Pub Date : 2025-03-20DOI: 10.1016/j.chempr.2025.102486
J. Luis Carrillo, Andrew A. Ezazi, Saul Perez-Beltran, Carlos A. Larriuz, Harris Kohl, Jaime A. Ayala, Arnab Maji, Stanislav Verkhoturov, Mohammed Al-Hashimi, Hassan Bazzi, Conan Weiland, Cherno Jaye, Daniel A. Fischer, Lucia Zuin, Jian Wang, Sarbajit Banerjee
The renaissance of nuclear energy has generated substantial demand for 6Li as a target for nuclear bombardment reactions to produce tritium fuel in breeder reactors. Conventional isotope separation methods utilize differential solubility in mercury amalgams, which pose performance, toxicity, and sustainability concerns. Here, we show that hybrid capacitive deionization wherein Li ions are inserted from aqueous media within the 1D tunnels of a metastable polymorph, ζ-V2O5, can be used to selectively sequester 6Li ions. An enrichment factor of ca. 57‰ is achieved. X-ray scattering, spectroscopy, and operando spectromicroscopy studies indicate that Li ions are sequestered within 1D tunnels of ζ-V2O5 through faradaic processes. 6Li and 7Li ions are found to migrate at different rates because of subtly different coordination environments. The results illustrate that ζ-V2O5 can be utilized as a discriminating host to selectively sequester and enrich 6Li from natural abundance precursor flow streams and suggest a distinctive mode of achieving viable isotope separation.
{"title":"Electrochemical 6Li isotope enrichment based on selective insertion in 1D tunnel-structured V2O5","authors":"J. Luis Carrillo, Andrew A. Ezazi, Saul Perez-Beltran, Carlos A. Larriuz, Harris Kohl, Jaime A. Ayala, Arnab Maji, Stanislav Verkhoturov, Mohammed Al-Hashimi, Hassan Bazzi, Conan Weiland, Cherno Jaye, Daniel A. Fischer, Lucia Zuin, Jian Wang, Sarbajit Banerjee","doi":"10.1016/j.chempr.2025.102486","DOIUrl":"https://doi.org/10.1016/j.chempr.2025.102486","url":null,"abstract":"The renaissance of nuclear energy has generated substantial demand for <sup>6</sup>Li as a target for nuclear bombardment reactions to produce tritium fuel in breeder reactors. Conventional isotope separation methods utilize differential solubility in mercury amalgams, which pose performance, toxicity, and sustainability concerns. Here, we show that hybrid capacitive deionization wherein Li ions are inserted from aqueous media within the 1D tunnels of a metastable polymorph, ζ-V<sub>2</sub>O<sub>5</sub>, can be used to selectively sequester <sup>6</sup>Li ions. An enrichment factor of ca. 57‰ is achieved. X-ray scattering, spectroscopy, and operando spectromicroscopy studies indicate that Li ions are sequestered within 1D tunnels of ζ-V<sub>2</sub>O<sub>5</sub> through faradaic processes. <sup>6</sup>Li and <sup>7</sup>Li ions are found to migrate at different rates because of subtly different coordination environments. The results illustrate that ζ-V<sub>2</sub>O<sub>5</sub> can be utilized as a discriminating host to selectively sequester and enrich <sup>6</sup>Li from natural abundance precursor flow streams and suggest a distinctive mode of achieving viable isotope separation.","PeriodicalId":268,"journal":{"name":"Chem","volume":"61 1","pages":""},"PeriodicalIF":23.5,"publicationDate":"2025-03-20","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143660511","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Pub Date : 2025-03-19DOI: 10.1016/j.chempr.2025.102524
Yoshio Barrera, Florian F. Mulks
Houk, Garg, and colleagues report in Nature a new and intriguing synthetic method for coupling strained cyclic allenes and bicyclo[1.1.0]butanes through σ-bond insertion along a diradical pathway under mild conditions and ambient temperature. Geometric distortion induces diradical behavior, driving the reaction. This study enables the direct synthesis of functionalized bicyclo[2.1.1]hexanes, opening new avenues in drug discovery.
{"title":"Strained diradicaloids for σ-bond-insertion reactions: A breakthrough in drug discovery","authors":"Yoshio Barrera, Florian F. Mulks","doi":"10.1016/j.chempr.2025.102524","DOIUrl":"https://doi.org/10.1016/j.chempr.2025.102524","url":null,"abstract":"Houk, Garg, and colleagues report in <em>Nature</em> a new and intriguing synthetic method for coupling strained cyclic allenes and bicyclo[1.1.0]butanes through <strong><em>σ</em></strong>-bond insertion along a diradical pathway under mild conditions and ambient temperature. Geometric distortion induces diradical behavior, driving the reaction. This study enables the direct synthesis of functionalized bicyclo[2.1.1]hexanes, opening new avenues in drug discovery.","PeriodicalId":268,"journal":{"name":"Chem","volume":"88 1","pages":""},"PeriodicalIF":23.5,"publicationDate":"2025-03-19","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143654260","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Pub Date : 2025-03-17DOI: 10.1016/j.chempr.2025.102499
Ruyi Zhou, Jicheng Yu, Zhen Gu
Disrupting redox homeostasis in cancer cells represents a promising strategy for minimizing toxicity and improving chemotherapy outcomes. In Cell Biomaterials, Chen, Ma, and colleagues describe an approach that employs a selenium electrophilic center with rapid electron-shuttle properties to boost mitochondrial electron leakage and thus convert antioxidants into pro-oxidants for cancer therapy.
{"title":"Electrophilic selenium drives electron leakage","authors":"Ruyi Zhou, Jicheng Yu, Zhen Gu","doi":"10.1016/j.chempr.2025.102499","DOIUrl":"https://doi.org/10.1016/j.chempr.2025.102499","url":null,"abstract":"Disrupting redox homeostasis in cancer cells represents a promising strategy for minimizing toxicity and improving chemotherapy outcomes. In <em>Cell Biomaterials</em>, Chen, Ma, and colleagues describe an approach that employs a selenium electrophilic center with rapid electron-shuttle properties to boost mitochondrial electron leakage and thus convert antioxidants into pro-oxidants for cancer therapy.","PeriodicalId":268,"journal":{"name":"Chem","volume":"89 1","pages":""},"PeriodicalIF":23.5,"publicationDate":"2025-03-17","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143635553","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Pub Date : 2025-03-13DOI: 10.1016/j.chempr.2024.10.004
Jingzhen Du , Benjamin E. Atkinson , John A. Seed , Rebecca F. Sheppard , Floriana Tuna , Ashley J. Wooles , Nicholas F. Chilton , Stephen T. Liddle
The dominant form of elemental nitrogen on Earth is dinitrogen, but elemental phosphorus is found predominantly as white phosphorus or other singly bonded allotropes. Thus, there is interest in studying diphosphorus derivatives, most notably trapping between metal ions affording diphosphorus in +2, +1⋅, 0, 1−⋅, 2−, and 4− charge states. However, the diphosphorus radical trianion form had previously remained elusive due to the instability of main-group diatomics with large, odd negative charges. Here, we disclose a crystalline diuranium diphosphorus radical trianion complex with strong antiferromagnetic uranium-phosphorus magnetic exchange coupling parameters of up to −731 cm−1. This value is over five times greater than that of lanthanide analogues and is comparable to or exceeds d-block metal-metal and metal-ligand exchange couplings, despite being based on a 5f metal, which is typically regarded as possessing contracted valence orbitals compared with d-block ions. This highlights exchange-coupled f-element-p-block radical bridged character that can be engendered in molecular magnetism.
{"title":"Strong uranium-phosphorus antiferromagnetic exchange coupling in a crystalline diphosphorus radical trianion actinide complex","authors":"Jingzhen Du , Benjamin E. Atkinson , John A. Seed , Rebecca F. Sheppard , Floriana Tuna , Ashley J. Wooles , Nicholas F. Chilton , Stephen T. Liddle","doi":"10.1016/j.chempr.2024.10.004","DOIUrl":"10.1016/j.chempr.2024.10.004","url":null,"abstract":"<div><div>The dominant form of elemental nitrogen on Earth is dinitrogen, but elemental phosphorus is found predominantly as white phosphorus or other singly bonded allotropes. Thus, there is interest in studying diphosphorus derivatives, most notably trapping between metal ions affording diphosphorus in +2, +1⋅, 0, 1−⋅, 2−, and 4− charge states. However, the diphosphorus radical trianion form had previously remained elusive due to the instability of main-group diatomics with large, odd negative charges. Here, we disclose a crystalline diuranium diphosphorus radical trianion complex with strong antiferromagnetic uranium-phosphorus magnetic exchange coupling parameters of up to −731 cm<sup>−1</sup>. This value is over five times greater than that of lanthanide analogues and is comparable to or exceeds d-block metal-metal and metal-ligand exchange couplings, despite being based on a 5f metal, which is typically regarded as possessing contracted valence orbitals compared with d-block ions. This highlights exchange-coupled f-element-p-block radical bridged character that can be engendered in molecular magnetism.</div></div>","PeriodicalId":268,"journal":{"name":"Chem","volume":"11 3","pages":"Article 102337"},"PeriodicalIF":19.1,"publicationDate":"2025-03-13","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142562033","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"OA","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Pub Date : 2025-03-13DOI: 10.1016/j.chempr.2024.09.024
Kaina Wang , Jipeng Fu , Sibo Zhan , Hongliang Dong , Chenjie Lou , Tianyi Sun , Jinru Liu , Bingyu Huang , Long Tian , Lihong Jiang , Ran Pang , Su Zhang , Huajie Luo , Mathieu Allix , Xiaojun Kuang , Shiqing Xu , Hongjie Zhang , Mingxue Tang
Near-infrared (NIR) luminescence materials with narrow-band emissions are essential for brain and muscle activity imaging based on the absorption difference of oxygenated proteins. However, most known NIR-emitting materials are limited by low external quantum efficiency (EQE) and broadband properties. This work presents the careful design of Tm, Na-doped strontium sulfide (SrS: Tm3+, Na+) phosphor for NIR light-emitting diode (LED), which shows a narrow emitting band of 27 nm. The successful incorporation of Na+ into SrS: Tm3+ contributes to the suppression of lattice phonons, resulting in significant improvement in EQE from 33.6% to 53.7% and an increase in thermal stability. The efficient host absorption and energy transfer are facilitated by the crystallographic Sr defects and the distortion in the symmetric crystal, disclosed by solid-state NMR, electron paramagnetic resonance (EPR), transient spectra, and X-ray total scattering analysis. Subsequently, efficient identification of vascular patterns based on the differential absorption of hemoglobin enables the potential application of rare-earth luminescent materials in NIR phosphor-converted light-emitting diodes (pc-LEDs) and bioimaging.
基于含氧蛋白质的吸收差异，具有窄带发射的近红外（NIR）发光材料对于大脑和肌肉活动成像至关重要。然而，大多数已知的近红外发光材料都受限于较低的外部量子效率（EQE）和宽带特性。本研究精心设计了掺 Tm、Na 的硫化锶（SrS：Tm3+、Na+）荧光粉，用于近红外发光二极管（LED）。将 Na+ 成功加入 SrS：Tm3+ 中成功掺入 Na+ 有助于抑制晶格声子，从而将 EQE 从 33.6% 显著提高到 53.7%，并增强了热稳定性。固态核磁共振（NMR）、电子顺磁共振（EPR）、瞬态光谱和 X 射线全散射分析表明，晶体学上的 Sr 缺陷和对称晶体的畸变促进了高效的宿主吸收和能量转移。随后，根据血红蛋白的差异吸收有效识别血管模式，使稀土发光材料有望应用于近红外荧光粉转换发光二极管（pc-LED）和生物成像。
{"title":"Boosting narrow-band near-infrared-emitting efficiency of thulium by lattice modulation for reflective absorption bioimaging","authors":"Kaina Wang , Jipeng Fu , Sibo Zhan , Hongliang Dong , Chenjie Lou , Tianyi Sun , Jinru Liu , Bingyu Huang , Long Tian , Lihong Jiang , Ran Pang , Su Zhang , Huajie Luo , Mathieu Allix , Xiaojun Kuang , Shiqing Xu , Hongjie Zhang , Mingxue Tang","doi":"10.1016/j.chempr.2024.09.024","DOIUrl":"10.1016/j.chempr.2024.09.024","url":null,"abstract":"<div><div>Near-infrared (NIR) luminescence materials with narrow-band emissions are essential for brain and muscle activity imaging based on the absorption difference of oxygenated proteins. However, most known NIR-emitting materials are limited by low external quantum efficiency (EQE) and broadband properties. This work presents the careful design of Tm, Na-doped strontium sulfide (SrS: Tm<sup>3+</sup>, Na<sup>+</sup>) phosphor for NIR light-emitting diode (LED), which shows a narrow emitting band of 27 nm. The successful incorporation of Na<sup>+</sup> into SrS: Tm<sup>3+</sup> contributes to the suppression of lattice phonons, resulting in significant improvement in EQE from 33.6% to 53.7% and an increase in thermal stability. The efficient host absorption and energy transfer are facilitated by the crystallographic Sr defects and the distortion in the symmetric crystal, disclosed by solid-state NMR, electron paramagnetic resonance (EPR), transient spectra, and X-ray total scattering analysis. Subsequently, efficient identification of vascular patterns based on the differential absorption of hemoglobin enables the potential application of rare-earth luminescent materials in NIR phosphor-converted light-emitting diodes (pc-LEDs) and bioimaging.</div></div>","PeriodicalId":268,"journal":{"name":"Chem","volume":"11 3","pages":"Article 102325"},"PeriodicalIF":19.1,"publicationDate":"2025-03-13","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142452045","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Helical molecular assemblies have been widely created so far, taking inspiration from helical bioconstructs (e.g., DNAs and proteins). However, the host utilities of such synthetic helices remain largely underdeveloped, particularly as chiroptical nanotools. Here, we report the preparation of new polyaromatic capsules with right- or left-handed quadruple helicity, regulated by chiral saccharide-based side chains attached at the outer surface. The capsule quantitatively encapsulates achiral fluorescent dyes in the cavity. The resultant host-guest complexes display excellent circularly polarized luminescence properties (up to |glum| = 1.6 × 10−2) derived from the bound dyes, through efficient optical chirality transfer from the outer biochiral groups to the inner achiral dyes via the quadruple helical shell, which represents an unprecedented chiroptical strategy. This nanotool can be applied to spherical fullerene to induce its chirality with high efficiency in solution (up to |gabs| = 1.0 × 10−2) and in the solid state.
{"title":"Remote optical chirality transfer via helical polyaromatic capsules upon encapsulation","authors":"Hayate Sasafuchi , Mayuko Ueda , Natsuki Kishida , Tomohisa Sawada , Seika Suzuki , Yoshitane Imai , Michito Yoshizawa","doi":"10.1016/j.chempr.2024.09.031","DOIUrl":"10.1016/j.chempr.2024.09.031","url":null,"abstract":"<div><div>Helical molecular assemblies have been widely created so far, taking inspiration from helical bioconstructs (e.g., DNAs and proteins). However, the host utilities of such synthetic helices remain largely underdeveloped, particularly as chiroptical nanotools. Here, we report the preparation of new polyaromatic capsules with right- or left-handed quadruple helicity, regulated by chiral saccharide-based side chains attached at the outer surface. The capsule quantitatively encapsulates achiral fluorescent dyes in the cavity. The resultant host-guest complexes display excellent circularly polarized luminescence properties (up to |<em>g</em><sub>lum</sub>| = 1.6 × 10<sup>−2</sup>) derived from the bound dyes, through efficient optical chirality transfer from the outer biochiral groups to the inner achiral dyes via the quadruple helical shell, which represents an unprecedented chiroptical strategy. This nanotool can be applied to spherical fullerene to induce its chirality with high efficiency in solution (up to |<em>g</em><sub>abs</sub>| = 1.0 × 10<sup>−2</sup>) and in the solid state.</div></div>","PeriodicalId":268,"journal":{"name":"Chem","volume":"11 3","pages":"Article 102332"},"PeriodicalIF":19.1,"publicationDate":"2025-03-13","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142536376","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"OA","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Pub Date : 2025-03-13DOI: 10.1016/j.chempr.2025.102442
Yiheng Lu , Melina Knezevic , Alessandro Prescimone , Bernd Goldfuss , Konrad Tiefenbacher
Although the field of C(sp3)–H oxidation has progressed tremendously over the last decades, the selective oxidation of non-activated positions on hydrocarbon skeletons is still highly challenging. It usually requires the presence of a suitable functional handle in proximity to the desired oxidation site. Here, we present a novel approach to catalyst-directed C–H oxidation that relies on substrate binding via the solvophobic effect in fluorinated alcohols and thus is independent of specific functional groups on the substrate. The supramolecular catalyst Mn(mcp)-RS2 enables the preferential oxidation at the fifth position from the less-hindered side on aliphatic substrates.
{"title":"Site-selective C(sp3)–H oxidation of alkyl substrates devoid of functional handles","authors":"Yiheng Lu , Melina Knezevic , Alessandro Prescimone , Bernd Goldfuss , Konrad Tiefenbacher","doi":"10.1016/j.chempr.2025.102442","DOIUrl":"10.1016/j.chempr.2025.102442","url":null,"abstract":"<div><div>Although the field of C(sp<sup>3</sup>)–H oxidation has progressed tremendously over the last decades, the selective oxidation of non-activated positions on hydrocarbon skeletons is still highly challenging. It usually requires the presence of a suitable functional handle in proximity to the desired oxidation site. Here, we present a novel approach to catalyst-directed C–H oxidation that relies on substrate binding via the solvophobic effect in fluorinated alcohols and thus is independent of specific functional groups on the substrate. The supramolecular catalyst Mn(mcp)-RS<sub>2</sub> enables the preferential oxidation at the fifth position from the less-hindered side on aliphatic substrates.</div></div>","PeriodicalId":268,"journal":{"name":"Chem","volume":"11 3","pages":"Article 102442"},"PeriodicalIF":19.1,"publicationDate":"2025-03-13","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143486401","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"OA","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Pub Date : 2025-03-13DOI: 10.1016/j.chempr.2025.102492
Engui Zhao , Ting Ma
Precisely navigating stem cells is crucial for enhancing the therapeutic outcomes in treating spinal cord injury (SCI). In a recent study published in Matter, Shen et al. introduced a breakthrough strategy that uses computed tomography (CT)-guided magnetic-driven soft microrobots for long-distance, precise stem cell delivery. This innovative approach offers great potential to accelerate the clinical translation of stem cell therapy for SCI.
{"title":"Soft microrobots for long-span precise stem cell delivery and restoration of neural connections","authors":"Engui Zhao , Ting Ma","doi":"10.1016/j.chempr.2025.102492","DOIUrl":"10.1016/j.chempr.2025.102492","url":null,"abstract":"<div><div>Precisely navigating stem cells is crucial for enhancing the therapeutic outcomes in treating spinal cord injury (SCI). In a recent study published in <em>Matter</em>, Shen et al. introduced a breakthrough strategy that uses computed tomography (CT)-guided magnetic-driven soft microrobots for long-distance, precise stem cell delivery. This innovative approach offers great potential to accelerate the clinical translation of stem cell therapy for SCI.</div></div>","PeriodicalId":268,"journal":{"name":"Chem","volume":"11 3","pages":"Article 102492"},"PeriodicalIF":19.1,"publicationDate":"2025-03-13","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143561045","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Pub Date : 2025-03-13DOI: 10.1016/j.chempr.2024.102406
Jie Zheng , Zhuang Mao Png , Xin Yi Oh , Huanning Zuo , Zibiao Li
Global plastic waste has reached a critical level, posing serious hazards to ecosystems and human health because of its persistent presence in landfills, oceans, and natural environments. Unlike heteroatom-backbone polymers, which feature a heterochain structure, homocarbon backbone polymers with nonpolar C–C backbones exhibit unprecedented durability and resistance to environmental factors, making them less prone to degradation. Consequently, the conversion of such plastic waste into valuable chemicals via chemical recycling presents a crucial solution to address the issues stemming from plastic waste. This review aims to summarize the latest developments in the closed-loop recycling and upcycling of homocarbon backbone polymers with a specific focus on the conversion of waste plastics into their original monomers and/or value-added chemicals through bio-, thermo-, and photocatalysis, which promotes a circular economy. Notably, the development of highly active catalysts and related depolymerization systems accelerates the evolution of plastic degradation and enhances product controllability, rendering the recycling of plastic waste feasible and affordable.
{"title":"Recycling homocarbon backbone polymers toward a circular materials economy","authors":"Jie Zheng , Zhuang Mao Png , Xin Yi Oh , Huanning Zuo , Zibiao Li","doi":"10.1016/j.chempr.2024.102406","DOIUrl":"10.1016/j.chempr.2024.102406","url":null,"abstract":"<div><div>Global plastic waste has reached a critical level, posing serious hazards to ecosystems and human health because of its persistent presence in landfills, oceans, and natural environments. Unlike heteroatom-backbone polymers, which feature a heterochain structure, homocarbon backbone polymers with nonpolar C–C backbones exhibit unprecedented durability and resistance to environmental factors, making them less prone to degradation. Consequently, the conversion of such plastic waste into valuable chemicals via chemical recycling presents a crucial solution to address the issues stemming from plastic waste. This review aims to summarize the latest developments in the closed-loop recycling and upcycling of homocarbon backbone polymers with a specific focus on the conversion of waste plastics into their original monomers and/or value-added chemicals through bio-, thermo-, and photocatalysis, which promotes a circular economy. Notably, the development of highly active catalysts and related depolymerization systems accelerates the evolution of plastic degradation and enhances product controllability, rendering the recycling of plastic waste feasible and affordable.</div></div>","PeriodicalId":268,"journal":{"name":"Chem","volume":"11 3","pages":"Article 102406"},"PeriodicalIF":19.1,"publicationDate":"2025-03-13","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143375294","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Pub Date : 2025-03-13DOI: 10.1016/j.chempr.2024.10.009
Javier Corpas , Eva Rivera-Chao , Enrique M. Arpa , Miguel Gomez-Mendoza , Yuri Katayama , Victor A. de la Peña O’Shea , Céline Bouchel , Clément Jacob , Pierre-Georges Echeverria , Alessandro Ruffoni , Daniele Leonori
The Birch reaction is a classical process used for the partial reduction of aromatics into non-conjugated cyclohexadienes that can be further functionalized. This strategy and its more modern variants are all based on an initial single-electron transfer event converting the arene into the corresponding radical anion for either protonation or hydrogen-atom transfer. Herein, we demonstrate an umpolung approach where the aromatic is first protonated to its corresponding carbocation and then reduced using the Lewis acid-base complex Et3N−BH3. This strategy requires aromatic photoexcitation so that protonation is favored by charge-transfer and driven by excited-state antiaromaticity relief. This means that aromatic excited-state basicity rather than ground-state redox potential needs to be considered when approaching reaction development. The mild conditions and the avoidance of strong reductants have enabled tolerance of functionalities generally not compatible under standard Birch conditions.
{"title":"Excited-state protonation and reduction enable the umpolung Birch reduction of naphthalenes","authors":"Javier Corpas , Eva Rivera-Chao , Enrique M. Arpa , Miguel Gomez-Mendoza , Yuri Katayama , Victor A. de la Peña O’Shea , Céline Bouchel , Clément Jacob , Pierre-Georges Echeverria , Alessandro Ruffoni , Daniele Leonori","doi":"10.1016/j.chempr.2024.10.009","DOIUrl":"10.1016/j.chempr.2024.10.009","url":null,"abstract":"<div><div>The Birch reaction is a classical process used for the partial reduction of aromatics into non-conjugated cyclohexadienes that can be further functionalized. This strategy and its more modern variants are all based on an initial single-electron transfer event converting the arene into the corresponding radical anion for either protonation or hydrogen-atom transfer. Herein, we demonstrate an umpolung approach where the aromatic is first protonated to its corresponding carbocation and then reduced using the Lewis acid-base complex Et<sub>3</sub>N−BH<sub>3</sub>. This strategy requires aromatic photoexcitation so that protonation is favored by charge-transfer and driven by excited-state antiaromaticity relief. This means that aromatic excited-state basicity rather than ground-state redox potential needs to be considered when approaching reaction development. The mild conditions and the avoidance of strong reductants have enabled tolerance of functionalities generally not compatible under standard Birch conditions.</div></div>","PeriodicalId":268,"journal":{"name":"Chem","volume":"11 3","pages":"Article 102342"},"PeriodicalIF":19.1,"publicationDate":"2025-03-13","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142684996","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"OA","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
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