Pub Date : 2024-10-31DOI: 10.1016/j.chempr.2024.10.003
Sangbin Park, Gyumin Kang, Wantae Kim, Sieun Jeon, Myung-Kun Chung, Hee-Seung Lee, Dong Ki Yoon, Sunkyu Han
In general, natural products exist in their most thermodynamically stable form. Therefore, final stage-reaction conditions leading to thermodynamic equilibrium often facilitate the production of the desired natural products. On the other hand, syntheses of contra-thermodynamic natural products pose greater challenges, as the thermodynamic bias should be overcome. Herein, we present the synthesis of contra-thermodynamic securinega alkaloid securingine B, derived from the more thermodynamically stable isomer secu’amamine D. Harnessing the disparity in triplet energy between two natural products, we have established a photochemical equilibrium favoring securingine B. Conversely, secu’amamine D was reformed from securingine B under thermodynamic equilibrium conditions. Inspired by these observations, we devised a novel type of photoswitching platform by introducing a push-pull system to the securinega framework. By leveraging this new photoswitching scaffold, we have developed a securingine B-inspired photochromic material and, subsequently, exploited it as a photoresponsive chiral dopant.
{"title":"Synthesis of securingine B enables photoresponsive materials design","authors":"Sangbin Park, Gyumin Kang, Wantae Kim, Sieun Jeon, Myung-Kun Chung, Hee-Seung Lee, Dong Ki Yoon, Sunkyu Han","doi":"10.1016/j.chempr.2024.10.003","DOIUrl":"https://doi.org/10.1016/j.chempr.2024.10.003","url":null,"abstract":"In general, natural products exist in their most thermodynamically stable form. Therefore, final stage-reaction conditions leading to thermodynamic equilibrium often facilitate the production of the desired natural products. On the other hand, syntheses of contra-thermodynamic natural products pose greater challenges, as the thermodynamic bias should be overcome. Herein, we present the synthesis of contra-thermodynamic securinega alkaloid securingine B, derived from the more thermodynamically stable isomer secu’amamine D. Harnessing the disparity in triplet energy between two natural products, we have established a photochemical equilibrium favoring securingine B. Conversely, secu’amamine D was reformed from securingine B under thermodynamic equilibrium conditions. Inspired by these observations, we devised a novel type of photoswitching platform by introducing a push-pull system to the securinega framework. By leveraging this new photoswitching scaffold, we have developed a securingine B-inspired photochromic material and, subsequently, exploited it as a photoresponsive chiral dopant.","PeriodicalId":268,"journal":{"name":"Chem","volume":"239 1","pages":""},"PeriodicalIF":23.5,"publicationDate":"2024-10-31","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142556281","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":"https://doi.org/10.1016/j.chempr.2024.09.031","url":null,"abstract":"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.","PeriodicalId":268,"journal":{"name":"Chem","volume":"1 1","pages":""},"PeriodicalIF":23.5,"publicationDate":"2024-10-29","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":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Enzymes are highly efficient, chemoselective, and sustainable biocatalysts, standing out as eco-friendly tools to advance the circular plastics economy. Herein, we explored enzymatic reactions of poly(ε-caprolactone)-poly(urethane) (PCL-PUs) in organic solvent under different reaction conditions using Novozym 435 (immobilized lipase) as the enzyme. PCL-PUs with triacetylated γ-cyclodextrin (TAcγCD)-based movable crosslinks (PCL-γCD-PU) not only exhibited excellent mechanical properties due to effective energy dissipation, but also efficient enzymatic degradation that was optimized for increases in TAcγCD content. Under reaction time control, molecular weight and mechanical properties of PCL-γCD-PU were enhanced by a novel enzymatic reinforcement strategy. Without sorting, the degraded products are versatile resources that can be enzymatically closed-loop recycled by switching reaction concentration or enzymatically upcycled into value-added polymers by mixing with selective substrates. The facile polymer structure design combined with enzymatic reactions is expected to provide a broad approach for toughening various polymeric materials and advancing their development as sustainable resources.
{"title":"Exploring enzymatic degradation, reinforcement, recycling, and upcycling of poly(ester)s-poly(urethane) with movable crosslinks","authors":"Jiaxiong Liu, Ryohei Ikura, Kenji Yamaoka, Akihide Sugawara, Yuya Takahashi, Bunsho Kure, Naomi Takenaka, Junsu Park, Hiroshi Uyama, Yoshinori Takashima","doi":"10.1016/j.chempr.2024.09.026","DOIUrl":"https://doi.org/10.1016/j.chempr.2024.09.026","url":null,"abstract":"Enzymes are highly efficient, chemoselective, and sustainable biocatalysts, standing out as eco-friendly tools to advance the circular plastics economy. Herein, we explored enzymatic reactions of poly(<em>ε</em>-caprolactone)-poly(urethane) (PCL-PUs) in organic solvent under different reaction conditions using Novozym 435 (immobilized lipase) as the enzyme. PCL-PUs with triacetylated γ-cyclodextrin (TAcγCD)-based movable crosslinks (PCL-γCD-PU) not only exhibited excellent mechanical properties due to effective energy dissipation, but also efficient enzymatic degradation that was optimized for increases in TAcγCD content. Under reaction time control, molecular weight and mechanical properties of PCL-γCD-PU were enhanced by a novel enzymatic reinforcement strategy. Without sorting, the degraded products are versatile resources that can be enzymatically closed-loop recycled by switching reaction concentration or enzymatically upcycled into value-added polymers by mixing with selective substrates. The facile polymer structure design combined with enzymatic reactions is expected to provide a broad approach for toughening various polymeric materials and advancing their development as sustainable resources.","PeriodicalId":268,"journal":{"name":"Chem","volume":"10 1","pages":""},"PeriodicalIF":23.5,"publicationDate":"2024-10-29","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142536378","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}
Heterogeneous multinuclear catalysts have clear advantages, such as high selectivity, cascading production, and specific chemical transformations, but they are difficult to synthesize due to their high structural complexity. Here, we fabricated crystalline, porous covalent organic frameworks (COFs) with high-density chelating sites by incorporating pyrimidine groups onto their pore wall. Using a molecular coordination imprint strategy, tri-coordination (2N, 1O) and di-coordination (1N, 1O) vacancies were proportionally prepared using Cu(II) ions as templates. Consequently, various hetero-multimetallic assemblies, including Cu(II)/Pd(II), Cu(II)/Fe(III), Cu(II)/Zn(II), and Co(II)/Pd(II), were obtained with tunable ion contents in the range of 3:0 to 3:3 on the COF skeleton. The Cu(II)/Cu(II)/Pd(II)-doped COF sample implemented a sustainable oxidization of olefin compounds, which outperformed all existing catalysts to date for the synthesis of value-added ketone, surpassing 620 times compared with the commercial catalyst (PdCl2/CuCl2).
{"title":"Modulating hetero-multimetallic atoms in covalent organic framework for efficient oxidization of olefin compounds","authors":"Qinghao Meng, Panzhe Qiao, Dan Deng, Cheng Zhang, Fengchao Cui, Xianghui Ruan, Yajie Yang, Jiarui Cao, Zeyu Wang, Xujiao Ma, Ye Yuan, Guangshan Zhu","doi":"10.1016/j.chempr.2024.10.001","DOIUrl":"https://doi.org/10.1016/j.chempr.2024.10.001","url":null,"abstract":"Heterogeneous multinuclear catalysts have clear advantages, such as high selectivity, cascading production, and specific chemical transformations, but they are difficult to synthesize due to their high structural complexity. Here, we fabricated crystalline, porous covalent organic frameworks (COFs) with high-density chelating sites by incorporating pyrimidine groups onto their pore wall. Using a molecular coordination imprint strategy, tri-coordination (2N, 1O) and di-coordination (1N, 1O) vacancies were proportionally prepared using Cu(II) ions as templates. Consequently, various hetero-multimetallic assemblies, including Cu(II)/Pd(II), Cu(II)/Fe(III), Cu(II)/Zn(II), and Co(II)/Pd(II), were obtained with tunable ion contents in the range of 3:0 to 3:3 on the COF skeleton. The Cu(II)/Cu(II)/Pd(II)-doped COF sample implemented a sustainable oxidization of olefin compounds, which outperformed all existing catalysts to date for the synthesis of value-added ketone, surpassing 620 times compared with the commercial catalyst (PdCl<sub>2</sub>/CuCl<sub>2</sub>).","PeriodicalId":268,"journal":{"name":"Chem","volume":"10 1","pages":""},"PeriodicalIF":23.5,"publicationDate":"2024-10-29","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142536379","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 : 2024-10-29DOI: 10.1016/j.chempr.2024.10.002
Dongsheng Mao, Wenxing Li, Xueliang Liu, Jingqi Chen, Dali Wei, Lei Luo, Qianqin Yuan, Yu Yang, Xiaoli Zhu, Weihong Tan
Enzymes with ingenious structures and diverse functions are crucial for biomedical applications but face challenges like instability, limited targetability, and delivery complexity. We developed core-shell DNA-enzyme conjugates using rolling circle amplification (RCA), creating RCA-based DNA-enzyme nanostructure (RCA-DEN) for efficient enzyme immobilization and functionalization. RCA-DEN, characterized by densely packed nucleic acids and negligible disruption of enzyme activity, increases the stability of enzymes and nucleic acids while reducing technical difficulties, making it a versatile platform for diverse biomedical applications. This approach facilitates the modular customization of enzymes and the incorporation of functionalities such as aptamers and DNAzymes. The efficacy of RCA-DEN has been demonstrated in several areas, including selective catalysis, cascade catalysis, dynamic monitoring of intracellular chemical processes, and synergistic therapeutic interventions against tumors. Overall, this work provides a new perspective on enzyme immobilization and functionalization, paving the way for broader biomedical applications of enzymes.
具有巧妙结构和多样化功能的酶对生物医学应用至关重要，但也面临着不稳定性、靶向性有限和传递复杂性等挑战。我们利用滚动圆扩增（RCA）技术开发了核壳DNA-酶共轭物，形成了基于RCA的DNA-酶纳米结构（RCA-DEN），实现了酶的高效固定和功能化。RCA-DEN 的特点是核酸密集包装，对酶活性的干扰微乎其微，在增加酶和核酸稳定性的同时降低了技术难度，使其成为一个可用于多种生物医学应用的多功能平台。这种方法有利于对酶进行模块化定制，并加入适配体和 DNA 酶等功能。RCA-DEN 的功效已在多个领域得到证实，包括选择性催化、级联催化、细胞内化学过程的动态监测以及针对肿瘤的协同治疗干预。总之，这项工作为酶的固定化和功能化提供了一个新的视角，为酶更广泛的生物医学应用铺平了道路。
{"title":"Rolling circle amplification-based DNA-enzyme nanostructure for immobilization and functionalization of enzymes","authors":"Dongsheng Mao, Wenxing Li, Xueliang Liu, Jingqi Chen, Dali Wei, Lei Luo, Qianqin Yuan, Yu Yang, Xiaoli Zhu, Weihong Tan","doi":"10.1016/j.chempr.2024.10.002","DOIUrl":"https://doi.org/10.1016/j.chempr.2024.10.002","url":null,"abstract":"Enzymes with ingenious structures and diverse functions are crucial for biomedical applications but face challenges like instability, limited targetability, and delivery complexity. We developed core-shell DNA-enzyme conjugates using rolling circle amplification (RCA), creating RCA-based DNA-enzyme nanostructure (RCA-DEN) for efficient enzyme immobilization and functionalization. RCA-DEN, characterized by densely packed nucleic acids and negligible disruption of enzyme activity, increases the stability of enzymes and nucleic acids while reducing technical difficulties, making it a versatile platform for diverse biomedical applications. This approach facilitates the modular customization of enzymes and the incorporation of functionalities such as aptamers and DNAzymes. The efficacy of RCA-DEN has been demonstrated in several areas, including selective catalysis, cascade catalysis, dynamic monitoring of intracellular chemical processes, and synergistic therapeutic interventions against tumors. Overall, this work provides a new perspective on enzyme immobilization and functionalization, paving the way for broader biomedical applications of enzymes.","PeriodicalId":268,"journal":{"name":"Chem","volume":"79 1","pages":""},"PeriodicalIF":23.5,"publicationDate":"2024-10-29","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142536375","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 : 2024-10-25DOI: 10.1016/j.chempr.2024.09.018
Tristan H. Borchers, Filip Topić, Mihails Arhangelskis, Michael Ferguson, Cameron B. Lennox, Patrick A. Julien, Tomislav Friščić
Low-frequency Raman, also known as terahertz-Raman (THz-Raman), spectroscopy offers a laboratory benchtop-based alternative to synchrotron X-ray diffraction for real-time, in situ monitoring of ball-milling mechanochemical reactions. Although direct monitoring of the long-range structure of materials during mechanochemical reactions is generally challenging by conventional Raman spectroscopy, and typically requires synchrotron X-ray diffraction, here we use THz-Raman spectroscopy to monitor mechanosynthesis of cocrystals, stoichiomorphs, and polymorphs, detect multi-step sequences, and discover solid-state phases in systems difficult to differentiate using fingerprint-region Raman spectroscopy—all through real-time observation of changes in lattice vibrational models. The methodology is augmented by periodic density functional theory (DFT), which enables structural interpretation of spectroscopic changes, notably the identification of THz-Raman bands associated with halogen bond transformations. Simultaneous monitoring of mechanochemical processes in both the fingerprint and low-frequency Raman regions enables real-time observation of changes to extended as well as molecular structure during milling, in a single laboratory benchtop experiment, without synchrotron radiation.
低频拉曼（又称太赫兹-拉曼，THz-Raman）光谱法为实验室台式同步辐射 X 射线衍射法提供了一种替代方法，可用于实时、原位监测球磨机械化学反应。虽然在机械化学反应过程中直接监测材料的长程结构通常是传统拉曼光谱法所无法实现的，而且通常需要同步辐射 X 射线衍射法，但在这里，我们使用太赫兹-拉曼光谱法监测共晶体、共晶和多晶体的机械合成，检测多步序列，并在使用指纹区拉曼光谱法难以区分的系统中发现固态相--所有这些都是通过实时观测晶格振动模型的变化实现的。周期性密度泛函理论（DFT）对该方法进行了增强，从而能够对光谱变化进行结构解释，特别是识别与卤素键转化相关的太赫兹-拉曼带。同时监测指纹区和低频拉曼区的机械化学过程，可在实验室台式实验中实时观察研磨过程中扩展分子结构的变化，而无需同步辐射。
{"title":"Terahertz-Raman spectroscopy for in situ benchtop monitoring of changes to extended, supramolecular structure in milling mechanochemistry","authors":"Tristan H. Borchers, Filip Topić, Mihails Arhangelskis, Michael Ferguson, Cameron B. Lennox, Patrick A. Julien, Tomislav Friščić","doi":"10.1016/j.chempr.2024.09.018","DOIUrl":"https://doi.org/10.1016/j.chempr.2024.09.018","url":null,"abstract":"Low-frequency Raman, also known as terahertz-Raman (THz-Raman), spectroscopy offers a laboratory benchtop-based alternative to synchrotron X-ray diffraction for real-time, <em>in situ</em> monitoring of ball-milling mechanochemical reactions. Although direct monitoring of the long-range structure of materials during mechanochemical reactions is generally challenging by conventional Raman spectroscopy, and typically requires synchrotron X-ray diffraction, here we use THz-Raman spectroscopy to monitor mechanosynthesis of cocrystals, stoichiomorphs, and polymorphs, detect multi-step sequences, and discover solid-state phases in systems difficult to differentiate using fingerprint-region Raman spectroscopy—all through real-time observation of changes in lattice vibrational models. The methodology is augmented by periodic density functional theory (DFT), which enables structural interpretation of spectroscopic changes, notably the identification of THz-Raman bands associated with halogen bond transformations. Simultaneous monitoring of mechanochemical processes in both the fingerprint and low-frequency Raman regions enables real-time observation of changes to extended as well as molecular structure during milling, in a single laboratory benchtop experiment, without synchrotron radiation.","PeriodicalId":268,"journal":{"name":"Chem","volume":"98 1","pages":""},"PeriodicalIF":23.5,"publicationDate":"2024-10-25","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142489464","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 : 2024-10-21DOI: 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":"https://doi.org/10.1016/j.chempr.2024.09.024","url":null,"abstract":"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.","PeriodicalId":268,"journal":{"name":"Chem","volume":"15 1","pages":""},"PeriodicalIF":23.5,"publicationDate":"2024-10-21","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}
Pub Date : 2024-10-21DOI: 10.1016/j.chempr.2024.09.029
Alexandros A. Kitos, Raúl Castañeda, Zachary J. Comeau, Niki Mavragani, Nicholas D. Calvert, Alexia Kirby, Francisco M. Martinez-Santiesteban, Peter J. Pallister, Timothy J. Scholl, Muralee Murugesu, Adam J. Shuhendler, Jaclyn L. Brusso
Transition metal molecular clusters hold great promise as magnetic resonance imaging (MRI) probes, where careful chemical design can afford control over the size, shape, and total spin state of the contrast agent (CA). Although such clusters can act as a single entity, exhibiting advanced in situ reactivity to key diagnostic biomolecules, their dissociation/speciation in biological media hinders their potential as MRI CAs. To resolve this, the N-2-pyrimidylimidoyl-2-pyrimidylamidine chelate was employed to selectively bind 3d metal ions, forming highly stable mixed-metal clusters. Through spectroscopic, electrochemical, and magnetic analysis, along with in vitro and in vivo studies, the application of iron and manganese homo- and heterometallic complexes as MRI CAs capable of mapping tumor redox status through a simple T1w/T2w ratiometric approach was demonstrated. The use of heteropolynuclear 3d super-atomic complexes suitable for semi-quantitative in vivo MRI of tissue redox status opens new avenues for non-invasive characterization of biochemical microenvironments by MRI.
过渡金属分子团簇很有希望成为磁共振成像（MRI）探针，精心的化学设计可以控制造影剂（CA）的大小、形状和总自旋状态。虽然此类团簇可以作为单一实体发挥作用，对关键的诊断生物分子表现出先进的原位反应性，但它们在生物介质中的解离/分化阻碍了它们作为磁共振成像造影剂的潜力。为了解决这个问题，我们采用了 N-2-嘧啶亚氨酰基-2-嘧啶脒螯合物来选择性地结合 3d 金属离子，形成高度稳定的混合金属团簇。通过光谱、电化学和磁性分析，以及体外和体内研究，证明了铁和锰同金属和异金属复合物作为磁共振成像 CAs 的应用，能够通过简单的 T1w/T2w 比率测量法绘制肿瘤氧化还原状态图。使用适用于组织氧化还原状态半定量活体磁共振成像的异多核 3d 超原子复合物，为通过磁共振成像无创描述生化微环境开辟了新途径。
{"title":"Cluster-based redox-responsive super-atomic MRI contrast agents","authors":"Alexandros A. Kitos, Raúl Castañeda, Zachary J. Comeau, Niki Mavragani, Nicholas D. Calvert, Alexia Kirby, Francisco M. Martinez-Santiesteban, Peter J. Pallister, Timothy J. Scholl, Muralee Murugesu, Adam J. Shuhendler, Jaclyn L. Brusso","doi":"10.1016/j.chempr.2024.09.029","DOIUrl":"https://doi.org/10.1016/j.chempr.2024.09.029","url":null,"abstract":"Transition metal molecular clusters hold great promise as magnetic resonance imaging (MRI) probes, where careful chemical design can afford control over the size, shape, and total spin state of the contrast agent (CA). Although such clusters can act as a single entity, exhibiting advanced <em>in situ</em> reactivity to key diagnostic biomolecules, their dissociation/speciation in biological media hinders their potential as MRI CAs. To resolve this, the <em>N</em>-2-pyrimidylimidoyl-2-pyrimidylamidine chelate was employed to selectively bind 3d metal ions, forming highly stable mixed-metal clusters. Through spectroscopic, electrochemical, and magnetic analysis, along with <em>in vitro</em> and <em>in vivo</em> studies, the application of iron and manganese homo- and heterometallic complexes as MRI CAs capable of mapping tumor redox status through a simple <em>T</em><sub>1</sub>w/<em>T</em><sub>2</sub>w ratiometric approach was demonstrated. The use of heteropolynuclear 3d super-atomic complexes suitable for semi-quantitative <em>in vivo</em> MRI of tissue redox status opens new avenues for non-invasive characterization of biochemical microenvironments by MRI.","PeriodicalId":268,"journal":{"name":"Chem","volume":"12 1","pages":""},"PeriodicalIF":23.5,"publicationDate":"2024-10-21","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142452210","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 : 2024-10-21DOI: 10.1016/j.chempr.2024.09.027
Chenchen Du, Alex C. Padgham, Anna G. Slater, Liang Zhang
The development of flow processes for metal-ligand self-assembly and ring-closing metathesis has facilitated the efficient and scalable preparation of iron(II) pentafoil knot and Star of David [2]catenane. Use of a flow reactor also enables the formation of the otherwise inaccessible coordinatively labile zinc(II) pentameric helicate, leading to an efficient two-step synthesis of the zinc(II) pentafoil knot. As the first example of topology-synthesis in flow, our work demonstrates that the metal-ligand self-assembly can be readily adapted to flow techniques, even for labile complexes that are difficult to prepare in batches. The method is well-positioned for expansion to other topological complexes made from the metal template approach. Transitioning from laboratory batch synthesis to efficient large-scale production using continuous flow reactors not only paves the way for new applications of flow synthesis in chemical topology but also enhances the accessibility of these “hard-to-make” entangled moieties, thereby opening avenues for exploring their applications in various fields.
{"title":"Efficient flow synthesis of a Star of David [2]catenane and a pentafoil knot","authors":"Chenchen Du, Alex C. Padgham, Anna G. Slater, Liang Zhang","doi":"10.1016/j.chempr.2024.09.027","DOIUrl":"https://doi.org/10.1016/j.chempr.2024.09.027","url":null,"abstract":"The development of flow processes for metal-ligand self-assembly and ring-closing metathesis has facilitated the efficient and scalable preparation of iron(II) pentafoil knot and Star of David [2]catenane. Use of a flow reactor also enables the formation of the otherwise inaccessible coordinatively labile zinc(II) pentameric helicate, leading to an efficient two-step synthesis of the zinc(II) pentafoil knot. As the first example of topology-synthesis in flow, our work demonstrates that the metal-ligand self-assembly can be readily adapted to flow techniques, even for labile complexes that are difficult to prepare in batches. The method is well-positioned for expansion to other topological complexes made from the metal template approach. Transitioning from laboratory batch synthesis to efficient large-scale production using continuous flow reactors not only paves the way for new applications of flow synthesis in chemical topology but also enhances the accessibility of these “hard-to-make” entangled moieties, thereby opening avenues for exploring their applications in various fields.","PeriodicalId":268,"journal":{"name":"Chem","volume":"12 1","pages":""},"PeriodicalIF":23.5,"publicationDate":"2024-10-21","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142452037","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 : 2024-10-21DOI: 10.1016/j.chempr.2024.09.030
Libo Zhu, Chang Chen, Tiantian Wu, Xu Yu, Han Tian, Fantao Kong, Ziwei Chang, Wenshu Luo, Xiangzhi Cui, Jianlin Shi
A promising fuel cell using the acidic hydrogen evolution reaction (HER) instead of kinetically sluggish oxygen reduction reaction to couple with the borohydride oxidation reaction (BOR) has been established. This BOR-HER fuel cell (BHFC) has achieved the concurrent electricity generation and hydrogen production. To catalyze HER/BOR, a copper (Cu)-doped cobalt phosphide nanosheet grown on Cu foam (Cu–CoP/CF) was developed, which exhibits significantly inhibited competitive NaBH4 hydrolysis during BOR, along with excellent HER performance and stability over 700 h. Specifically, the Cu(0), in situ formed on the surface of Cu–CoP/CF, plays a decisive role in creating an OH−-enriched local environment, resulting in significantly inhibited borohydride hydrolysis but greatly enhanced BOR selectivity of up to 85%, as well as the reduced thermodynamic barrier of BOR. The assembled BHFC equipped with Cu–CoP/CF is capable of generating a high power density of 114 mW cm−2 and concurrently producing hydrogen at a rate of at least 40 mol h−1 m−2 at cathode.
利用酸性氢进化反应（HER）代替动力学迟缓的氧还原反应，与硼氢化物氧化反应（BOR）耦合的燃料电池已经建立。这种 BOR-HER 燃料电池（BHFC）实现了同时发电和制氢。为了催化 HER/BOR，研究人员开发了一种生长在泡沫铜（Cu）上的掺铜磷化钴纳米片（Cu-CoP/CF），该纳米片在 BOR 过程中显著抑制了 NaBH4 的竞争性水解，同时还具有优异的 HER 性能和超过 700 小时的稳定性。具体来说，Cu-CoP/CF 表面原位形成的 Cu(0) 在创造富含 OH 的局部环境方面起着决定性作用，从而显著抑制了硼氢化物的水解，但大大提高了 BOR 的选择性（高达 85%），并降低了 BOR 的热力学势垒。装配有 Cu-CoP/CF 的 BHFC 能够产生 114 mW cm-2 的高功率密度，同时在阴极以至少 40 mol h-1 m-2 的速率产生氢气。
{"title":"Borohydride oxidation-water reduction fuel cells advanced by local hydroxyl enrichment-inhibited borohydride hydrolysis on Cu(0) sites","authors":"Libo Zhu, Chang Chen, Tiantian Wu, Xu Yu, Han Tian, Fantao Kong, Ziwei Chang, Wenshu Luo, Xiangzhi Cui, Jianlin Shi","doi":"10.1016/j.chempr.2024.09.030","DOIUrl":"https://doi.org/10.1016/j.chempr.2024.09.030","url":null,"abstract":"A promising fuel cell using the acidic hydrogen evolution reaction (HER) instead of kinetically sluggish oxygen reduction reaction to couple with the borohydride oxidation reaction (BOR) has been established. This BOR-HER fuel cell (BHFC) has achieved the concurrent electricity generation and hydrogen production. To catalyze HER/BOR, a copper (Cu)-doped cobalt phosphide nanosheet grown on Cu foam (Cu–CoP/CF) was developed, which exhibits significantly inhibited competitive NaBH<sub>4</sub> hydrolysis during BOR, along with excellent HER performance and stability over 700 h. Specifically, the Cu(0), <em>in situ</em> formed on the surface of Cu–CoP/CF, plays a decisive role in creating an OH<sup>−</sup>-enriched local environment, resulting in significantly inhibited borohydride hydrolysis but greatly enhanced BOR selectivity of up to 85%, as well as the reduced thermodynamic barrier of BOR. The assembled BHFC equipped with Cu–CoP/CF is capable of generating a high power density of 114 mW cm<sup>−2</sup> and concurrently producing hydrogen at a rate of at least 40 mol h<sup>−1</sup> m<sup>−2</sup> at cathode.","PeriodicalId":268,"journal":{"name":"Chem","volume":"24 1","pages":""},"PeriodicalIF":23.5,"publicationDate":"2024-10-21","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142452039","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}
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