The intrinsic catalytic activity of conventional spinel electrocatalysts hinders their electrocatalytic outcomes in lithium–oxygen batteries (LOBs), despite their appeal due to compositional variety and structural adaptability. In this work, we reveal that the electrocatalytic activities of these catalysts can be inherently enhanced by modulating metal–oxygen (M–O) bond covalency interactions through the introduction of the Cr element into the MnCo2O4 octahedral sites (MnCr0.5Co1.5O4). The introduction of Cr3+ directly alters the coordination structure of Co octahedral sites, which increases the Co3+–O distance and reduces the lattice symmetry, resulting in enhanced covalency interactions of the M–O bond. Computational analysis supports the effectiveness of Cr in altering the electronic structure of the active site, narrowing the energy gap between Co 3d and O 2p orbitals, evidencing the enhancement of the M–O covalency. In addition, this increased M–O covalency accelerates charge transfer in oxygen-related reactions, thereby facilitating the reversible formation and decomposition of the discharge products in LOBs. As a proof of concept, the MnCr0.5Co1.5O4 catalyzed LOBs exhibit a large discharge capacity of 16 388.3 mAh g–1 and maintain stability over 329 cycles. This work paves the way for the progression of reversible LOBs by manipulating the coordination structure of the spinel catalysts.
传统尖晶石电催化剂的内在催化活性阻碍了它们在锂-氧电池（LOB）中的电催化结果，尽管它们因成分多样性和结构适应性而具有吸引力。在这项研究中，我们发现通过在 MnCo2O4 八面体位点（MnCr0.5Co1.5O4）中引入 Cr 元素，调节金属-氧（M-O）键共价相互作用，可以从本质上增强这些催化剂的电催化活性。Cr3+ 的引入直接改变了 Co 八面体位点的配位结构，增加了 Co3+-O 间距，降低了晶格对称性，从而增强了 M-O 键的共价相互作用。计算分析证实了铬在改变活性位点电子结构方面的有效性，它缩小了 Co 3d 和 O 2p 轨道之间的能隙，证明了 M-O 共价作用的增强。此外，M-O 共价性的增强加快了氧相关反应中的电荷转移，从而促进了 LOB 中放电产物的可逆形成和分解。作为概念验证，MnCr0.5Co1.5O4 催化的 LOB 显示出 16 388.3 mAh g-1 的大放电容量，并在 329 次循环中保持稳定。这项工作为通过操纵尖晶石催化剂的配位结构来发展可逆 LOB 铺平了道路。
{"title":"Modulating Coordination Environment of Cobalt-Based Spinel Octahedral Metal Sites to Boost Metal–Oxygen Bond Covalency for Reversible Lithium–Oxygen Batteries","authors":"Yu Pan, Anjun Hu, Ruizhe Xu, Jingze Chen, Borui Yang, Ting Li, Kun Li, Yuanjian Li, Zhi Wei Seh, Jianping Long","doi":"10.1021/acssuschemeng.4c06092","DOIUrl":"https://doi.org/10.1021/acssuschemeng.4c06092","url":null,"abstract":"The intrinsic catalytic activity of conventional spinel electrocatalysts hinders their electrocatalytic outcomes in lithium–oxygen batteries (LOBs), despite their appeal due to compositional variety and structural adaptability. In this work, we reveal that the electrocatalytic activities of these catalysts can be inherently enhanced by modulating metal–oxygen (M–O) bond covalency interactions through the introduction of the Cr element into the MnCo<sub>2</sub>O<sub>4</sub> octahedral sites (MnCr<sub>0.5</sub>Co<sub>1.5</sub>O<sub>4</sub>). The introduction of Cr<sup>3+</sup> directly alters the coordination structure of Co octahedral sites, which increases the Co<sup>3+</sup>–O distance and reduces the lattice symmetry, resulting in enhanced covalency interactions of the M–O bond. Computational analysis supports the effectiveness of Cr in altering the electronic structure of the active site, narrowing the energy gap between Co 3d and O 2p orbitals, evidencing the enhancement of the M–O covalency. In addition, this increased M–O covalency accelerates charge transfer in oxygen-related reactions, thereby facilitating the reversible formation and decomposition of the discharge products in LOBs. As a proof of concept, the MnCr<sub>0.5</sub>Co<sub>1.5</sub>O<sub>4</sub> catalyzed LOBs exhibit a large discharge capacity of 16 388.3 mAh g<sup>–1</sup> and maintain stability over 329 cycles. This work paves the way for the progression of reversible LOBs by manipulating the coordination structure of the spinel catalysts.","PeriodicalId":7,"journal":{"name":"ACS Applied Polymer Materials","volume":"156 1","pages":""},"PeriodicalIF":8.4,"publicationDate":"2024-11-13","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142601333","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}
Pub Date : 2024-11-13DOI: 10.1016/j.envpol.2024.125205
Trifluralin, Chlorpyrifos, and Procymidone migration performance from polyethylene (PE) and biodegradable (Mater-Bi: M-B) mulching films was examined.…
{"title":"Factors that influence the migration of sorbed pesticides in polyethylene and biodegradable mesoplastics","authors":"","doi":"10.1016/j.envpol.2024.125205","DOIUrl":"https://doi.org/10.1016/j.envpol.2024.125205","url":null,"abstract":"Trifluralin, Chlorpyrifos, and Procymidone migration performance from polyethylene (PE) and biodegradable (Mater-Bi: M-B) mulching films was examined.…","PeriodicalId":7,"journal":{"name":"ACS Applied Polymer Materials","volume":"41 1","pages":""},"PeriodicalIF":8.9,"publicationDate":"2024-11-13","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142601184","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}
All-visible light-activated diarylethene (DAE) photoswitches are highly attractive for applications in smart photoresponsive materials. Photocyclization of DAE via the low-lying excited triplet state through triplet energy transfer (TET) from a sensitizer has been proven as an effective approach for the realization of this scheme. However, TET process is sensitive to oxygen and typically requires more than one sensitizer per photoswitch to facilitate sensitized photocyclization. Herein, we present a bi-component system comprising carboxylic acid-functionalized DAEs and CdS quantum dots (QDs) to achieve all-visible light-activated photoswithing. Due to the large surface area-to-volume ratio of CdS QDs and surface anchored DAEs, one CdS QD can activate at least 18 DAE molecules in the solution without oxygen exclusion. The efficiency of photocyclization of DAEs under visible light irradiation through energy transfer from CdS QDs is nearly comparable to direct UV light irradiation. Moreover, our strategy is adaptable to solid-state performance exposed in the air, enabling reversible writing and erasing of color and patterns by adjusting irradiation wavelengths in the visible region.
{"title":"An Efficient All-Visible Light-Activated Photoswitches Based on Diarylethenes and CdS Quantum Dots","authors":"Kezhou Chen, Jiayi Liu, Joakim Andréasson, Bo Albinsson, Tiegen Liu, Lili Hou","doi":"10.1039/d4sc06110a","DOIUrl":"https://doi.org/10.1039/d4sc06110a","url":null,"abstract":"All-visible light-activated diarylethene (DAE) photoswitches are highly attractive for applications in smart photoresponsive materials. Photocyclization of DAE via the low-lying excited triplet state through triplet energy transfer (TET) from a sensitizer has been proven as an effective approach for the realization of this scheme. However, TET process is sensitive to oxygen and typically requires more than one sensitizer per photoswitch to facilitate sensitized photocyclization. Herein, we present a bi-component system comprising carboxylic acid-functionalized DAEs and CdS quantum dots (QDs) to achieve all-visible light-activated photoswithing. Due to the large surface area-to-volume ratio of CdS QDs and surface anchored DAEs, one CdS QD can activate at least 18 DAE molecules in the solution without oxygen exclusion. The efficiency of photocyclization of DAEs under visible light irradiation through energy transfer from CdS QDs is nearly comparable to direct UV light irradiation. Moreover, our strategy is adaptable to solid-state performance exposed in the air, enabling reversible writing and erasing of color and patterns by adjusting irradiation wavelengths in the visible region.","PeriodicalId":7,"journal":{"name":"ACS Applied Polymer Materials","volume":"63 1","pages":""},"PeriodicalIF":8.4,"publicationDate":"2024-11-13","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142601879","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}
Pub Date : 2024-11-13DOI: 10.1021/acs.chemmater.4c01894
Yazhuo Kuang, Mingqun Yang, Langheng Pan, Gang Ye, Shuyan Shao, Chunhui Duan, Jian Liu
Effective charge transport properties and molecular doping efficiency are pivotal for achieving a high performance in organic thermoelectrics (OTEs). However, a significant challenge has been the scarcity of electron-deficient building blocks suitable for polymer construction. To address this shortfall, we introduce the quinoidal unit benzodipyrrolidone (BDP) into the realm of organic thermoelectrics for the first time. This work investigates the n-doping and thermoelectric properties of two BDP-based n-type polymers, PBDP-2F and PBDP-2CN. Notably, PBDP-2CN exhibited an ELUMO of −4.13 eV, representing a 0.11 eV reduction compared to PBDP-2F. Due to its high electron affinity, PBDP-2CN can be doped more easily than PBDP-2F, resulting in higher thermoelectric performance. Furthermore, our comparative analysis with Raman spectroscopy highlighted the exceptional structural stability of quinoidal-based polymers, as evidenced by the preservation of vibrational modes upon doping compared to P(NDI2OD-T2). This significant contribution heralds the innovative use of BDP as a building block in OTEs and yields crucial insights into the molecular design of n-type polymers for achieving a superior thermoelectric performance.
{"title":"Thermoelectric Performance of n-Type Conjugated Polymer Based on a Quinoidal Unit of Benzodipyrrolidone","authors":"Yazhuo Kuang, Mingqun Yang, Langheng Pan, Gang Ye, Shuyan Shao, Chunhui Duan, Jian Liu","doi":"10.1021/acs.chemmater.4c01894","DOIUrl":"https://doi.org/10.1021/acs.chemmater.4c01894","url":null,"abstract":"Effective charge transport properties and molecular doping efficiency are pivotal for achieving a high performance in organic thermoelectrics (OTEs). However, a significant challenge has been the scarcity of electron-deficient building blocks suitable for polymer construction. To address this shortfall, we introduce the quinoidal unit benzodipyrrolidone (BDP) into the realm of organic thermoelectrics for the first time. This work investigates the n-doping and thermoelectric properties of two BDP-based n-type polymers, PBDP-2F and PBDP-2CN. Notably, PBDP-2CN exhibited an <i>E</i><sub>LUMO</sub> of −4.13 eV, representing a 0.11 eV reduction compared to PBDP-2F. Due to its high electron affinity, PBDP-2CN can be doped more easily than PBDP-2F, resulting in higher thermoelectric performance. Furthermore, our comparative analysis with Raman spectroscopy highlighted the exceptional structural stability of quinoidal-based polymers, as evidenced by the preservation of vibrational modes upon doping compared to P(NDI2OD-T2). This significant contribution heralds the innovative use of BDP as a building block in OTEs and yields crucial insights into the molecular design of n-type polymers for achieving a superior thermoelectric performance.","PeriodicalId":7,"journal":{"name":"ACS Applied Polymer Materials","volume":"32 1","pages":""},"PeriodicalIF":8.6,"publicationDate":"2024-11-13","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142601785","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}
Lukas Bissegger, Theodora Alexandra Alexandra Constantin, Erhan Keles, Luka Raguž, Isobel Barlow-Busch, Clara Orbegozo, Thorsten Schaefer, Valentina Borlandelli, Thomas Bohnacker, Rohitha SriRamaratnam, Alexander Schäfer, Matthias Gstaiger, John E. Burke, Chiara Borsari, Matthias Wymann
Chemical probes have gained importance in the elucidation of signal transduction in biology. Insufficient selectivity and potency, lack of cellular activity and inappropriate use of chemical probes has major consequences on interpretation of biological results. The catalytic subunit of phosphoinositide 3-kinase α (PI3Kα) is one of the most frequently mutated genes in cancer, but fast-acting, high-quality probes to define PI3Kα's specific function to clearly separate it from other class I PI3K isoforms, are not available. Here, we present a series of novel covalent PI3Kα-targeting probes with optimized intracellular target access and kinetic parameters. On-target TR-FRET and off-target assays provided relevant kinetic parameters (kchem,kinact and Ki) to validate our chemical probes. Additional intracellular nanoBRET tracer displacement measurements showed rapid diffusion across the cell membrane and extremely fast target engagement, while investigations of signaling downstream of PI3Kα via protein kinase B (PKB/Akt) and forkhead box O (FOXO) revealed blunted pathway activity in cancer cell lines with constitutively activated PI3Kα lasting for several days. In contrast, persistent PI3Kα inhibition was rapidly bypassed by other class I PI3K isoforms in cells lacking functional Phosphatase and Tensin homolog (PTEN). Comparing the rapidly-diffusing, fast target-engaging chemical probe 9 to clinical reversible PI3Kα-selective inhibitors alpelisib, inavolisib and 9r, a reversible analogue of 9, revealed 9’s superior potency to inhibit growth (up to 600-fold) associated with sustained suppression of PI3Kα signaling in breast cancer cell lines. Finally, using a simple washout protocol, the utility of the highly-selective covalent PI3Kα probe 9 was demonstrated by the quantification of the coupling of insulin, EGF and CXCL12 receptors to distinct PI3K isoforms for signal transduction in response to ligand-dependent activation. Collectively, these findings along with the novel covalent chemical probes against PI3Kα provide insights into isoform-specific functions in cancer cells and highlight opportunities to achieve improved selectivity and long-lasting efficacy.
{"title":"Rapid, Potent, and Persistent Covalent Chemical Probes to Deconvolute PI3Kα Signaling","authors":"Lukas Bissegger, Theodora Alexandra Alexandra Constantin, Erhan Keles, Luka Raguž, Isobel Barlow-Busch, Clara Orbegozo, Thorsten Schaefer, Valentina Borlandelli, Thomas Bohnacker, Rohitha SriRamaratnam, Alexander Schäfer, Matthias Gstaiger, John E. Burke, Chiara Borsari, Matthias Wymann","doi":"10.1039/d4sc05459h","DOIUrl":"https://doi.org/10.1039/d4sc05459h","url":null,"abstract":"Chemical probes have gained importance in the elucidation of signal transduction in biology. Insufficient selectivity and potency, lack of cellular activity and inappropriate use of chemical probes has major consequences on interpretation of biological results. The catalytic subunit of phosphoinositide 3-kinase α (PI3Kα) is one of the most frequently mutated genes in cancer, but fast-acting, high-quality probes to define PI3Kα's specific function to clearly separate it from other class I PI3K isoforms, are not available. Here, we present a series of novel covalent PI3Kα-targeting probes with optimized intracellular target access and kinetic parameters. On-target TR-FRET and off-target assays provided relevant kinetic parameters (kchem,kinact and Ki) to validate our chemical probes. Additional intracellular nanoBRET tracer displacement measurements showed rapid diffusion across the cell membrane and extremely fast target engagement, while investigations of signaling downstream of PI3Kα via protein kinase B (PKB/Akt) and forkhead box O (FOXO) revealed blunted pathway activity in cancer cell lines with constitutively activated PI3Kα lasting for several days. In contrast, persistent PI3Kα inhibition was rapidly bypassed by other class I PI3K isoforms in cells lacking functional Phosphatase and Tensin homolog (PTEN). Comparing the rapidly-diffusing, fast target-engaging chemical probe 9 to clinical reversible PI3Kα-selective inhibitors alpelisib, inavolisib and 9r, a reversible analogue of 9, revealed 9’s superior potency to inhibit growth (up to 600-fold) associated with sustained suppression of PI3Kα signaling in breast cancer cell lines. Finally, using a simple washout protocol, the utility of the highly-selective covalent PI3Kα probe 9 was demonstrated by the quantification of the coupling of insulin, EGF and CXCL12 receptors to distinct PI3K isoforms for signal transduction in response to ligand-dependent activation. Collectively, these findings along with the novel covalent chemical probes against PI3Kα provide insights into isoform-specific functions in cancer cells and highlight opportunities to achieve improved selectivity and long-lasting efficacy.","PeriodicalId":7,"journal":{"name":"ACS Applied Polymer Materials","volume":"23 1","pages":""},"PeriodicalIF":8.4,"publicationDate":"2024-11-12","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142600033","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}
Pub Date : 2024-11-12DOI: 10.1109/tgrs.2024.3496812
Tianze Zhang, Daniel Trad, Kristopher Innanen
{"title":"Integrated networks for viscoelastic FWI: mapping from Q to relaxation variables and quantifying modelling error","authors":"Tianze Zhang, Daniel Trad, Kristopher Innanen","doi":"10.1109/tgrs.2024.3496812","DOIUrl":"https://doi.org/10.1109/tgrs.2024.3496812","url":null,"abstract":"","PeriodicalId":7,"journal":{"name":"ACS Applied Polymer Materials","volume":"107 1","pages":""},"PeriodicalIF":8.2,"publicationDate":"2024-11-12","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142600920","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}
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