首页 > 最新文献

化学•材料最新文献

英文 中文
IF:
Advancements in flexible perovskite solar cells enabling self-powered systems
IF 16.3 1区 工程技术 Q1 ENERGY & FUELS Pub Date : 2025-02-18 DOI: 10.1016/j.rser.2025.115488
Savisha Mahalingam , Abreeza Manap , Dita Floresyona , Ramisha Rabeya , Nurfanizan Afandi , Zaimah Hasan , Agung Nugroho
Flexible perovskite solar cells (FPSCs) have emerged as promising renewable energy technologies for powering self-sustaining systems. By combining the high efficiency of perovskite materials with the flexibility of lightweight substrates, FPSCs offer a versatile solution for solar energy harvesting. This review delves into advancements in FPSC technology, highlighting key components, fabrication techniques, and performance improvements. Integrating FPSCs with flexible energy storage devices such as supercapacitors and batteries is crucial for realizing self-powered systems. This review discusses the challenges and opportunities associated with this integration, including power management, durability, and scalability. Although significant progress has been made, challenges such as long-term stability, hysteresis, and scalability remain. Addressing these challenges is essential for commercializing FPSCs and their widespread adoption in self-powering applications. Moreover, the environmental impacts of FPSCs, including material sourcing, manufacturing processes, and end-of-life considerations, must be carefully evaluated. By addressing these challenges and considering their environmental impact, FPSCs have the potential to revolutionize the field of renewable energy and contribute to a sustainable future. This review provides a comprehensive overview of the current state-of-the-art and future perspectives for FPSCs, with the aim of stimulating further research and development in this exciting field. Specifically, future research should focus on improving the long-term stability of FPSCs, developing low-cost and scalable fabrication techniques, and optimizing the integration of FPSCs with energy storage devices. By addressing these key issues, FPSCs can become a practical and sustainable solution for powering a wide range of devices and applications.
{"title":"Advancements in flexible perovskite solar cells enabling self-powered systems","authors":"Savisha Mahalingam ,&nbsp;Abreeza Manap ,&nbsp;Dita Floresyona ,&nbsp;Ramisha Rabeya ,&nbsp;Nurfanizan Afandi ,&nbsp;Zaimah Hasan ,&nbsp;Agung Nugroho","doi":"10.1016/j.rser.2025.115488","DOIUrl":"10.1016/j.rser.2025.115488","url":null,"abstract":"<div><div>Flexible perovskite solar cells (FPSCs) have emerged as promising renewable energy technologies for powering self-sustaining systems. By combining the high efficiency of perovskite materials with the flexibility of lightweight substrates, FPSCs offer a versatile solution for solar energy harvesting. This review delves into advancements in FPSC technology, highlighting key components, fabrication techniques, and performance improvements. Integrating FPSCs with flexible energy storage devices such as supercapacitors and batteries is crucial for realizing self-powered systems. This review discusses the challenges and opportunities associated with this integration, including power management, durability, and scalability. Although significant progress has been made, challenges such as long-term stability, hysteresis, and scalability remain. Addressing these challenges is essential for commercializing FPSCs and their widespread adoption in self-powering applications. Moreover, the environmental impacts of FPSCs, including material sourcing, manufacturing processes, and end-of-life considerations, must be carefully evaluated. By addressing these challenges and considering their environmental impact, FPSCs have the potential to revolutionize the field of renewable energy and contribute to a sustainable future. This review provides a comprehensive overview of the current state-of-the-art and future perspectives for FPSCs, with the aim of stimulating further research and development in this exciting field. Specifically, future research should focus on improving the long-term stability of FPSCs, developing low-cost and scalable fabrication techniques, and optimizing the integration of FPSCs with energy storage devices. By addressing these key issues, FPSCs can become a practical and sustainable solution for powering a wide range of devices and applications.</div></div>","PeriodicalId":418,"journal":{"name":"Renewable and Sustainable Energy Reviews","volume":"213 ","pages":"Article 115488"},"PeriodicalIF":16.3,"publicationDate":"2025-02-18","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143427693","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"工程技术","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
引用次数: 0
Hexafluoroisopropanol (HFIP)-Promoted Hydrodifluoroalkylation of Furans and Vinyl Ethers Using Difluorinated Silyl Enol Ethers for the Synthesis of gem-Difluorinated Ethers
IF 4.354 2区 化学 Q1 CHEMISTRY, ORGANIC Pub Date : 2025-02-18 DOI: 10.1021/acs.joc.4c02420
Xiaogang Zhou, Jing Zhang, Manman Sun, Hai-Qin Yang, Zhiming Wang, Jianguo Yang, Guo-Bo Huang
A hexafluoroisopropanol (HFIP)-promoted hydrodifluoroalkylation of furans and vinyl ethers with difluorinated silyl enol ethers has been developed. Because of the inherent electron richer nature of furans and the poor nucleophilicity of difluorinated silyl enol ethers, the employment of simple furans as the substrates for nucleophilic dearomatization without a metal or stoichiometric chemical oxidizing reagent is challenging, especially considering the rearomatization driving force and ring fragmentation of the furan ring system. This protocol exploits the formation of oxocarbenium intermediate from furans using HFIP as a proton source to allow the nucleophilic addition of difluorinated silyl enol ethers, which provides an efficient synthetic strategy to install a gem-difluorinated group into heterocycles.
{"title":"Hexafluoroisopropanol (HFIP)-Promoted Hydrodifluoroalkylation of Furans and Vinyl Ethers Using Difluorinated Silyl Enol Ethers for the Synthesis of gem-Difluorinated Ethers","authors":"Xiaogang Zhou, Jing Zhang, Manman Sun, Hai-Qin Yang, Zhiming Wang, Jianguo Yang, Guo-Bo Huang","doi":"10.1021/acs.joc.4c02420","DOIUrl":"https://doi.org/10.1021/acs.joc.4c02420","url":null,"abstract":"A hexafluoroisopropanol (HFIP)-promoted hydrodifluoroalkylation of furans and vinyl ethers with difluorinated silyl enol ethers has been developed. Because of the inherent electron richer nature of furans and the poor nucleophilicity of difluorinated silyl enol ethers, the employment of simple furans as the substrates for nucleophilic dearomatization without a metal or stoichiometric chemical oxidizing reagent is challenging, especially considering the rearomatization driving force and ring fragmentation of the furan ring system. This protocol exploits the formation of oxocarbenium intermediate from furans using HFIP as a proton source to allow the nucleophilic addition of difluorinated silyl enol ethers, which provides an efficient synthetic strategy to install a <i>gem</i>-difluorinated group into heterocycles.","PeriodicalId":57,"journal":{"name":"Journal of Organic Chemistry","volume":"236 1","pages":""},"PeriodicalIF":4.354,"publicationDate":"2025-02-18","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143435533","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
引用次数: 0
Synthesis of Trifluoroacetamidoketones by Acylation of Ferrocene with In Situ Protected Amino Acids
IF 4.354 2区 化学 Q1 CHEMISTRY, ORGANIC Pub Date : 2025-02-18 DOI: 10.1021/acs.joc.4c02717
Michał Piotrowicz, Natasza Masłowska, Róża Dziewiątkowska, Anna Makal, Bogna Rudolf
The Friedel–Crafts acylation of ferrocene with amino acids carried out under mild conditions (metal-free catalytic system, room temperature, and a short reaction time of 1 h) has been reported. The acylating agent is generated in situ by N-protection of the amino group of the amino acid, followed by formation of mixed anhydride. This one-pot triflic-acid-promoted reaction provides N-trifluoroacetyl-protected amidoketones in good to excellent yields. Moreover, the trifluoroacetyl group can be easily removed or replaced with another protecting group under mild conditions in a one-pot procedure.
{"title":"Synthesis of Trifluoroacetamidoketones by Acylation of Ferrocene with In Situ Protected Amino Acids","authors":"Michał Piotrowicz, Natasza Masłowska, Róża Dziewiątkowska, Anna Makal, Bogna Rudolf","doi":"10.1021/acs.joc.4c02717","DOIUrl":"https://doi.org/10.1021/acs.joc.4c02717","url":null,"abstract":"The Friedel–Crafts acylation of ferrocene with amino acids carried out under mild conditions (metal-free catalytic system, room temperature, and a short reaction time of 1 h) has been reported. The acylating agent is generated in situ by N-protection of the amino group of the amino acid, followed by formation of mixed anhydride. This one-pot triflic-acid-promoted reaction provides <i>N</i>-trifluoroacetyl-protected amidoketones in good to excellent yields. Moreover, the trifluoroacetyl group can be easily removed or replaced with another protecting group under mild conditions in a one-pot procedure.","PeriodicalId":57,"journal":{"name":"Journal of Organic Chemistry","volume":"88 1","pages":""},"PeriodicalIF":4.354,"publicationDate":"2025-02-18","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143435536","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
引用次数: 0
Interfacial and Electrical Properties of Si/APS/MAPbI3 Heterostructure: An Ab Initio Study
IF 4.126 3区 化学 Q2 CHEMISTRY, PHYSICAL Pub Date : 2025-02-18 DOI: 10.1021/acs.jpcc.4c07083
Farhad Assareh Pour, Ghafar Darvish, Rahim Faez
In this study, we propose using 3-aminopropyl silane (APS) in the silicon/methylammonium lead iodide (MAPbI3) heterostructure to enhance interface properties. A first-principles study of the Si/APS/MAPbI3 heterostructure can provide a new approach to using this structure in advanced semiconductor devices. Using density functional theory and density-functional-based tight-binding methods, we investigated the electronic properties of the Si/APS/MAPbI3 heterostructure, including the density of states, band-edge orbitals, and electron deformation density. The effect of passivating compounds on the silicon surface has also been studied. The interface passivating structures used in this study include APS, OH molecules, and oxygen atoms, which are consistent with the experimental processes of APS attachment on the silicon surface. In such a structure, the amine group of the APS molecule acts as a cation in the perovskite structure, while the oxygen atoms of APS are bonded to the silicon substrate. In addition, other dangling bonds on the silicon surface are passivated by oxygen atoms and hydroxide molecules. The obtained results show that APS molecules can effectively passivate dangling interface bonds. However, the bonds on the surface of silicon change the Fermi energy (as an n-type semiconductor), and we have proposed a solution to control these changes. Our calculations show that the Fermi energy of the silicon surface can be more than 0.2 eV inside the conduction band. Also, the examination of band-edge orbitals shows that the effect of interfacial compounds on the formation of trap states is insignificant. The impressive optical properties of perovskite materials, together with the availability of silicon substrates, can provide significant progress in the development of low-cost and high-performance devices based on such structures.
{"title":"Interfacial and Electrical Properties of Si/APS/MAPbI3 Heterostructure: An Ab Initio Study","authors":"Farhad Assareh Pour, Ghafar Darvish, Rahim Faez","doi":"10.1021/acs.jpcc.4c07083","DOIUrl":"https://doi.org/10.1021/acs.jpcc.4c07083","url":null,"abstract":"In this study, we propose using 3-aminopropyl silane (APS) in the silicon/methylammonium lead iodide (MAPbI<sub>3</sub>) heterostructure to enhance interface properties. A first-principles study of the Si/APS/MAPbI<sub>3</sub> heterostructure can provide a new approach to using this structure in advanced semiconductor devices. Using density functional theory and density-functional-based tight-binding methods, we investigated the electronic properties of the Si/APS/MAPbI<sub>3</sub> heterostructure, including the density of states, band-edge orbitals, and electron deformation density. The effect of passivating compounds on the silicon surface has also been studied. The interface passivating structures used in this study include APS, OH molecules, and oxygen atoms, which are consistent with the experimental processes of APS attachment on the silicon surface. In such a structure, the amine group of the APS molecule acts as a cation in the perovskite structure, while the oxygen atoms of APS are bonded to the silicon substrate. In addition, other dangling bonds on the silicon surface are passivated by oxygen atoms and hydroxide molecules. The obtained results show that APS molecules can effectively passivate dangling interface bonds. However, the bonds on the surface of silicon change the Fermi energy (as an n-type semiconductor), and we have proposed a solution to control these changes. Our calculations show that the Fermi energy of the silicon surface can be more than 0.2 eV inside the conduction band. Also, the examination of band-edge orbitals shows that the effect of interfacial compounds on the formation of trap states is insignificant. The impressive optical properties of perovskite materials, together with the availability of silicon substrates, can provide significant progress in the development of low-cost and high-performance devices based on such structures.","PeriodicalId":61,"journal":{"name":"The Journal of Physical Chemistry C","volume":"5 1","pages":""},"PeriodicalIF":4.126,"publicationDate":"2025-02-18","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143435700","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}
引用次数: 0
Development of Aromatic Foldamer Building Blocks Bearing Multiple Biogenic Side Chains
IF 4.354 2区 化学 Q1 CHEMISTRY, ORGANIC Pub Date : 2025-02-18 DOI: 10.1021/acs.joc.4c02900
Márton Zwillinger, Petra Sőregi, Florian Sanchez, Céline Douat, Márton Csékei, Ivan Huc, András Kotschy
Aromatic oligoamides, with their intrinsic rigidity and well-defined conformations, are recognized for their potential in medical applications. Similar structures are present in several naturally occurring antibiotics and have been explored for their ability to bind to various proteins and B-DNA (canonical right-handed DNA helix). This study introduces a synthetic approach to produce quinoline amino acid monomers bearing diversified side chain combinations in positions 4, 5, and 6 of the quinoline ring, designed to enhance the side chain density on helical foldamers. By increasing the number of side chains on each monomer, we aim to mimic the dense side chain presentation of α-peptides, thus improving the potential for protein surface recognition. This synthetic strategy involves efficient functionalization through cross-coupling reactions, enabling the installation of diverse side chains at strategic positions on the quinoline ring. The process has been optimized for automated solid-phase synthesis, successfully producing a 20-unit oligoamide with good purity. This foldamer, featuring multiple cationic, anionic, polar, and hydrophobic side chains, demonstrates the potential for molecular recognition in drug discovery and therapeutic applications. The methodology described here represents a significant advancement in the construction of aromatic oligoamide foldamers, providing a robust platform for further exploration of biological systems.
{"title":"Development of Aromatic Foldamer Building Blocks Bearing Multiple Biogenic Side Chains","authors":"Márton Zwillinger, Petra Sőregi, Florian Sanchez, Céline Douat, Márton Csékei, Ivan Huc, András Kotschy","doi":"10.1021/acs.joc.4c02900","DOIUrl":"https://doi.org/10.1021/acs.joc.4c02900","url":null,"abstract":"Aromatic oligoamides, with their intrinsic rigidity and well-defined conformations, are recognized for their potential in medical applications. Similar structures are present in several naturally occurring antibiotics and have been explored for their ability to bind to various proteins and B-DNA (canonical right-handed DNA helix). This study introduces a synthetic approach to produce quinoline amino acid monomers bearing diversified side chain combinations in positions 4, 5, and 6 of the quinoline ring, designed to enhance the side chain density on helical foldamers. By increasing the number of side chains on each monomer, we aim to mimic the dense side chain presentation of α-peptides, thus improving the potential for protein surface recognition. This synthetic strategy involves efficient functionalization through cross-coupling reactions, enabling the installation of diverse side chains at strategic positions on the quinoline ring. The process has been optimized for automated solid-phase synthesis, successfully producing a 20-unit oligoamide with good purity. This foldamer, featuring multiple cationic, anionic, polar, and hydrophobic side chains, demonstrates the potential for molecular recognition in drug discovery and therapeutic applications. The methodology described here represents a significant advancement in the construction of aromatic oligoamide foldamers, providing a robust platform for further exploration of biological systems.","PeriodicalId":57,"journal":{"name":"Journal of Organic Chemistry","volume":"13 1","pages":""},"PeriodicalIF":4.354,"publicationDate":"2025-02-18","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143435534","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
引用次数: 0
Magnetic Moment and Spin-State Transitions in Twisted Graphene Nanostructures
IF 6.475 2区 化学 Q2 CHEMISTRY, PHYSICAL Pub Date : 2025-02-18 DOI: 10.1021/acs.jpclett.4c03542
F. N. N. Pansini, F. A. L. de Souza, V. C. Mota, Wendel S. Paz
The emergence of magnetic moments and spin-state transitions in the AA-stacking regions of twisted graphene nanoflakes is analyzed by using Density Functional Theory (DFT). Systems of different sizes (C192H48, C300H60, and C432H72) are employed to model some possible stacking angles. Potential Energy Curves (PECs) are computed for different interlayer distances and twist angles, revealing that the triplet ground state appears only in the repulsive region of the PEC, with the transition distance depending on the flake size. The results indicate that interlayer repulsion and twisted angle play significant roles in determining magnetic properties, while spin density analysis confirms that edge effects and AB-region confinement are fundamental to the emergence of magnetic moments in twisted graphene bilayers.
{"title":"Magnetic Moment and Spin-State Transitions in Twisted Graphene Nanostructures","authors":"F. N. N. Pansini, F. A. L. de Souza, V. C. Mota, Wendel S. Paz","doi":"10.1021/acs.jpclett.4c03542","DOIUrl":"https://doi.org/10.1021/acs.jpclett.4c03542","url":null,"abstract":"The emergence of magnetic moments and spin-state transitions in the AA-stacking regions of twisted graphene nanoflakes is analyzed by using Density Functional Theory (DFT). Systems of different sizes (C<sub>192</sub>H<sub>48</sub>, C<sub>300</sub>H<sub>60</sub>, and C<sub>432</sub>H<sub>72</sub>) are employed to model some possible stacking angles. Potential Energy Curves (PECs) are computed for different interlayer distances and twist angles, revealing that the triplet ground state appears only in the repulsive region of the PEC, with the transition distance depending on the flake size. The results indicate that interlayer repulsion and twisted angle play significant roles in determining magnetic properties, while spin density analysis confirms that edge effects and AB-region confinement are fundamental to the emergence of magnetic moments in twisted graphene bilayers.","PeriodicalId":62,"journal":{"name":"The Journal of Physical Chemistry Letters","volume":"28 1","pages":""},"PeriodicalIF":6.475,"publicationDate":"2025-02-18","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143435570","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
引用次数: 0
Toward Low Energetic Disorder in Organic Solar Cells: The Critical Role of Polymer Donors
IF 6.475 2区 化学 Q2 CHEMISTRY, PHYSICAL Pub Date : 2025-02-18 DOI: 10.1021/acs.jpclett.5c00132
Xiaodan Miao, Yaogang Zhang, Guangchao Han, Lingyun Zhu, Yuanping Yi
Compared with those of inorganic and perovskite solar cells, the power conversion efficiencies of organic solar cells (OSCs) are severely limited by a large energetic disorder. However, the origin of energetic disorder for OSCs remains poorly understood. Herein, we systematically investigate the energetic disorder in representative OSCs and the effect of both the acceptors and polymer donors by combining atomistic molecular dynamics simulations with density functional theory calculations. The results indicate that regardless of whether the OSCs are based on fullerene or acceptor–donor–acceptor (A–D–A) acceptors, the energetic disorder in the ionization potentials of the polymer donors is significantly larger than that in the electron affinities of the acceptors. Moreover, the energetic disorder of the donors matched with the fullerene acceptors is noticeably greater than that of the donors matched with the A–D–A acceptors. This implies that, different from our intuition, the reduction in the energetic disorder from the fullerene-based to A–D–A acceptor-based OSCs is primarily attributed to the change in the polymer donors rather than the acceptors. This work underscores the vital importance of optimizing polymer donors toward low energetic disorder for high-efficiency OSCs.
{"title":"Toward Low Energetic Disorder in Organic Solar Cells: The Critical Role of Polymer Donors","authors":"Xiaodan Miao, Yaogang Zhang, Guangchao Han, Lingyun Zhu, Yuanping Yi","doi":"10.1021/acs.jpclett.5c00132","DOIUrl":"https://doi.org/10.1021/acs.jpclett.5c00132","url":null,"abstract":"Compared with those of inorganic and perovskite solar cells, the power conversion efficiencies of organic solar cells (OSCs) are severely limited by a large energetic disorder. However, the origin of energetic disorder for OSCs remains poorly understood. Herein, we systematically investigate the energetic disorder in representative OSCs and the effect of both the acceptors and polymer donors by combining atomistic molecular dynamics simulations with density functional theory calculations. The results indicate that regardless of whether the OSCs are based on fullerene or acceptor–donor–acceptor (A–D–A) acceptors, the energetic disorder in the ionization potentials of the polymer donors is significantly larger than that in the electron affinities of the acceptors. Moreover, the energetic disorder of the donors matched with the fullerene acceptors is noticeably greater than that of the donors matched with the A–D–A acceptors. This implies that, different from our intuition, the reduction in the energetic disorder from the fullerene-based to A–D–A acceptor-based OSCs is primarily attributed to the change in the polymer donors rather than the acceptors. This work underscores the vital importance of optimizing polymer donors toward low energetic disorder for high-efficiency OSCs.","PeriodicalId":62,"journal":{"name":"The Journal of Physical Chemistry Letters","volume":"49 1","pages":""},"PeriodicalIF":6.475,"publicationDate":"2025-02-18","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143435572","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
引用次数: 0
Manipulation of Metal Halide Perovskite: Photoelectric Conversion or Light Emission?
IF 6.475 2区 化学 Q2 CHEMISTRY, PHYSICAL Pub Date : 2025-02-18 DOI: 10.1021/acs.jpclett.4c03556
Jun Zhan, Xiao Huang, Hongzhe Du, Xinli Wang, Yang Sun, Yi Wang, Xi-Cheng Ai, Li-Min Fu, Jian-Ping Zhang
Metal halide perovskites (MHPs) display a range of superior photophysical properties, rendering them promising as a candidate for the active medium of high-efficiency photovoltaic and electroluminescence devices. In order to maximize their efficacy in photoelectric conversion or light emission, it is essential to regulate the charge separation efficiency of MHPs in a desired manner. Herein, we demonstrate that the extent of charge separation can be effectively manipulated upon thermal annealing treatment on MHPs. As the annealing time is extended from 10 to 30 min, the accumulation of excess lead halides is observed at the boundaries of MHP grains, resulting in the construction of a quasi-Type II band alignment between the lead halide and the MHP. This facilitates the separation of electron–hole pairs, reducing the exciton binding energy from approximately 102 meV to a level comparable with kBT. Our findings elucidate the transition of MHPs from a light-emission material to a photoelectric-conversion material along with continuous heating treatment, which is anticipated to guide the flexible regulation of MHPs to meet the requirements of specific practical applications.
{"title":"Manipulation of Metal Halide Perovskite: Photoelectric Conversion or Light Emission?","authors":"Jun Zhan, Xiao Huang, Hongzhe Du, Xinli Wang, Yang Sun, Yi Wang, Xi-Cheng Ai, Li-Min Fu, Jian-Ping Zhang","doi":"10.1021/acs.jpclett.4c03556","DOIUrl":"https://doi.org/10.1021/acs.jpclett.4c03556","url":null,"abstract":"Metal halide perovskites (MHPs) display a range of superior photophysical properties, rendering them promising as a candidate for the active medium of high-efficiency photovoltaic and electroluminescence devices. In order to maximize their efficacy in photoelectric conversion or light emission, it is essential to regulate the charge separation efficiency of MHPs in a desired manner. Herein, we demonstrate that the extent of charge separation can be effectively manipulated upon thermal annealing treatment on MHPs. As the annealing time is extended from 10 to 30 min, the accumulation of excess lead halides is observed at the boundaries of MHP grains, resulting in the construction of a quasi-Type II band alignment between the lead halide and the MHP. This facilitates the separation of electron–hole pairs, reducing the exciton binding energy from approximately 10<sup>2</sup> meV to a level comparable with <i>k</i><sub>B</sub><i>T</i>. Our findings elucidate the transition of MHPs from a light-emission material to a photoelectric-conversion material along with continuous heating treatment, which is anticipated to guide the flexible regulation of MHPs to meet the requirements of specific practical applications.","PeriodicalId":62,"journal":{"name":"The Journal of Physical Chemistry Letters","volume":"13 1","pages":""},"PeriodicalIF":6.475,"publicationDate":"2025-02-18","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143435571","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
引用次数: 0
Seven-Membered Ring Formation in Triterpene Biosynthesis: A Key Cyclopropane Rearrangement in Ilelic Acid Biosynthesis
IF 4.354 2区 化学 Q1 CHEMISTRY, ORGANIC Pub Date : 2025-02-17 DOI: 10.1021/acs.joc.4c02541
Moe Nakano, Kazuma Hiasa, Satoko Sato-Shimizu, Hajime Sato
Triterpenes represent a crucial class of natural compounds with diverse biological activities and structural complexity. Among the various skeletal modifications in triterpene biosynthesis, the formation of seven-membered rings through ring expansion reactions significantly contributes to their structural diversity and, consequently, their functional versatility. This study elucidates the detailed reaction mechanism of a key seven-membered ring formation via cyclopropane rearrangement in the biosynthesis of ilelic acid. Using density functional theory (DFT) calculations, we thoroughly investigated the biosynthetic pathway of ilelic acid, focusing on the critical ring expansion step. Our computational analysis reveals that the seven-membered ring formation proceeds through a cationic mechanism rather than a radical-mediated process. Notably, we found that the inherent instability of the secondary carbocation intermediate drives a concerted reaction pathway, avoiding the formation of high-energy intermediates. This mechanistic understanding not only sheds light on the biosynthesis of ilelic acid but also offers broader implications for comprehending similar transformations in other triterpene biosynthetic pathways. Our findings contribute to the fundamental understanding of triterpene skeletal diversity and pave the way for potential biomimetic approaches in the synthesis of complex seven-membered ring-containing terpenes. Furthermore, this work underscores the power of computational methods in unraveling intricate biosynthetic mechanisms.
{"title":"Seven-Membered Ring Formation in Triterpene Biosynthesis: A Key Cyclopropane Rearrangement in Ilelic Acid Biosynthesis","authors":"Moe Nakano, Kazuma Hiasa, Satoko Sato-Shimizu, Hajime Sato","doi":"10.1021/acs.joc.4c02541","DOIUrl":"https://doi.org/10.1021/acs.joc.4c02541","url":null,"abstract":"Triterpenes represent a crucial class of natural compounds with diverse biological activities and structural complexity. Among the various skeletal modifications in triterpene biosynthesis, the formation of seven-membered rings through ring expansion reactions significantly contributes to their structural diversity and, consequently, their functional versatility. This study elucidates the detailed reaction mechanism of a key seven-membered ring formation via cyclopropane rearrangement in the biosynthesis of ilelic acid. Using density functional theory (DFT) calculations, we thoroughly investigated the biosynthetic pathway of ilelic acid, focusing on the critical ring expansion step. Our computational analysis reveals that the seven-membered ring formation proceeds through a cationic mechanism rather than a radical-mediated process. Notably, we found that the inherent instability of the secondary carbocation intermediate drives a concerted reaction pathway, avoiding the formation of high-energy intermediates. This mechanistic understanding not only sheds light on the biosynthesis of ilelic acid but also offers broader implications for comprehending similar transformations in other triterpene biosynthetic pathways. Our findings contribute to the fundamental understanding of triterpene skeletal diversity and pave the way for potential biomimetic approaches in the synthesis of complex seven-membered ring-containing terpenes. Furthermore, this work underscores the power of computational methods in unraveling intricate biosynthetic mechanisms.","PeriodicalId":57,"journal":{"name":"Journal of Organic Chemistry","volume":"12 1","pages":""},"PeriodicalIF":4.354,"publicationDate":"2025-02-17","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143427365","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
引用次数: 0
NHC-BH3-Mediated Reduction of Sulfonyl Hydrazides into Disulfides and Further Cross-Coupling with Chlorostibine and Bioactivities
IF 4.354 2区 化学 Q1 CHEMISTRY, ORGANIC Pub Date : 2025-02-17 DOI: 10.1021/acs.joc.4c02638
Wenjun Zhou, Liyuan Le, Youwen Chen, Wuxing Xie, Yi Chen, Shuang-Feng Yin, Renhua Qiu
This paper presents a novel NHC-BH3-promoted one-step synthesis of disulfides and stibine sulfides using odorless sulfonyl hydrazides. The protocol tolerates various functional groups as well as heterocyclic compounds. Mechanistic studies show that NHC-BH3 plays two roles: (1) reducing sulfonyl hydrazides into disulfides and (2) promoting the cross-coupling of chlorostibine with the disulfides. The synthesized stibine sulfides also exhibit satisfactory anticancer activity against 4T1 and MDA-MB-231 cancerous cells.
{"title":"NHC-BH3-Mediated Reduction of Sulfonyl Hydrazides into Disulfides and Further Cross-Coupling with Chlorostibine and Bioactivities","authors":"Wenjun Zhou, Liyuan Le, Youwen Chen, Wuxing Xie, Yi Chen, Shuang-Feng Yin, Renhua Qiu","doi":"10.1021/acs.joc.4c02638","DOIUrl":"https://doi.org/10.1021/acs.joc.4c02638","url":null,"abstract":"This paper presents a novel NHC-BH<sub>3</sub>-promoted one-step synthesis of disulfides and stibine sulfides using odorless sulfonyl hydrazides. The protocol tolerates various functional groups as well as heterocyclic compounds. Mechanistic studies show that NHC-BH<sub>3</sub> plays two roles: (1) reducing sulfonyl hydrazides into disulfides and (2) promoting the cross-coupling of chlorostibine with the disulfides. The synthesized stibine sulfides also exhibit satisfactory anticancer activity against 4T1 and MDA-MB-231 cancerous cells.","PeriodicalId":57,"journal":{"name":"Journal of Organic Chemistry","volume":"19 1","pages":""},"PeriodicalIF":4.354,"publicationDate":"2025-02-17","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143435535","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
引用次数: 0
×
引用
GB/T 7714-2015
复制
MLA
复制
APA
复制
导出至
BibTeX EndNote RefMan NoteFirst NoteExpress
×
0
微信
客服QQ
Book学术公众号 扫码关注我们
反馈
×
意见反馈
请填写您的意见或建议
请填写您的手机或邮箱
×
提示
您的信息不完整,为了账户安全,请先补充。
现在去补充
×
提示
您因"违规操作"
具体请查看互助需知
我知道了
×
提示
现在去查看 取消
×
提示
确定
Book学术官方微信
Book学术文献互助
Book学术文献互助群
群 号:481959085
Book学术
文献互助 智能选刊 最新文献 互助须知 联系我们:info@booksci.cn
Book学术提供免费学术资源搜索服务,方便国内外学者检索中英文文献。致力于提供最便捷和优质的服务体验。
Copyright © 2023 Book学术 All rights reserved.
ghs 京公网安备 11010802042870号 京ICP备2023020795号-1