Matthew M Hausladen, Esteban Baca, Kyle A Nogales, Leah N Appelhans, Bryan Kaehr, Craig M Hamel, Samuel C Leguizamon
Polymerization in the solid state is generally infeasible due to restrictions on mobility. However, in this work, the solid-state photopolymerization of crystalline dicyclopentadiene is demonstrated via photoinitiated ring-opening metathesis polymerization. The source of mobility in the solid state is attributed to the plastic crystal nature of dicyclopentadiene, which yields local short-range mobility due to orientational degrees of freedom. Polymerization in the solid state enables photopatterning, volumetric additive manufacturing of free-standing structures, and fabrication with embedded components. Solid-state photopolymerization of dicyclopentadiene offers a new paradigm for advanced and freeform fabrication of high-performance thermosets.
{"title":"Volumetric Additive Manufacturing of Dicyclopentadiene by Solid-State Photopolymerization.","authors":"Matthew M Hausladen, Esteban Baca, Kyle A Nogales, Leah N Appelhans, Bryan Kaehr, Craig M Hamel, Samuel C Leguizamon","doi":"10.1002/advs.202402385","DOIUrl":"https://doi.org/10.1002/advs.202402385","url":null,"abstract":"<p><p>Polymerization in the solid state is generally infeasible due to restrictions on mobility. However, in this work, the solid-state photopolymerization of crystalline dicyclopentadiene is demonstrated via photoinitiated ring-opening metathesis polymerization. The source of mobility in the solid state is attributed to the plastic crystal nature of dicyclopentadiene, which yields local short-range mobility due to orientational degrees of freedom. Polymerization in the solid state enables photopatterning, volumetric additive manufacturing of free-standing structures, and fabrication with embedded components. Solid-state photopolymerization of dicyclopentadiene offers a new paradigm for advanced and freeform fabrication of high-performance thermosets.</p>","PeriodicalId":117,"journal":{"name":"Advanced Science","volume":null,"pages":null},"PeriodicalIF":14.3,"publicationDate":"2024-07-05","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"141532944","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"材料科学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Fancong Zeng, Lin Xu, Jiahe Xing, Yanjie Wu, Yuhong Zhang, Huan Zhang, Chencheng Hu, Biao Dong, Xue Bai, Hongwei Song
The trap states at both the upper and bottom interfaces of perovskite layers significantly impact non-radiative carrier recombination. The widely used solvent-based passivation methods result in the disordered distribution of surface components, posing challenges for the commercial application of large-area perovskite solar cells (PSCs). To address this issue, a novel NH3 gas-assisted all-inorganic dual-interfaces passivation strategy is proposed. Through the gas treatment of the perovskite surface, NH3 molecules significantly enhanced the iodine vacancy formation energy (1.54 eV) and bonded with uncoordinated Pb2+ to achieve non-destructive passivation. Meanwhile, the reduction of the film defect states is accompanied by a decrease in the work function, which promotes carrier transport between the interface. Further, a stable passivation layer is constructed to manage the bottom interfacial defects using inorganic potassium tripolyphosphate (PT), whose ─P═O group effectively mitigated the charged defects and lowered the carrier transport barriers and nucleation barriers of PVK, while the gradient distribution of K+ improved the crystalline quality of PVK film. Based on the dual-interface synergistic effect, the optimal MA-contained PSCs with an effective area of 0.1 cm2 achieved an efficiency of 24.51% and can maintain 90% of the initial value after aging (10-20% RH and 20 °C) for 2000 h.
{"title":"Gas Molecule Assisted All-Inorganic Dual-Interface Passivation Strategy for High-Performance Perovskite Solar Cells.","authors":"Fancong Zeng, Lin Xu, Jiahe Xing, Yanjie Wu, Yuhong Zhang, Huan Zhang, Chencheng Hu, Biao Dong, Xue Bai, Hongwei Song","doi":"10.1002/advs.202404444","DOIUrl":"https://doi.org/10.1002/advs.202404444","url":null,"abstract":"<p><p>The trap states at both the upper and bottom interfaces of perovskite layers significantly impact non-radiative carrier recombination. The widely used solvent-based passivation methods result in the disordered distribution of surface components, posing challenges for the commercial application of large-area perovskite solar cells (PSCs). To address this issue, a novel NH<sub>3</sub> gas-assisted all-inorganic dual-interfaces passivation strategy is proposed. Through the gas treatment of the perovskite surface, NH<sub>3</sub> molecules significantly enhanced the iodine vacancy formation energy (1.54 eV) and bonded with uncoordinated Pb<sup>2+</sup> to achieve non-destructive passivation. Meanwhile, the reduction of the film defect states is accompanied by a decrease in the work function, which promotes carrier transport between the interface. Further, a stable passivation layer is constructed to manage the bottom interfacial defects using inorganic potassium tripolyphosphate (PT), whose ─P═O group effectively mitigated the charged defects and lowered the carrier transport barriers and nucleation barriers of PVK, while the gradient distribution of K<sup>+</sup> improved the crystalline quality of PVK film. Based on the dual-interface synergistic effect, the optimal MA-contained PSCs with an effective area of 0.1 cm<sup>2</sup> achieved an efficiency of 24.51% and can maintain 90% of the initial value after aging (10-20% RH and 20 °C) for 2000 h.</p>","PeriodicalId":117,"journal":{"name":"Advanced Science","volume":null,"pages":null},"PeriodicalIF":14.3,"publicationDate":"2024-07-04","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"141532940","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"材料科学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
In the quest to enhance Zn-air batteries (ZABs) for operating across a wide spectrum of temperatures, synthesizing robust oxygen electrocatalysts is paramount. Conventional strategies focusing on orbital hybridization of d-d and p-d aim to moderate the excessive interaction between the d-band of the transition metal active site and oxygen intermediate, yet often yield suboptimal performance. Herein, an innovative s-block metal modulation is reported to refine the electronic structure and catalytic behavior of Co─NC catalysts. Employing density functional theory (DFT) calculations, it is revealed that incorporating Mg markedly depresses the d-band center of Co sites, thereby fine-tuning the adsorption energy of the oxygen reduction reaction (ORR) intermediate. Consequently, the Mg-modified Co─NC catalyst (MgCo─NC) unveils remarkable intrinsic ORR activity with a significantly reduced activation energy (Ea) of 10.0 kJ mol-1, outstripping the performance of both Co─NC (17.6 kJ mol-1), benchmark Pt/C (15.9 kJ mol-1), and many recent reports. Moreover, ZABs outfitted with the finely tuned Mg0.1Co0.9─NC realize a formidable power density of 157.0 mW cm-2, paired with an extremely long cycle life of 1700 h, and an exceptionally minimal voltage gap decay rate of 0.006 mV h-1. Further, the Mg0.1Co0.9─NC-based flexible ZAB presents a mere 2% specific capacity degradation when the temperature fluctuates from 25 to -20 °C, underscoring its robustness and suitability for practical deployment in diverse environmental conditions.
{"title":"S-Block Metal Mg-Mediated Co─N─C as Efficient Oxygen Electrocatalyst for Durable and Temperature-Adapted Zn-Air Batteries.","authors":"Henan Wang, Xinxin Niu, Wenxian Liu, Ruilian Yin, Jiale Dai, Wei Guo, Chao Kong, Lu Ma, Xia Ding, Fangfang Wu, Wenhui Shi, Tianqi Deng, Xiehong Cao","doi":"10.1002/advs.202403865","DOIUrl":"https://doi.org/10.1002/advs.202403865","url":null,"abstract":"<p><p>In the quest to enhance Zn-air batteries (ZABs) for operating across a wide spectrum of temperatures, synthesizing robust oxygen electrocatalysts is paramount. Conventional strategies focusing on orbital hybridization of d-d and p-d aim to moderate the excessive interaction between the d-band of the transition metal active site and oxygen intermediate, yet often yield suboptimal performance. Herein, an innovative s-block metal modulation is reported to refine the electronic structure and catalytic behavior of Co─NC catalysts. Employing density functional theory (DFT) calculations, it is revealed that incorporating Mg markedly depresses the d-band center of Co sites, thereby fine-tuning the adsorption energy of the oxygen reduction reaction (ORR) intermediate. Consequently, the Mg-modified Co─NC catalyst (MgCo─NC) unveils remarkable intrinsic ORR activity with a significantly reduced activation energy (Ea) of 10.0 kJ mol<sup>-1</sup>, outstripping the performance of both Co─NC (17.6 kJ mol<sup>-1</sup>), benchmark Pt/C (15.9 kJ mol<sup>-1</sup>), and many recent reports. Moreover, ZABs outfitted with the finely tuned Mg<sub>0.1</sub>Co<sub>0.9</sub>─NC realize a formidable power density of 157.0 mW cm<sup>-2</sup>, paired with an extremely long cycle life of 1700 h, and an exceptionally minimal voltage gap decay rate of 0.006 mV h<sup>-1</sup>. Further, the Mg<sub>0.1</sub>Co<sub>0.9</sub>─NC-based flexible ZAB presents a mere 2% specific capacity degradation when the temperature fluctuates from 25 to -20 °C, underscoring its robustness and suitability for practical deployment in diverse environmental conditions.</p>","PeriodicalId":117,"journal":{"name":"Advanced Science","volume":null,"pages":null},"PeriodicalIF":14.3,"publicationDate":"2024-07-04","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"141532943","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"材料科学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Da Won Lee, Seongkeun Oh, Dong Hyun David Lee, Ho Young Woo, Junhyuk Ahn, Seung Hyeon Kim, Byung Ku Jung, Yoonjoo Choi, Dagam Kim, Mi Yeon Yu, Chun Gwon Park, Hongseok Yun, Tae-Hyung Kim, Myung Joon Han, Soong Ju Oh, Taejong Paik
In this study, a novel synthesis of ultrathin, highly uniform colloidal bismuth sulfohalide (BiSX where X = Cl, Br, I) nanowires (NWs) and NW bundles (NBs) for room-temperature and solution-processed flexible photodetectors are presented. High-aspect-ratio bismuth sulfobromide (BiSBr) NWs are synthesized via a heat-up method using bismuth bromide and elemental S as precursors and 1-dodecanethiol as a solvent. Bundling of the BiSBr NWs occurs upon the addition of 1-octadecene as a co-solvent. The morphologies of the BiSBr NBs are easily tailored from sheaf-like structures to spherulite nanostructures by changing the solvent ratio. The optical bandgaps are modulated from 1.91 (BiSCl) and 1.88 eV (BiSBr) to 1.53 eV (BiSI) by changing the halide compositions. The optical bandgap of the ultrathin BiSBr NWs and NBs exhibits blueshift, whose origin is investigated through density functional theory-based first-principles calculations. Visible-light photodetectors are fabricated using BiSBr NWs and NBs via solution-based deposition followed by solid-state ligand exchanges. High photo-responsivities and external quantum efficiencies (EQE) are obtained for BiSBr NW and NB films even under strain, which offer a unique opportunity for the application of the novel BiSX NWs and NBs in flexible and environmentally friendly optoelectronic devices.
本研究介绍了一种用于室温和溶液加工柔性光电探测器的超细、高度均匀的胶体硫化铋(BiSX,其中 X = Cl、Br、I)纳米线(NWs)和 NW 束(NBs)的新型合成方法。以溴化铋和元素 S 为前驱体,以 1-dodecanethiol 为溶剂,通过加热法合成了高光谱比溴化硫铋(BiSBr)纳米线。在加入 1-十八烯作为辅助溶剂后,BiSBr NWs 出现捆绑。通过改变溶剂比例,BiSBr NBs 的形态很容易从片状结构调整为球状纳米结构。通过改变卤化物成分,光带隙可从 1.91 eV(BiSCl)和 1.88 eV(BiSBr)调制到 1.53 eV(BiSI)。超薄 BiSBr NWs 和 NBs 的光带隙呈现蓝移现象,我们通过基于密度泛函理论的第一原理计算研究了蓝移的起源。利用 BiSBr NW 和 NB,通过溶液沉积和固态配体交换制造出了可见光光电探测器。即使在应变条件下,BiSBr NW 和 NB 薄膜也能获得很高的光响应率和外部量子效率 (EQE),这为新型 BiSX NW 和 NB 在柔性环保光电器件中的应用提供了独特的机会。
{"title":"Ultrathin, High-Aspect-Ratio Bismuth Sulfohalide Nanowire Bundles for Solution-Processed Flexible Photodetectors.","authors":"Da Won Lee, Seongkeun Oh, Dong Hyun David Lee, Ho Young Woo, Junhyuk Ahn, Seung Hyeon Kim, Byung Ku Jung, Yoonjoo Choi, Dagam Kim, Mi Yeon Yu, Chun Gwon Park, Hongseok Yun, Tae-Hyung Kim, Myung Joon Han, Soong Ju Oh, Taejong Paik","doi":"10.1002/advs.202403463","DOIUrl":"https://doi.org/10.1002/advs.202403463","url":null,"abstract":"<p><p>In this study, a novel synthesis of ultrathin, highly uniform colloidal bismuth sulfohalide (BiSX where X = Cl, Br, I) nanowires (NWs) and NW bundles (NBs) for room-temperature and solution-processed flexible photodetectors are presented. High-aspect-ratio bismuth sulfobromide (BiSBr) NWs are synthesized via a heat-up method using bismuth bromide and elemental S as precursors and 1-dodecanethiol as a solvent. Bundling of the BiSBr NWs occurs upon the addition of 1-octadecene as a co-solvent. The morphologies of the BiSBr NBs are easily tailored from sheaf-like structures to spherulite nanostructures by changing the solvent ratio. The optical bandgaps are modulated from 1.91 (BiSCl) and 1.88 eV (BiSBr) to 1.53 eV (BiSI) by changing the halide compositions. The optical bandgap of the ultrathin BiSBr NWs and NBs exhibits blueshift, whose origin is investigated through density functional theory-based first-principles calculations. Visible-light photodetectors are fabricated using BiSBr NWs and NBs via solution-based deposition followed by solid-state ligand exchanges. High photo-responsivities and external quantum efficiencies (EQE) are obtained for BiSBr NW and NB films even under strain, which offer a unique opportunity for the application of the novel BiSX NWs and NBs in flexible and environmentally friendly optoelectronic devices.</p>","PeriodicalId":117,"journal":{"name":"Advanced Science","volume":null,"pages":null},"PeriodicalIF":14.3,"publicationDate":"2024-07-04","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"141496435","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"材料科学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Helicobacter pylori (HP), a common microanaerobic bacteria that lives in the human mouth and stomach, is reported to infect ≈50% of the global population. The current diagnostic methods for HP are either invasive, time-consuming, or harmful. Therefore, a noninvasive and label-free HP diagnostic method needs to be developed urgently. Herein, reduced graphene oxide (rGO) is composited with different metal-based materials to construct a graphene-based electronic nose (e-nose), which exhibits excellent sensitivity and cross-reactive response to several gases in exhaled breath (EB). Principal component analysis (PCA) shows that four typical types of gases in EB can be well discriminated. Additionally, the potential of the e-nose in label-free detection of HP infection is demonstrated through the measurement and analysis of EB samples. Furthermore, a prototype of an e-nose device is designed and constructed for automatic EB detection and HP diagnosis. The accuracy of the prototype machine integrated with the graphene-based e-nose can reach 92% and 91% in the training and validation sets, respectively. These results demonstrate that the highly sensitive graphene-based e-nose has great potential for the label-free diagnosis of HP and may become a novel tool for non-invasive disease screening and diagnosis.
幽门螺杆菌(HP)是一种生活在人类口腔和胃部的常见微需氧菌,据报道,全球有 50% 的人口感染了这种细菌。目前的幽门螺杆菌诊断方法要么是侵入性的、耗时的,要么是有害的。因此,一种无创、无标记的 HP 诊断方法亟待开发。在本文中,还原氧化石墨烯(rGO)与不同的金属基材料复合,构建了基于石墨烯的电子鼻(e-nose),该电子鼻对呼出气体(EB)中的多种气体具有出色的灵敏度和交叉反应响应。主成分分析(PCA)显示,电子鼻可以很好地区分呼气中的四种典型气体。此外,通过测量和分析 EB 样品,证明了电子鼻在无标记检测 HP 感染方面的潜力。此外,还设计并构建了用于自动 EB 检测和 HP 诊断的电子鼻设备原型。集成了石墨烯电子鼻的原型机在训练集和验证集上的准确率分别达到 92% 和 91%。这些结果表明,高灵敏度的石墨烯基电子鼻在无标记诊断 HP 方面具有巨大的潜力,有可能成为无创疾病筛查和诊断的新型工具。
{"title":"A Prototype of Graphene E-Nose for Exhaled Breath Detection and Label-Free Diagnosis of Helicobacter Pylori Infection.","authors":"Xuemei Liu, Qiaofen Chen, Shiyuan Xu, Jiaying Wu, Jingwen Zhao, Zhengfu He, Aiwu Pan, Jianmin Wu","doi":"10.1002/advs.202401695","DOIUrl":"https://doi.org/10.1002/advs.202401695","url":null,"abstract":"<p><p>Helicobacter pylori (HP), a common microanaerobic bacteria that lives in the human mouth and stomach, is reported to infect ≈50% of the global population. The current diagnostic methods for HP are either invasive, time-consuming, or harmful. Therefore, a noninvasive and label-free HP diagnostic method needs to be developed urgently. Herein, reduced graphene oxide (rGO) is composited with different metal-based materials to construct a graphene-based electronic nose (e-nose), which exhibits excellent sensitivity and cross-reactive response to several gases in exhaled breath (EB). Principal component analysis (PCA) shows that four typical types of gases in EB can be well discriminated. Additionally, the potential of the e-nose in label-free detection of HP infection is demonstrated through the measurement and analysis of EB samples. Furthermore, a prototype of an e-nose device is designed and constructed for automatic EB detection and HP diagnosis. The accuracy of the prototype machine integrated with the graphene-based e-nose can reach 92% and 91% in the training and validation sets, respectively. These results demonstrate that the highly sensitive graphene-based e-nose has great potential for the label-free diagnosis of HP and may become a novel tool for non-invasive disease screening and diagnosis.</p>","PeriodicalId":117,"journal":{"name":"Advanced Science","volume":null,"pages":null},"PeriodicalIF":14.3,"publicationDate":"2024-07-04","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"141532937","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"材料科学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Zhangjie Luo, Zhiming Zhang, Junwei Tai, Lei Zhang, Chenglong Gao, Hui Feng Ma, Wei Xiang Jiang, Qiang Cheng, Tie Jun Cui
Harmonic generation and utilization are significant topics in nonlinear science. Although the progress in the microwave region has been expedited by the development of time-modulated metasurfaces, one major issue of these devices is the strong entanglement of multiple harmonics, leading to criticism of their use in frequency-division multiplexing (FDM) applications. Previous studies have attempted to overcome this limitation, but they suffer from designing complexity or insufficient controlling capability. Here a new space-time-coding metasurface (STCM) is proposed to independently and precisely synthesize not only the phases but also the amplitudes of various harmonics. This promising feature is successfully demonstrated in wireless space- and frequency-division multiplexing experiments, where modulated and unmodulated signals are simultaneously transmitted via different harmonics using a shared STCM. To illustrate the advantages, binary frequency shift keying (BFSK) and quadrature phase shift keying (QPSK) modulation schemes are respectively implemented. Behind the intriguing functionality, the mechanism of the space-time coding strategy and the analytical designing method are elaborated, which are validated numerically and experimentally. It is believed that the achievements can potentially propel the time-vary metasurfaces in the next-generation wireless applications.
{"title":"Fully Breaking Entanglement of Multiple Harmonics for Space- and Frequency-Division Multiplexing Wireless Applications via Space-Time-Coding Metasurface.","authors":"Zhangjie Luo, Zhiming Zhang, Junwei Tai, Lei Zhang, Chenglong Gao, Hui Feng Ma, Wei Xiang Jiang, Qiang Cheng, Tie Jun Cui","doi":"10.1002/advs.202404558","DOIUrl":"https://doi.org/10.1002/advs.202404558","url":null,"abstract":"<p><p>Harmonic generation and utilization are significant topics in nonlinear science. Although the progress in the microwave region has been expedited by the development of time-modulated metasurfaces, one major issue of these devices is the strong entanglement of multiple harmonics, leading to criticism of their use in frequency-division multiplexing (FDM) applications. Previous studies have attempted to overcome this limitation, but they suffer from designing complexity or insufficient controlling capability. Here a new space-time-coding metasurface (STCM) is proposed to independently and precisely synthesize not only the phases but also the amplitudes of various harmonics. This promising feature is successfully demonstrated in wireless space- and frequency-division multiplexing experiments, where modulated and unmodulated signals are simultaneously transmitted via different harmonics using a shared STCM. To illustrate the advantages, binary frequency shift keying (BFSK) and quadrature phase shift keying (QPSK) modulation schemes are respectively implemented. Behind the intriguing functionality, the mechanism of the space-time coding strategy and the analytical designing method are elaborated, which are validated numerically and experimentally. It is believed that the achievements can potentially propel the time-vary metasurfaces in the next-generation wireless applications.</p>","PeriodicalId":117,"journal":{"name":"Advanced Science","volume":null,"pages":null},"PeriodicalIF":14.3,"publicationDate":"2024-07-04","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"141532939","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"材料科学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
The transition metal-catalyzed multi-component cross-electrophile sulfonylation, which incorporates SO2 as a linker within organic frameworks, has proven to be a powerful, efficient, and cost-effective means of synthesizing challenging alkyl-alkyl sulfones. Transition metal catalysts play a crucial role in this method by transferring electrons from reductants to electrophilic organohalides, thereby causing undesirable side reactions such as homocoupling, protodehalogenation, β-hydride elimination, etc. It is worth noting that tertiary alkyl halides have rarely been demonstrated to be compatible with current methods owing to various undesired side reactions. In this work, a zinc-promoted cross-electrophile sulfonylation is developed through a radical-polar crossover pathway. This approach enables the synthesis of various alkyl-alkyl sulfones, including 1°-1°, 2°-1°, 3°-1°, 2°-2°, and 3°-2° types, from inexpensive and readily available alkyl halides. Various functional groups are well tolerated in the work, resulting in yields of up to 93%. Additionally, this protocol has been successfully applied to intramolecular sulfonylation and homo-sulfonylation reactions. The insights gained from this work shall be useful for the further development of cross-electrophile sulfonylation to access alkyl-alkyl sulfones.
{"title":"Zinc Promoted Cross-Electrophile Sulfonylation to Access Alkyl-Alkyl Sulfones.","authors":"Zhuochen Wang, Rui Ma, Chang Gu, Xiaoqian He, Haiwei Shi, Ruopeng Bai, Renyi Shi","doi":"10.1002/advs.202406228","DOIUrl":"https://doi.org/10.1002/advs.202406228","url":null,"abstract":"<p><p>The transition metal-catalyzed multi-component cross-electrophile sulfonylation, which incorporates SO<sub>2</sub> as a linker within organic frameworks, has proven to be a powerful, efficient, and cost-effective means of synthesizing challenging alkyl-alkyl sulfones. Transition metal catalysts play a crucial role in this method by transferring electrons from reductants to electrophilic organohalides, thereby causing undesirable side reactions such as homocoupling, protodehalogenation, β-hydride elimination, etc. It is worth noting that tertiary alkyl halides have rarely been demonstrated to be compatible with current methods owing to various undesired side reactions. In this work, a zinc-promoted cross-electrophile sulfonylation is developed through a radical-polar crossover pathway. This approach enables the synthesis of various alkyl-alkyl sulfones, including 1°-1°, 2°-1°, 3°-1°, 2°-2°, and 3°-2° types, from inexpensive and readily available alkyl halides. Various functional groups are well tolerated in the work, resulting in yields of up to 93%. Additionally, this protocol has been successfully applied to intramolecular sulfonylation and homo-sulfonylation reactions. The insights gained from this work shall be useful for the further development of cross-electrophile sulfonylation to access alkyl-alkyl sulfones.</p>","PeriodicalId":117,"journal":{"name":"Advanced Science","volume":null,"pages":null},"PeriodicalIF":14.3,"publicationDate":"2024-07-04","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"141496437","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"材料科学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
The confinement of waves in open systems represents a fundamental phenomenon extensively explored across various branches of wave physics. Recently, significant attention is directed toward bound states in the continuum (BIC), a class of modes that are trapped but do not decay in an otherwise unbounded continuum. Here, the theoretical investigation and experimental demonstration of the existence of quasi-bound states in the continuum (QBIC) for ultrasonic waves are achieved by leveraging an elastic Fabry-Pérot metasurface resonator. Several intriguing properties of the ultrasound quasi-bound states in the continuum that are robust to parameter scanning are unveiled, and experimental evidence of a remarkable Q-factor of 350 at ≈1 MHz frequency, far exceeding the state-of-the-art using a fully acoustic underwater system is presented. The findings contribute novel insights into the understanding of BIC for acoustic waves, offering a new paradigm for the design of efficient, ultra-high Q-factor ultrasound devices.
{"title":"Observation of Ultra-High-Q Resonators in the Ultrasound via Bound States in the Continuum.","authors":"Mohamed Farhat, Younes Achaoui, Julio Andrés Iglesias Martínez, Mahmoud Addouche, Ying Wu, Abdelkrim Khelif","doi":"10.1002/advs.202402917","DOIUrl":"https://doi.org/10.1002/advs.202402917","url":null,"abstract":"<p><p>The confinement of waves in open systems represents a fundamental phenomenon extensively explored across various branches of wave physics. Recently, significant attention is directed toward bound states in the continuum (BIC), a class of modes that are trapped but do not decay in an otherwise unbounded continuum. Here, the theoretical investigation and experimental demonstration of the existence of quasi-bound states in the continuum (QBIC) for ultrasonic waves are achieved by leveraging an elastic Fabry-Pérot metasurface resonator. Several intriguing properties of the ultrasound quasi-bound states in the continuum that are robust to parameter scanning are unveiled, and experimental evidence of a remarkable Q-factor of 350 at ≈1 MHz frequency, far exceeding the state-of-the-art using a fully acoustic underwater system is presented. The findings contribute novel insights into the understanding of BIC for acoustic waves, offering a new paradigm for the design of efficient, ultra-high Q-factor ultrasound devices.</p>","PeriodicalId":117,"journal":{"name":"Advanced Science","volume":null,"pages":null},"PeriodicalIF":14.3,"publicationDate":"2024-07-04","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"141496431","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"材料科学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Shuai Ben, Zhutao Ding, Junyi Xin, Feng Li, Yifei Cheng, Silu Chen, Lulu Fan, Qin Zhang, Shuwei Li, Mulong Du, Zhengdong Zhang, Gong-Hong Wei, Gong Cheng, Meilin Wang
Genetic and epigenetic alterations occur in many physiological and pathological processes. The existing knowledge regarding the association of PIWI-interacting RNAs (piRNAs) and their genetic variants on risk and progression of prostate cancer (PCa) is limited. In this study, three genome-wide association study datasets are combined, including 85,707 PCa cases and 166,247 controls, to uncover genetic variants in piRNAs. Functional investigations involved manipulating piRNA expression in cellular and mouse models to study its oncogenetic role in PCa. A specific genetic variant, rs17201241 is identified, associated with increased expression of PROPER (piRNA overexpressed in prostate cancer) in tumors and are located within the gene, conferring an increased risk and malignant progression of PCa. Mechanistically, PROPER coupled with YTHDF2 to recognize N6-methyladenosine (m6A) and facilitated RNA-binding protein interactions between EIF2S3 at 5'-untranslated region (UTR) and YTHDF2/YBX3 at 3'-UTR to promote DUSP1 circularization. This m6A-dependent mRNA-looping pattern enhanced DUSP1 degradation and inhibited DUSP1 translation, ultimately reducing DUSP1 expression and promoting PCa metastasis via the p38 mitogen-activated protein kinase (MAPK) signaling pathway. Inhibition of PROPER expression using antagoPROPER effectively suppressed xenograft growth, suggesting its potential as a therapeutic target. Thus, targeting piRNA PROPER-mediated genetic and epigenetic fine control is a promising strategy for the concurrent prevention and treatment of PCa.
{"title":"piRNA PROPER Suppresses DUSP1 Translation by Targeting N<sup>6</sup>-Methyladenosine-Mediated RNA Circularization to Promote Oncogenesis of Prostate Cancer.","authors":"Shuai Ben, Zhutao Ding, Junyi Xin, Feng Li, Yifei Cheng, Silu Chen, Lulu Fan, Qin Zhang, Shuwei Li, Mulong Du, Zhengdong Zhang, Gong-Hong Wei, Gong Cheng, Meilin Wang","doi":"10.1002/advs.202402954","DOIUrl":"https://doi.org/10.1002/advs.202402954","url":null,"abstract":"<p><p>Genetic and epigenetic alterations occur in many physiological and pathological processes. The existing knowledge regarding the association of PIWI-interacting RNAs (piRNAs) and their genetic variants on risk and progression of prostate cancer (PCa) is limited. In this study, three genome-wide association study datasets are combined, including 85,707 PCa cases and 166,247 controls, to uncover genetic variants in piRNAs. Functional investigations involved manipulating piRNA expression in cellular and mouse models to study its oncogenetic role in PCa. A specific genetic variant, rs17201241 is identified, associated with increased expression of PROPER (piRNA overexpressed in prostate cancer) in tumors and are located within the gene, conferring an increased risk and malignant progression of PCa. Mechanistically, PROPER coupled with YTHDF2 to recognize N<sup>6</sup>-methyladenosine (m<sup>6</sup>A) and facilitated RNA-binding protein interactions between EIF2S3 at 5'-untranslated region (UTR) and YTHDF2/YBX3 at 3'-UTR to promote DUSP1 circularization. This m<sup>6</sup>A-dependent mRNA-looping pattern enhanced DUSP1 degradation and inhibited DUSP1 translation, ultimately reducing DUSP1 expression and promoting PCa metastasis via the p38 mitogen-activated protein kinase (MAPK) signaling pathway. Inhibition of PROPER expression using antagoPROPER effectively suppressed xenograft growth, suggesting its potential as a therapeutic target. Thus, targeting piRNA PROPER-mediated genetic and epigenetic fine control is a promising strategy for the concurrent prevention and treatment of PCa.</p>","PeriodicalId":117,"journal":{"name":"Advanced Science","volume":null,"pages":null},"PeriodicalIF":14.3,"publicationDate":"2024-07-04","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"141496432","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"材料科学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Daniel Naveed Tavakol, Trevor R Nash, Youngbin Kim, Pamela L Graney, Martin Liberman, Sharon Fleischer, Roberta I Lock, Aaron O'Donnell, Leah Andrews, Derek Ning, Keith Yeager, Andrew Harken, Naresh Deoli, Sally A Amundson, Guy Garty, Kam W Leong, David J Brenner, Gordana Vunjak-Novakovic
Galactic cosmic radiation (GCR) is one of the most serious risks posed to astronauts during missions to the Moon and Mars. Experimental models capable of recapitulating human physiology are critical to understanding the effects of radiation on human organs and developing radioprotective measures against space travel exposures. The effects of systemic radiation are studied using a multi-organ-on-a-chip (multi-OoC) platform containing engineered tissue models of human bone marrow (site of hematopoiesis and acute radiation damage), cardiac muscle (site of chronic radiation damage) and liver (site of metabolism), linked by vascular circulation with an endothelial barrier separating individual tissue chambers from the vascular perfusate. Following protracted neutron radiation, the most damaging radiation component in deep space, a greater deviation of tissue function is observed as compared to the same cumulative dose delivered acutely. Further, by characterizing engineered bone marrow (eBM)-derived immune cells in circulation, 58 unique genes specific to the effects of protracted neutron dosing are identified, as compared to acutely irradiated and healthy tissues. It propose that this bioengineered platform allows studies of human responses to extended radiation exposure in an "astronaut-on-a-chip" model that can inform measures for mitigating cosmic radiation injury.
{"title":"Modeling the Effects of Protracted Cosmic Radiation in a Human Organ-on-Chip Platform.","authors":"Daniel Naveed Tavakol, Trevor R Nash, Youngbin Kim, Pamela L Graney, Martin Liberman, Sharon Fleischer, Roberta I Lock, Aaron O'Donnell, Leah Andrews, Derek Ning, Keith Yeager, Andrew Harken, Naresh Deoli, Sally A Amundson, Guy Garty, Kam W Leong, David J Brenner, Gordana Vunjak-Novakovic","doi":"10.1002/advs.202401415","DOIUrl":"https://doi.org/10.1002/advs.202401415","url":null,"abstract":"<p><p>Galactic cosmic radiation (GCR) is one of the most serious risks posed to astronauts during missions to the Moon and Mars. Experimental models capable of recapitulating human physiology are critical to understanding the effects of radiation on human organs and developing radioprotective measures against space travel exposures. The effects of systemic radiation are studied using a multi-organ-on-a-chip (multi-OoC) platform containing engineered tissue models of human bone marrow (site of hematopoiesis and acute radiation damage), cardiac muscle (site of chronic radiation damage) and liver (site of metabolism), linked by vascular circulation with an endothelial barrier separating individual tissue chambers from the vascular perfusate. Following protracted neutron radiation, the most damaging radiation component in deep space, a greater deviation of tissue function is observed as compared to the same cumulative dose delivered acutely. Further, by characterizing engineered bone marrow (eBM)-derived immune cells in circulation, 58 unique genes specific to the effects of protracted neutron dosing are identified, as compared to acutely irradiated and healthy tissues. It propose that this bioengineered platform allows studies of human responses to extended radiation exposure in an \"astronaut-on-a-chip\" model that can inform measures for mitigating cosmic radiation injury.</p>","PeriodicalId":117,"journal":{"name":"Advanced Science","volume":null,"pages":null},"PeriodicalIF":14.3,"publicationDate":"2024-07-04","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"141532941","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"材料科学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}