitance was obtained 88.1% after 5000 consecutive charge-discharge cycles. An asymmetric supercapacitor (ASC) was constructed from rGO2-2 as the positive electrode and rGO as the negative electrode with a working potential of 1.5 V. The as-prepared device delivered a specific energy of 17.4 Wh kg-1 at 350 W kg-1. Hence, manganese (III) phthalocyanine-reduced graphene oxide electrodes can be considered outstanding materials for energy storage applications in the future.</p>","PeriodicalId":145,"journal":{"name":"Chemistry - An Asian Journal","volume":null,"pages":null},"PeriodicalIF":3.5,"publicationDate":"2024-09-22","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142277551","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
The synthesis of novel spirobenzazepinoindole derivatives has been achieved through a highly efficient and synthetic route. The approach involves a two-step reaction, utilizing indole derivatives, 2-amino benzyl alcohol, and ninhydrin as key starting materials under mild reaction conditions. The reaction proceeds via a sequential cascade process involving cyclization, condensation and spiro-annulation, leading to the formation of the spirobenzazepinoindole core structure in good to excellent yields. The method offers broad substrate scope, high atom economy, and operational simplicity. The synthesized spirobenzazepinoindoles were fully characterized by spectroscopic techniques, including NMR (1H & 13C), IR and mass spectrometry. The methodology provides a valuable tool for the rapid generation of structurally complex spirobenzazepinoindoles, which could serve as scaffolds for the development of new therapeutic agents.
{"title":"Syntheses of Novel Spirobenzazepinoindole Derivatives via Lewis-Acid Catalyzed Pictet-Spengler Cyclization.","authors":"Diksha Bansal, Gokulprasanth Nataraj, Pooja Sivaganesan, Mrinal Kanti Das, Saikat Chaudhuri","doi":"10.1002/asia.202401025","DOIUrl":"https://doi.org/10.1002/asia.202401025","url":null,"abstract":"<p><p>The synthesis of novel spirobenzazepinoindole derivatives has been achieved through a highly efficient and synthetic route. The approach involves a two-step reaction, utilizing indole derivatives, 2-amino benzyl alcohol, and ninhydrin as key starting materials under mild reaction conditions. The reaction proceeds via a sequential cascade process involving cyclization, condensation and spiro-annulation, leading to the formation of the spirobenzazepinoindole core structure in good to excellent yields. The method offers broad substrate scope, high atom economy, and operational simplicity. The synthesized spirobenzazepinoindoles were fully characterized by spectroscopic techniques, including NMR (1H & 13C), IR and mass spectrometry. The methodology provides a valuable tool for the rapid generation of structurally complex spirobenzazepinoindoles, which could serve as scaffolds for the development of new therapeutic agents.</p>","PeriodicalId":145,"journal":{"name":"Chemistry - An Asian Journal","volume":null,"pages":null},"PeriodicalIF":3.5,"publicationDate":"2024-09-22","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142277552","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Sheshanath V Bhosale, Sumit D Ambore, Sidhanath V Bhosale, Sheshanath V Bhosale
For the first time acceptor-π-donor-π-acceptor (A-π-D-π-A) based Y-type organic electrode material have been designed and successfully utilized in supercapacitor (SC) application. This Y-type molecular architecture coined as AQ-Im-PTZ-Im-AQ based on anthraquinone (AQ) (A)-imidazole (Im) (π)- phenothiazine (PTZ) (D)- imidazole (Im) (π)-anthraquinone (AQ) (A) in combination with graphite foil (GF). As-fabricated PTZ-Im-AQ/GF and AQ-Im-PTZ-Im-AQ/GF electrode have shown the good energy storage properties in three-electrode supercapacitor system. Moreover, two-electrode symmetric supercapacitor (SSC) device based on AQ-Im-PTZ-Im-AQ/GF electrode exhibited specific capacitance (Csp) of 68.97 F g-1 at 1 A g-1 current density. The specific electron density (ED) of SSC was observed to be 12.06 Wh kg-1 at a specific power density (PD) of 1798.50 W kg-1. The SSC device exhibited 81.62% of Csp retention after 5000 galvanostatic charge-discharge (GCD) cycles. For real world applications, AQ-Im-PTZ-Im-AQ/GF electrode was tested in symmetric Csp coin cell with applied potential voltage window of -0.4 to 1.0 V was found to be 112.32 F g-1 at 0.5 A g-1. Moreover, it realized high specific capacitance and high energy density of 19.66 Wh kg-1 at 891.94 W kg-1 power density. As a results, AQ-Im-PTZ-Im-AQ/GF make as an attractive electrode material for application in next-generation SCs.
首次设计出基于受体-π-供体-π-受体(A-π-D-π-A)的 Y 型有机电极材料,并成功将其应用于超级电容器(SC)。这种 Y 型分子结构被称为 AQ-Im-PTZ-Im-AQ,基于蒽醌(AQ)(A)-咪唑(Im)(π)-吩噻嗪(PTZ)(D)-咪唑(Im)(π)-蒽醌(AQ)(A)与石墨箔(GF)的结合。制备的 PTZ-Im-AQ/GF 和 AQ-Im-PTZ-Im-AQ/GF 电极在三电极超级电容器系统中显示出良好的储能特性。此外,基于 AQ-Im-PTZ-Im-AQ/GF 电极的双电极对称超级电容器(SSC)装置在 1 A g-1 电流密度下的比电容(Csp)为 68.97 F g-1。在比功率密度(PD)为 1798.50 W kg-1 时,SSC 的比电子密度(ED)为 12.06 Wh kg-1。经过 5000 次电静态充放电(GCD)循环后,SSC 器件的 Csp 保持率达到 81.62%。 在实际应用中,AQ-Im-PTZ-Im-AQ/GF 电极在-0.4 至 1.0 V 的对称 Csp 纽扣电池中进行了测试,发现在 0.5 A g-1 的条件下,AQ-Im-PTZ-Im-AQ/GF 电极的电位为 112.32 F g-1。此外,它还实现了高比电容和高能量密度(19.66 Wh kg-1,功率密度为 891.94 W kg-1)。因此,AQ-Im-PTZ-Im-AQ/GF 是一种极具吸引力的电极材料,可应用于下一代太阳能电池。
{"title":"Y-Shaped Acceptor-π-Donor-π-Acceptor Configured Anthraquinone-Tethered Phenothiazine Molecular Scaffold for High-Performance Organic Pseudocapacitors.","authors":"Sheshanath V Bhosale, Sumit D Ambore, Sidhanath V Bhosale, Sheshanath V Bhosale","doi":"10.1002/asia.202400691","DOIUrl":"https://doi.org/10.1002/asia.202400691","url":null,"abstract":"<p><p>For the first time acceptor-π-donor-π-acceptor (A-π-D-π-A) based Y-type organic electrode material have been designed and successfully utilized in supercapacitor (SC) application. This Y-type molecular architecture coined as AQ-Im-PTZ-Im-AQ based on anthraquinone (AQ) (A)-imidazole (Im) (π)- phenothiazine (PTZ) (D)- imidazole (Im) (π)-anthraquinone (AQ) (A) in combination with graphite foil (GF). As-fabricated PTZ-Im-AQ/GF and AQ-Im-PTZ-Im-AQ/GF electrode have shown the good energy storage properties in three-electrode supercapacitor system. Moreover, two-electrode symmetric supercapacitor (SSC) device based on AQ-Im-PTZ-Im-AQ/GF electrode exhibited specific capacitance (Csp) of 68.97 F g-1 at 1 A g-1 current density. The specific electron density (ED) of SSC was observed to be 12.06 Wh kg-1 at a specific power density (PD) of 1798.50 W kg-1. The SSC device exhibited 81.62% of Csp retention after 5000 galvanostatic charge-discharge (GCD) cycles. For real world applications, AQ-Im-PTZ-Im-AQ/GF electrode was tested in symmetric Csp coin cell with applied potential voltage window of -0.4 to 1.0 V was found to be 112.32 F g-1 at 0.5 A g-1. Moreover, it realized high specific capacitance and high energy density of 19.66 Wh kg-1 at 891.94 W kg-1 power density. As a results, AQ-Im-PTZ-Im-AQ/GF make as an attractive electrode material for application in next-generation SCs.</p>","PeriodicalId":145,"journal":{"name":"Chemistry - An Asian Journal","volume":null,"pages":null},"PeriodicalIF":3.5,"publicationDate":"2024-09-21","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142277554","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Xinxiang Huang, Yingying Yang, Qiping He, Chang Liu, Mingquan Yuan, Yi Jin
2,3'-Bisindoles with C-C linkages have attracted interest in medicinal chemistry, yet their synthesis is intricate with many steps. Notably, direct C-H/C-H cross-coupling of non-directed heteroaromatics remains challenging, often requiring precious metals and oxidants to enhance coupling efficiency. Herein, we present a copper-catalyzed C-H/C-H cross-coupling method for N-substituted indoles without directing groups, facilitated by molecular oxygen under gentle conditions. It showed reasonable functional group compatibility and provided one-pot access to a variety of 2,3'-bisindoles derivatives in moderate to good yields.
{"title":"Copper-Catalyzed Aerobic Cross-Dehydrogenation Coupling of Indoles for Synthesis of 2,3'-Bisindoles.","authors":"Xinxiang Huang, Yingying Yang, Qiping He, Chang Liu, Mingquan Yuan, Yi Jin","doi":"10.1002/asia.202401015","DOIUrl":"https://doi.org/10.1002/asia.202401015","url":null,"abstract":"<p><p>2,3'-Bisindoles with C-C linkages have attracted interest in medicinal chemistry, yet their synthesis is intricate with many steps. Notably, direct C-H/C-H cross-coupling of non-directed heteroaromatics remains challenging, often requiring precious metals and oxidants to enhance coupling efficiency. Herein, we present a copper-catalyzed C-H/C-H cross-coupling method for N-substituted indoles without directing groups, facilitated by molecular oxygen under gentle conditions. It showed reasonable functional group compatibility and provided one-pot access to a variety of 2,3'-bisindoles derivatives in moderate to good yields.</p>","PeriodicalId":145,"journal":{"name":"Chemistry - An Asian Journal","volume":null,"pages":null},"PeriodicalIF":3.5,"publicationDate":"2024-09-21","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142277549","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Ryosuke Hirozumi, Mayu Hakamada, Takashi Minowa, Yuko Cho, Yuta Kudo, Keiichi Konoki, Yasukatsu Oshima, Kazuo Nagasawa, Mari Yotsu-Yamashita
The synthesis and biosynthesis of the complex saxitoxin (STX) structure have garnered significant interest. Previously, we hypothesized that the tricyclic skeleton of STX originates from the monocyclic precursor 11-hydroxy-IntC'2 during biosynthesis, although direct evidence has been lacking. In this study, we identified conditions to synthesize a proposed tricyclic biosynthetic intermediate, 12,12-dideoxy-decarbamoyloxySTX (dd-doSTX), along with its 6-epimer (6-epi-dd-doSTX) and a bicyclic compound, in a single step from di-Boc protected 11-hydroxy-IntC'2. The reaction mechanism involves successive aza-Michael addition of a guanidino amine to the conjugated olefin. Notably, both dd-doSTX and 6-epi-dd-doSTX were detected in a toxin-producing cyanobacterium, suggesting that the biosynthetic enzymes may generate these compounds via similar mechanisms.
{"title":"Synthesis of Saxitoxin Biosynthetic Intermediates: Reveal the Mechanism for Formation of its Tricyclic Skeleton in Biosynthesis.","authors":"Ryosuke Hirozumi, Mayu Hakamada, Takashi Minowa, Yuko Cho, Yuta Kudo, Keiichi Konoki, Yasukatsu Oshima, Kazuo Nagasawa, Mari Yotsu-Yamashita","doi":"10.1002/asia.202400834","DOIUrl":"https://doi.org/10.1002/asia.202400834","url":null,"abstract":"<p><p>The synthesis and biosynthesis of the complex saxitoxin (STX) structure have garnered significant interest. Previously, we hypothesized that the tricyclic skeleton of STX originates from the monocyclic precursor 11-hydroxy-IntC'2 during biosynthesis, although direct evidence has been lacking. In this study, we identified conditions to synthesize a proposed tricyclic biosynthetic intermediate, 12,12-dideoxy-decarbamoyloxySTX (dd-doSTX), along with its 6-epimer (6-epi-dd-doSTX) and a bicyclic compound, in a single step from di-Boc protected 11-hydroxy-IntC'2. The reaction mechanism involves successive aza-Michael addition of a guanidino amine to the conjugated olefin. Notably, both dd-doSTX and 6-epi-dd-doSTX were detected in a toxin-producing cyanobacterium, suggesting that the biosynthetic enzymes may generate these compounds via similar mechanisms.</p>","PeriodicalId":145,"journal":{"name":"Chemistry - An Asian Journal","volume":null,"pages":null},"PeriodicalIF":3.5,"publicationDate":"2024-09-20","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142277553","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Mohammed Enamullah, Imdadul Haque, Amina Khan Resma, Nisat Taslum Jhumur, Dennis Woschko, Abdulrahman Mohabbat, Jan van Leusen, Paul Kögerler, Christoph Janiak
Reaction of the phenolate or naphthalen-2-olate based Schiff base ligands, (E)-1-((2-ethylphenylimino)methyl)phenol (HL1) or (E)-1-((2-ethylphenylimino)methyl)naphthalen-2-ol (HL2) with nickel(II) and copper(II) acetate provides the complexes bis[(E)-1-((2-ethylphenylimino)methyl)phenolato-ĸ2N,O]Ni/Cu(II), [Ni(L1)2] (1) and [Cu(L1)2] (2), or bis[(E)-1-((2-ethylphenylimino)methyl)naphthalen-2-olato-ĸ2N,O]Ni/Cu(II), [Ni(L2)2] (3) and [Cu(L2)2] (4), respectively. Single crystal X-ray structure determinations for 1, 3 and 4 reveal N2,O2-metal coordination of two chelating Schiff base ligands in a square-planar geometry. Powder X-ray diffractograms confirm the phase purity of the bulk microcrystalline samples. Thermal analyses by differential scanning calorimetry (DSC) and polarized light microscopic (PLM) indicate the copper(II) complexes to exhibit cold crystal (2) and liquid crystal (4) property. Cyclic voltammograms suggest an irreversible electrochemical process with two one electron charge transfer processes in N,N-dimethylformamide. Variable temperature magnetic measurements at the solid-state prove the diamagnetic nature of the low-spin Ni2+ centres in 1 or 3, as expected from the square-planar coordination geometry with rather strong ligands. The complexes expose medium level of antioxidant activity in methanol. Optimized geometry and excited state property by DFT/TD-DFT correspond well to the experimental results of the electronic and molecular structure at the ground state.
{"title":"Cold and Liquid Crystal Properties of Square-Planar Copper(II) Versus Nickel(II)-iminophenolate/naphthalen-2-olate Schiff Base Complexes.","authors":"Mohammed Enamullah, Imdadul Haque, Amina Khan Resma, Nisat Taslum Jhumur, Dennis Woschko, Abdulrahman Mohabbat, Jan van Leusen, Paul Kögerler, Christoph Janiak","doi":"10.1002/asia.202400915","DOIUrl":"https://doi.org/10.1002/asia.202400915","url":null,"abstract":"<p><p>Reaction of the phenolate or naphthalen-2-olate based Schiff base ligands, (E)-1-((2-ethylphenylimino)methyl)phenol (HL1) or (E)-1-((2-ethylphenylimino)methyl)naphthalen-2-ol (HL2) with nickel(II) and copper(II) acetate provides the complexes bis[(E)-1-((2-ethylphenylimino)methyl)phenolato-ĸ2N,O]Ni/Cu(II), [Ni(L1)2] (1) and [Cu(L1)2] (2), or bis[(E)-1-((2-ethylphenylimino)methyl)naphthalen-2-olato-ĸ2N,O]Ni/Cu(II), [Ni(L2)2] (3) and [Cu(L2)2] (4), respectively. Single crystal X-ray structure determinations for 1, 3 and 4 reveal N2,O2-metal coordination of two chelating Schiff base ligands in a square-planar geometry. Powder X-ray diffractograms confirm the phase purity of the bulk microcrystalline samples. Thermal analyses by differential scanning calorimetry (DSC) and polarized light microscopic (PLM) indicate the copper(II) complexes to exhibit cold crystal (2) and liquid crystal (4) property. Cyclic voltammograms suggest an irreversible electrochemical process with two one electron charge transfer processes in N,N-dimethylformamide. Variable temperature magnetic measurements at the solid-state prove the diamagnetic nature of the low-spin Ni2+ centres in 1 or 3, as expected from the square-planar coordination geometry with rather strong ligands. The complexes expose medium level of antioxidant activity in methanol. Optimized geometry and excited state property by DFT/TD-DFT correspond well to the experimental results of the electronic and molecular structure at the ground state.</p>","PeriodicalId":145,"journal":{"name":"Chemistry - An Asian Journal","volume":null,"pages":null},"PeriodicalIF":3.5,"publicationDate":"2024-09-20","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142277548","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}