首页 > 最新文献

Chem最新文献

英文 中文
Electrocatalytic grafting of polyvinyl chloride plastics 聚氯乙烯塑料的电催化接枝工艺
IF 19.1 1区 化学 Q1 CHEMISTRY, MULTIDISCIPLINARY Pub Date : 2025-01-09 DOI: 10.1016/j.chempr.2024.08.021
Jordan L.S. Zackasee , Valmuri Srivardhan , Blaise L. Truesdell , Elizabeth J. Vrana , Christo S. Sevov
Polyvinyl chloride (PVC) plastics require high loadings of plasticizers and stabilizers to achieve commercially useful bulk properties. However, these non-covalent additives leach from PVC over time, resulting in the loss of their tailored functionality. This work details the electrocatalytic functionalization of PVC to covalently graft plasticizing additives directly onto the polymer backbone. Here, mechanistic insights guided the design of electrocatalysts capable of modifying C–Cl bonds of PVC under mild conditions with high selectivity while suppressing side reactions such as elimination and chain scission. Functional groups that mimic PVC plasticizers are covalently installed into the backbone of PVC to create new materials with distinct bulk properties from the original polymer. The degree of polymer grafting is easily controlled by simply changing the redox capacity that is passed during electrolysis. This strategy is employed to create chemically and leach-resistant PVC materials by directly electrolyzing mixtures of consumer PVC products.
聚氯乙烯(PVC)塑料需要添加大量增塑剂和稳定剂,才能获得商业上有用的体积特性。然而,随着时间的推移,这些非共价添加剂会从聚氯乙烯中渗出,导致其定制功能丧失。这项研究详细介绍了聚氯乙烯的电催化功能化,将增塑添加剂直接共价接枝到聚合物骨架上。在此,对机理的深入了解指导了电催化剂的设计,使其能够在温和条件下以高选择性改性聚氯乙烯的 C-Cl 键,同时抑制消除和链裂等副反应。模仿聚氯乙烯增塑剂的功能基团以共价方式安装到聚氯乙烯的骨架上,从而制造出具有不同于原始聚合物体积特性的新材料。聚合物接枝的程度很容易控制,只需改变电解过程中通过的氧化还原容量即可。通过直接电解消费类聚氯乙烯产品的混合物,可采用这种策略制造出耐化学腐蚀和耐浸渍的聚氯乙烯材料。
{"title":"Electrocatalytic grafting of polyvinyl chloride plastics","authors":"Jordan L.S. Zackasee ,&nbsp;Valmuri Srivardhan ,&nbsp;Blaise L. Truesdell ,&nbsp;Elizabeth J. Vrana ,&nbsp;Christo S. Sevov","doi":"10.1016/j.chempr.2024.08.021","DOIUrl":"10.1016/j.chempr.2024.08.021","url":null,"abstract":"<div><div>Polyvinyl chloride (PVC) plastics require high loadings of plasticizers and stabilizers to achieve commercially useful bulk properties. However, these non-covalent additives leach from PVC over time, resulting in the loss of their tailored functionality. This work details the electrocatalytic functionalization of PVC to covalently graft plasticizing additives directly onto the polymer backbone. Here, mechanistic insights guided the design of electrocatalysts capable of modifying C–Cl bonds of PVC under mild conditions with high selectivity while suppressing side reactions such as elimination and chain scission. Functional groups that mimic PVC plasticizers are covalently installed into the backbone of PVC to create new materials with distinct bulk properties from the original polymer. The degree of polymer grafting is easily controlled by simply changing the redox capacity that is passed during electrolysis. This strategy is employed to create chemically and leach-resistant PVC materials by directly electrolyzing mixtures of consumer PVC products.</div></div>","PeriodicalId":268,"journal":{"name":"Chem","volume":"11 1","pages":"Article 102298"},"PeriodicalIF":19.1,"publicationDate":"2025-01-09","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142246239","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}
引用次数: 0
In-depth understanding and precise modulation of surface reconstruction during heterogeneous electrocatalysis: From model to practical catalyst 深入了解和精确调制多相电催化过程中的表面重构:从模型到实际催化剂
IF 19.1 1区 化学 Q1 CHEMISTRY, MULTIDISCIPLINARY Pub Date : 2025-01-09 DOI: 10.1016/j.chempr.2024.10.012
Weidong Dai , Kaiwei Wan , Kanglei Pang , Jun Guo , Siyuan Liu , Keying Wu , Chiyao Tang , Yanjuan Sun , Xinghua Shi , Zhiyong Tang , Chang Long , Fan Dong
Renewable energy-driven heterogeneous electrocatalysis holds tremendous potential in converting earth-abundant small molecules and industrial pollutants into value-added or environmentally friendly chemicals, sparking global research interest. The catalyst-electrolyte interface has long been at the forefront of heterogeneous electrocatalysis, dealing with the structure-performance relationship between the performance and the catalytic system, consisting of catalysts, electrolytes, and external biases, at the molecular or atomic level. However, recent observations of numerous surface reconstruction phenomena have challenged the traditional research paradigm that relies on static interface models to elucidate structure-performance relationships. This perspective focuses on the catalyst-electrolyte interface model and rationalizes the underlying principles of catalyst surface reconstruction behavior in terms of free energy. It then showcases the influence of pre-catalyst structure, electrolyte (including additives and reaction intermediates), and external bias on surface reconstruction, alongside state-of-the-art modulation strategies based on the current understanding of surface construction. Finally, we highlight critical issues for future research on catalyst surface reconstruction, including the unexplored factors influencing reconstruction and reaction types, the necessary developments in in situ characterization and simulation techniques, and the currently overlooked problem of catalyst deactivation.
可再生能源驱动的多相电催化在将地球上丰富的小分子和工业污染物转化为增值或环保化学品方面具有巨大的潜力,引起了全球的研究兴趣。催化剂-电解质界面一直是多相电催化研究的前沿,在分子或原子水平上处理由催化剂、电解质和外部偏置组成的催化体系与性能之间的结构-性能关系。然而,最近对许多表面重建现象的观察挑战了依赖静态界面模型来阐明结构-性能关系的传统研究范式。这一观点侧重于催化剂-电解质界面模型,并从自由能的角度合理化催化剂表面重构行为的基本原理。然后展示了预催化剂结构、电解质(包括添加剂和反应中间体)和外部偏置对表面重构的影响,以及基于当前对表面构建的理解的最先进的调制策略。最后,我们强调了未来催化剂表面重构研究的关键问题,包括尚未探索的影响重构和反应类型的因素,原位表征和模拟技术的必要发展,以及目前被忽视的催化剂失活问题。
{"title":"In-depth understanding and precise modulation of surface reconstruction during heterogeneous electrocatalysis: From model to practical catalyst","authors":"Weidong Dai ,&nbsp;Kaiwei Wan ,&nbsp;Kanglei Pang ,&nbsp;Jun Guo ,&nbsp;Siyuan Liu ,&nbsp;Keying Wu ,&nbsp;Chiyao Tang ,&nbsp;Yanjuan Sun ,&nbsp;Xinghua Shi ,&nbsp;Zhiyong Tang ,&nbsp;Chang Long ,&nbsp;Fan Dong","doi":"10.1016/j.chempr.2024.10.012","DOIUrl":"10.1016/j.chempr.2024.10.012","url":null,"abstract":"<div><div>Renewable energy-driven heterogeneous electrocatalysis holds tremendous potential in converting earth-abundant small molecules and industrial pollutants into value-added or environmentally friendly chemicals, sparking global research interest. The catalyst-electrolyte interface has long been at the forefront of heterogeneous electrocatalysis, dealing with the structure-performance relationship between the performance and the catalytic system, consisting of catalysts, electrolytes, and external biases, at the molecular or atomic level. However, recent observations of numerous surface reconstruction phenomena have challenged the traditional research paradigm that relies on static interface models to elucidate structure-performance relationships. This perspective focuses on the catalyst-electrolyte interface model and rationalizes the underlying principles of catalyst surface reconstruction behavior in terms of free energy. It then showcases the influence of pre-catalyst structure, electrolyte (including additives and reaction intermediates), and external bias on surface reconstruction, alongside state-of-the-art modulation strategies based on the current understanding of surface construction. Finally, we highlight critical issues for future research on catalyst surface reconstruction, including the unexplored factors influencing reconstruction and reaction types, the necessary developments in <em>in situ</em> characterization and simulation techniques, and the currently overlooked problem of catalyst deactivation.</div></div>","PeriodicalId":268,"journal":{"name":"Chem","volume":"11 1","pages":"Article 102345"},"PeriodicalIF":19.1,"publicationDate":"2025-01-09","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142937582","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}
引用次数: 0
Guest binding is governed by multiple stimuli in low-symmetry metal-organic cages containing bis-pyridyl(imine) vertices 在含有双吡啶(亚胺)顶点的低对称金属有机笼中,客体结合受多重刺激的影响
IF 19.1 1区 化学 Q1 CHEMISTRY, MULTIDISCIPLINARY Pub Date : 2025-01-09 DOI: 10.1016/j.chempr.2024.08.011
Yuchong Yang , Tanya K. Ronson , Paula C.P. Teeuwen , Yuyin Du , Jieyu Zheng , David J. Wales , Jonathan R. Nitschke
Inspired by natural systems, metal-organic cages with well-defined shapes and cavities can be tuned for different guest-binding functions. Here, we report the construction of two types of cage frameworks: an MII12L8 (M = ZnII and CoII) pseudo-cuboctahedral architecture 1 and a rarer MII9L8 (M = ZnII and CoII) pseudo-Johnson-solid-type (J51) framework 2. Both structures form from the same boron-containing triamine subcomponent, and each one incorporates hexacoordinate metal vertices chelated by only two bidentate pyridyl(imine) arms. Such vertices provide the cages with the flexibility required to form lower-symmetry architectures, and they also facilitate reversible disassembly in response to fluoride. These cages were also shown to respond to other chemical stimuli enabling transformation between cage structures. Cage 1 bound different guest molecules, including the anticancer drug paclitaxel, C-methylcalix[4]resorcinarene, and tetraphenylborates. The release of paclitaxel by 1 was stimulated by fluoride or chloride, highlighting the potential for applications in natural product separation and drug delivery.
受自然系统的启发,具有明确形状和空腔的金属有机笼可以针对不同的客体结合功能进行调整。在此,我们报告了两种笼形框架的构建:一种是 MII12L8(M = ZnII 和 CoII)伪立方体结构 1,另一种是较罕见的 MII9L8(M = ZnII 和 CoII)伪约翰逊固体型(J51)框架 2。这两种结构都由相同的含硼三胺亚组分形成,每种结构都包含六配位金属顶点,仅由两个双齿吡啶(亚胺)臂螯合。这些顶点为笼子提供了形成低对称性结构所需的灵活性,而且还有助于在氟化物作用下进行可逆拆解。研究还表明,这些笼子还能对其他化学刺激做出反应,从而实现笼子结构之间的转换。笼 1 结合了不同的客体分子,包括抗癌药物紫杉醇、C-甲基钙[4]间苯二酚和四苯基硼酸盐。氟化物或氯化物可刺激笼 1 释放紫杉醇,这凸显了笼 1 在天然产品分离和药物输送方面的应用潜力。
{"title":"Guest binding is governed by multiple stimuli in low-symmetry metal-organic cages containing bis-pyridyl(imine) vertices","authors":"Yuchong Yang ,&nbsp;Tanya K. Ronson ,&nbsp;Paula C.P. Teeuwen ,&nbsp;Yuyin Du ,&nbsp;Jieyu Zheng ,&nbsp;David J. Wales ,&nbsp;Jonathan R. Nitschke","doi":"10.1016/j.chempr.2024.08.011","DOIUrl":"10.1016/j.chempr.2024.08.011","url":null,"abstract":"<div><div>Inspired by natural systems, metal-organic cages with well-defined shapes and cavities can be tuned for different guest-binding functions. Here, we report the construction of two types of cage frameworks: an M<sup>II</sup><sub>12</sub>L<sub>8</sub> (M = Zn<sup>II</sup> and Co<sup>II</sup>) <em>pseudo</em>-cuboctahedral architecture <strong>1</strong> and a rarer M<sup>II</sup><sub>9</sub>L<sub>8</sub> (M = Zn<sup>II</sup> and Co<sup>II</sup>) <em>pseudo</em>-Johnson-solid-type (<em>J</em><sub>51</sub>) framework <strong>2</strong>. Both structures form from the same boron-containing triamine subcomponent, and each one incorporates hexacoordinate metal vertices chelated by only two bidentate pyridyl(imine) arms. Such vertices provide the cages with the flexibility required to form lower-symmetry architectures, and they also facilitate reversible disassembly in response to fluoride. These cages were also shown to respond to other chemical stimuli enabling transformation between cage structures. Cage <strong>1</strong> bound different guest molecules, including the anticancer drug paclitaxel, <em>C</em>-methylcalix[4]resorcinarene, and tetraphenylborates. The release of paclitaxel by <strong>1</strong> was stimulated by fluoride or chloride, highlighting the potential for applications in natural product separation and drug delivery.</div></div>","PeriodicalId":268,"journal":{"name":"Chem","volume":"11 1","pages":"Article 102288"},"PeriodicalIF":19.1,"publicationDate":"2025-01-09","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142221774","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"OA","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
引用次数: 0
Bridging gaps between lab- and fab-oriented anode design for proton exchange membrane water electrolyzers 弥合质子交换膜水电解槽实验室阳极设计与工厂阳极设计之间的差距
IF 19.1 1区 化学 Q1 CHEMISTRY, MULTIDISCIPLINARY Pub Date : 2025-01-09 DOI: 10.1016/j.chempr.2024.09.004
Jun Xu , Yuting Yang , Huanyu Jin , Yao Zheng , Shi-Zhang Qiao
Rationally designing anode electrocatalysts is crucial for advancing next-generation proton exchange membrane water electrolyzers (PEMWEs). However, the most developed oxygen evolution catalysts in labs often cannot be directly applied to commercial PEMWEs due to differences in durability, performance, and cost. In this perspective, we review these gaps between fundamental lab research and practical device requirements and propose solutions to bridge them. We cover degradation mechanisms and durability evaluations in lab-scale aqueous model systems (AMSs) and PEMWEs. The need for performance benchmarking for anode screening and assessment is addressed, emphasizing reliable test protocols in AMSs and PEMWEs. Additionally, we discuss the importance of cost reduction in anodic catalyst design for future PEMWEs systems. Finally, we highlight major challenges and propose outlooks for anode design in fab-oriented applications to achieve the ultimate green hydrogen goal of “1 kg H2 produced by 1 USD in 1 decade” (“111” goal).
合理设计阳极电催化剂对于推动下一代质子交换膜水电解器(PEMWEs)的发展至关重要。然而,由于耐久性、性能和成本方面的差异,实验室中最先进的氧进化催化剂往往不能直接应用于商用 PEMWE。在本文中,我们回顾了实验室基础研究与实际设备要求之间的差距,并提出了弥合这些差距的解决方案。我们将对实验室规模的水模型系统(AMS)和 PEMWE 的降解机制和耐用性进行评估。我们讨论了阳极筛选和评估对性能基准的需求,强调了 AMS 和 PEMWEs 中可靠的测试协议。此外,我们还讨论了为未来的 PEMWEs 系统降低阳极催化剂设计成本的重要性。最后,我们强调了在面向晶圆厂的应用中阳极设计所面临的主要挑战并提出了展望,以实现 "十年内用 1 美元生产 1 千克 H2"("111 "目标)的绿色氢气终极目标。
{"title":"Bridging gaps between lab- and fab-oriented anode design for proton exchange membrane water electrolyzers","authors":"Jun Xu ,&nbsp;Yuting Yang ,&nbsp;Huanyu Jin ,&nbsp;Yao Zheng ,&nbsp;Shi-Zhang Qiao","doi":"10.1016/j.chempr.2024.09.004","DOIUrl":"10.1016/j.chempr.2024.09.004","url":null,"abstract":"<div><div>Rationally designing anode electrocatalysts is crucial for advancing next-generation proton exchange membrane water electrolyzers (PEMWEs). However, the most developed oxygen evolution catalysts in labs often cannot be directly applied to commercial PEMWEs due to differences in durability, performance, and cost. In this perspective, we review these gaps between fundamental lab research and practical device requirements and propose solutions to bridge them. We cover degradation mechanisms and durability evaluations in lab-scale aqueous model systems (AMSs) and PEMWEs. The need for performance benchmarking for anode screening and assessment is addressed, emphasizing reliable test protocols in AMSs and PEMWEs. Additionally, we discuss the importance of cost reduction in anodic catalyst design for future PEMWEs systems. Finally, we highlight major challenges and propose outlooks for anode design in fab-oriented applications to achieve the ultimate green hydrogen goal of “1 kg H<sub>2</sub> produced by 1 USD in 1 decade” (“111” goal).</div></div>","PeriodicalId":268,"journal":{"name":"Chem","volume":"11 1","pages":"Article 102305"},"PeriodicalIF":19.1,"publicationDate":"2025-01-09","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142398237","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}
引用次数: 0
Energy transfer-based X-ray imaging scintillators 基于能量转移的 X 射线成像闪烁体
IF 19.1 1区 化学 Q1 CHEMISTRY, MULTIDISCIPLINARY Pub Date : 2025-01-09 DOI: 10.1016/j.chempr.2024.07.035
Jian-Xin Wang , Osama Shekhah , Osman M. Bakr , Mohamed Eddaoudi , Omar F. Mohammed
X-ray imaging scintillators are essential for numerous technologies that impact our daily lives, including medical radiography, computed tomography, and security inspection. Organic materials have emerged as potential alternatives for X-ray imaging scintillators due to their low toxicity, high stability, and large-area fabrication. However, their low X-ray absorption cross-section and inefficient exciton utilization efficiency limit their practical applications and commercialization. Nevertheless, these drawbacks can be mitigated through efficient energy transfer from suitable X-ray sensitizers. In this review, we summarize recent progress in fabricating high-performance energy transfer-based scintillators using a variety of X-ray sensitizers and emission centers and provide a detailed interpretation of the corresponding energy transfer mechanisms and their tremendous impact on the operation of X-ray imaging scintillators. Furthermore, we have also carefully considered the impact of various factors within the imaging system, including the X-ray source, light-matter interaction, and photodetector, on the overall imaging performance.
X 射线成像闪烁体对于影响我们日常生活的众多技术来说至关重要,其中包括医疗射线照相术、计算机断层扫描和安全检查。有机材料因其低毒性、高稳定性和大面积制造而成为 X 射线成像闪烁体的潜在替代品。然而,有机材料对 X 射线的吸收截面小、激子利用效率低,限制了其实际应用和商业化。不过,这些缺点可以通过合适的 X 射线敏化剂进行有效的能量转移来缓解。在本综述中,我们总结了利用各种 X 射线敏化剂和发射中心制造基于能量转移的高性能闪烁体的最新进展,并详细解释了相应的能量转移机制及其对 X 射线成像闪烁体工作的巨大影响。此外,我们还仔细考虑了成像系统中各种因素(包括 X 射线源、光物质相互作用和光电探测器)对整体成像性能的影响。
{"title":"Energy transfer-based X-ray imaging scintillators","authors":"Jian-Xin Wang ,&nbsp;Osama Shekhah ,&nbsp;Osman M. Bakr ,&nbsp;Mohamed Eddaoudi ,&nbsp;Omar F. Mohammed","doi":"10.1016/j.chempr.2024.07.035","DOIUrl":"10.1016/j.chempr.2024.07.035","url":null,"abstract":"<div><div>X-ray imaging scintillators are essential for numerous technologies that impact our daily lives, including medical radiography, computed tomography, and security inspection. Organic materials have emerged as potential alternatives for X-ray imaging scintillators due to their low toxicity, high stability, and large-area fabrication. However, their low X-ray absorption cross-section and inefficient exciton utilization efficiency limit their practical applications and commercialization. Nevertheless, these drawbacks can be mitigated through efficient energy transfer from suitable X-ray sensitizers. In this review, we summarize recent progress in fabricating high-performance energy transfer-based scintillators using a variety of X-ray sensitizers and emission centers and provide a detailed interpretation of the corresponding energy transfer mechanisms and their tremendous impact on the operation of X-ray imaging scintillators. Furthermore, we have also carefully considered the impact of various factors within the imaging system, including the X-ray source, light-matter interaction, and photodetector, on the overall imaging performance.</div></div>","PeriodicalId":268,"journal":{"name":"Chem","volume":"11 1","pages":"Article 102273"},"PeriodicalIF":19.1,"publicationDate":"2025-01-09","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142138189","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}
引用次数: 0
The cyclotriborate trianion 环三硼酸盐三阴离子
IF 19.1 1区 化学 Q1 CHEMISTRY, MULTIDISCIPLINARY Pub Date : 2025-01-09 DOI: 10.1016/j.chempr.2024.09.002
Manjur O. Akram , Caleb D. Martin
In this issue of Chem, Kinjo and Feng report the synthesis of a cyclotriborate trianion (B3R63−), a highly charged boron ring system with discrete two-center two-electron bonds. With three contiguous borates, the B33− core of the feature compound defies Coulomb’s law and represents the first homocyclic boron analog of the ubiquitous cyclopropane. The remarkable stability enabled full characterization and opens new vistas in the field of multiply charged boron ions.
在本期《化学》杂志上,Kinjo 和 Feng 报告了一种环三硼酸盐三阴离子(B3R63-)的合成,这是一种具有离散双中心双电子键的高电荷硼环系统。由于具有三个连续的硼酸盐,该特征化合物的 B33- 核心违背了库仑定律,代表了无处不在的环丙烷的第一个同环硼类似物。其出色的稳定性使其得以全面表征,并为多电荷硼离子领域开辟了新的前景。
{"title":"The cyclotriborate trianion","authors":"Manjur O. Akram ,&nbsp;Caleb D. Martin","doi":"10.1016/j.chempr.2024.09.002","DOIUrl":"10.1016/j.chempr.2024.09.002","url":null,"abstract":"<div><div>In this issue of <em>Chem</em>, Kinjo and Feng report the synthesis of a cyclotriborate trianion (B<sub>3</sub>R<sub>6</sub><sup>3−</sup>), a highly charged boron ring system with discrete two-center two-electron bonds. With three contiguous borates, the B<sub>3</sub><sup>3−</sup> core of the feature compound defies Coulomb’s law and represents the first homocyclic boron analog of the ubiquitous cyclopropane. The remarkable stability enabled full characterization and opens new vistas in the field of multiply charged boron ions.</div></div>","PeriodicalId":268,"journal":{"name":"Chem","volume":"11 1","pages":"Article 102303"},"PeriodicalIF":19.1,"publicationDate":"2025-01-09","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142439926","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}
引用次数: 0
Biocatalytic programming of protocell-embodied logic gates and circuits 原生细胞逻辑门与电路的生物催化编程
IF 23.5 1区 化学 Q1 CHEMISTRY, MULTIDISCIPLINARY Pub Date : 2025-01-08 DOI: 10.1016/j.chempr.2024.11.017
Ananya Mishra, Avinash J. Patil, Stephen Mann
The construction of biomimetic agents capable of generating precise outcomes in response to specific molecular inputs is a central challenge for the development of programmable synthetic cells with integrated biomimetic functions. Here, we harness acoustic standing waves to generate periodic microarrays of enzyme-encoded coacervate microdroplets for the implementation of embodied enzyme logic circuits (EELCs). We describe a range of biocatalytic communication channels capable of performing localized and distributed Boolean logic functions in single or segregated populations of model protocells by using a range of molecular inputs, fluorescence or hydrogelation outputs, and programmable response dynamics. To implement long-range collective signal processing, we integrate EELC modules across spatially segregated protocell populations to generate distributed time-regulated logic operations involving negative feedback, pulse generation, and redirected output-input connectivity. Our results provide a step toward the non-DNA programming of model protocell communication and computational networks for miniaturized autonomous sensing devices capable of chemical-based information processing.
构建能够根据特定分子输入产生精确结果的仿生制剂是开发具有综合仿生功能的可编程合成细胞的核心挑战。在这里,我们利用声波驻波来产生酶编码凝聚微滴的周期性微阵列,以实现嵌入酶逻辑电路(EELCs)。我们描述了一系列生物催化通信通道,能够在单个或分离的模型原始细胞群体中执行局部和分布式布尔逻辑功能,通过使用一系列分子输入,荧光或hydrogelation输出以及可编程的响应动力学。为了实现远程集体信号处理,我们在空间隔离的原始细胞群体中集成EELC模块,以产生分布式的时间调节逻辑操作,包括负反馈、脉冲产生和重定向输出输入连接。我们的研究结果为能够基于化学信息处理的小型化自主传感设备的模型原始细胞通信和计算网络的非dna编程提供了一步。
{"title":"Biocatalytic programming of protocell-embodied logic gates and circuits","authors":"Ananya Mishra, Avinash J. Patil, Stephen Mann","doi":"10.1016/j.chempr.2024.11.017","DOIUrl":"https://doi.org/10.1016/j.chempr.2024.11.017","url":null,"abstract":"The construction of biomimetic agents capable of generating precise outcomes in response to specific molecular inputs is a central challenge for the development of programmable synthetic cells with integrated biomimetic functions. Here, we harness acoustic standing waves to generate periodic microarrays of enzyme-encoded coacervate microdroplets for the implementation of embodied enzyme logic circuits (EELCs). We describe a range of biocatalytic communication channels capable of performing localized and distributed Boolean logic functions in single or segregated populations of model protocells by using a range of molecular inputs, fluorescence or hydrogelation outputs, and programmable response dynamics. To implement long-range collective signal processing, we integrate EELC modules across spatially segregated protocell populations to generate distributed time-regulated logic operations involving negative feedback, pulse generation, and redirected output-input connectivity. Our results provide a step toward the non-DNA programming of model protocell communication and computational networks for miniaturized autonomous sensing devices capable of chemical-based information processing.","PeriodicalId":268,"journal":{"name":"Chem","volume":"56 1","pages":""},"PeriodicalIF":23.5,"publicationDate":"2025-01-08","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142936132","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}
引用次数: 0
Biosynthesis and genetic encoding of activated nitriles for fast protein conjugation and tunable fluorogenic labeling 用于快速蛋白偶联和可调荧光标记的活性腈的生物合成和遗传编码
IF 23.5 1区 化学 Q1 CHEMISTRY, MULTIDISCIPLINARY Pub Date : 2025-01-06 DOI: 10.1016/j.chempr.2024.12.003
Elwy H. Abdelkader, Haocheng Qianzhu, Gottfried Otting, Thomas Huber
Few chemistries are suitable for in-cell protein labeling, and the required reagents are costly. We present an approach for the coupled biosynthesis and genetic encoding of activated nitriles, delivering a facile way to furnish proteins with biocompatible reactive handles suitable for subsequent site-specific modifications both in cell and in vitro. The strategy utilizes the endogenous bacterial cysteine biosynthetic machinery to produce the nitrile-bearing non-canonical amino acids (ncAAs) in situ and then perform genetic encoding through an engineered orthogonal translation system. We demonstrate the utility of our system for rapid site-specific bioconjugation and macrocyclization through the nitrile-aminothiol (NAT) click reaction. In addition, we introduce the aromatic condensation NAT (arcNAT) click reaction as a tool for generating a diverse array of turn-on fluorophores. arcNAT achieves fluorogenic labeling of proteins for live-cell microscopy without requiring washing steps. Our approach provides a uniquely convenient, versatile, and cost-effective platform for the post-translational diversification of proteins.
很少有化学物质适合细胞内蛋白质标记,而且所需的试剂价格昂贵。我们提出了一种激活腈的耦合生物合成和遗传编码方法,提供了一种简便的方法来为蛋白质提供生物相容性反应处理,适用于随后在细胞和体外的位点特异性修饰。该策略利用内源性细菌半胱氨酸生物合成机制在原位产生含腈非规范氨基酸(ncAAs),然后通过工程正交翻译系统进行遗传编码。我们展示了我们的系统通过腈-氨基硫醇(NAT)点击反应进行快速位点特异性生物偶联和大环化的实用性。此外,我们还介绍了芳香缩合NAT (arcNAT)点击反应作为一种工具,用于生成各种各样的开启荧光团。arcNAT实现了活细胞显微镜下蛋白质的荧光标记,不需要洗涤步骤。我们的方法为蛋白质的翻译后多样化提供了一个独特、方便、通用和经济的平台。
{"title":"Biosynthesis and genetic encoding of activated nitriles for fast protein conjugation and tunable fluorogenic labeling","authors":"Elwy H. Abdelkader, Haocheng Qianzhu, Gottfried Otting, Thomas Huber","doi":"10.1016/j.chempr.2024.12.003","DOIUrl":"https://doi.org/10.1016/j.chempr.2024.12.003","url":null,"abstract":"Few chemistries are suitable for in-cell protein labeling, and the required reagents are costly. We present an approach for the coupled biosynthesis and genetic encoding of activated nitriles, delivering a facile way to furnish proteins with biocompatible reactive handles suitable for subsequent site-specific modifications both in cell and <em>in vitro</em>. The strategy utilizes the endogenous bacterial cysteine biosynthetic machinery to produce the nitrile-bearing non-canonical amino acids (ncAAs) <em>in situ</em> and then perform genetic encoding through an engineered orthogonal translation system. We demonstrate the utility of our system for rapid site-specific bioconjugation and macrocyclization through the nitrile-aminothiol (NAT) click reaction. In addition, we introduce the aromatic condensation NAT (arcNAT) click reaction as a tool for generating a diverse array of turn-on fluorophores. arcNAT achieves fluorogenic labeling of proteins for live-cell microscopy without requiring washing steps. Our approach provides a uniquely convenient, versatile, and cost-effective platform for the post-translational diversification of proteins.","PeriodicalId":268,"journal":{"name":"Chem","volume":"4 1","pages":""},"PeriodicalIF":23.5,"publicationDate":"2025-01-06","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142929625","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}
引用次数: 0
Beyond natural synthesis via solar-decoupled biohybrid photosynthetic system 超越自然合成通过太阳解耦的生物杂交光合系统
IF 23.5 1区 化学 Q1 CHEMISTRY, MULTIDISCIPLINARY Pub Date : 2025-01-03 DOI: 10.1016/j.chempr.2024.11.019
Na Chen, Jing Xi, Tianpei He, Ruichen Shen, Rui Zhao, Haoming Chi, Jia Yao, Na Du, Lilei Yu, Yun Zhang, Tianyou Peng, Tiangang Liu, Quan Yuan
Inspired by the solar energy storage process during photosynthesis, we report herein a solar-decoupled photosynthetic biohybrid strategy through integrating a persistent photocatalyst with photoautotrophic microbes for sustainable and all-weather biomanufacturing, allowing for overcoming the intrinsic intermittent nature of solar energy availability by introducing energy storage and release processes. The results demonstrate that the apparent photo conversion efficiency (APCE) for of the persistent catalyst/R. palustris hybrid system reaches 8.30%, much higher than the 4.36% observed in bare R. palustris. Additionally, the proposed solar-decoupled biohybrid strategy not only shows considerable potential in coupling the practical power plant for the capture and utilization of CO2 from the flue gas but also exhibits universal applicability in different photosynthetic microorganisms. This concept-proving research offers new ideas to extend photocatalysis reactions without in situ irradiation and could pave new ways for sustainable solar energy utilization as well as biomanufacturing in space, where solar energy might be limited.
受光合作用过程中太阳能储存过程的启发,我们在此报告了一种太阳能解耦光合生物杂交策略,通过将持久性光催化剂与光自养微生物相结合,实现可持续和全天候的生物制造,从而通过引入能量储存和释放过程来克服太阳能可用性固有的间歇性。结果表明,该催化剂的表观光转化效率(APCE)比R。斑马草杂交系统达到8.30%,远高于裸斑马草的4.36%。此外,所提出的太阳能解耦生物混合策略不仅在耦合实际电厂以捕获和利用烟气中的CO2方面显示出相当大的潜力,而且在不同的光合微生物中也具有普遍适用性。这一证明概念的研究为延长光催化反应提供了新的思路,而无需原位辐照,并可能为太阳能的可持续利用以及太阳能可能有限的太空生物制造铺平新的道路。
{"title":"Beyond natural synthesis via solar-decoupled biohybrid photosynthetic system","authors":"Na Chen, Jing Xi, Tianpei He, Ruichen Shen, Rui Zhao, Haoming Chi, Jia Yao, Na Du, Lilei Yu, Yun Zhang, Tianyou Peng, Tiangang Liu, Quan Yuan","doi":"10.1016/j.chempr.2024.11.019","DOIUrl":"https://doi.org/10.1016/j.chempr.2024.11.019","url":null,"abstract":"Inspired by the solar energy storage process during photosynthesis, we report herein a solar-decoupled photosynthetic biohybrid strategy through integrating a persistent photocatalyst with photoautotrophic microbes for sustainable and all-weather biomanufacturing, allowing for overcoming the intrinsic intermittent nature of solar energy availability by introducing energy storage and release processes. The results demonstrate that the apparent photo conversion efficiency (APCE) for of the persistent catalyst/<em>R</em>. <em>palustris</em> hybrid system reaches 8.30%, much higher than the 4.36% observed in bare <em>R. palustris</em>. Additionally, the proposed solar-decoupled biohybrid strategy not only shows considerable potential in coupling the practical power plant for the capture and utilization of CO<sub>2</sub> from the flue gas but also exhibits universal applicability in different photosynthetic microorganisms. This concept-proving research offers new ideas to extend photocatalysis reactions without <em>in situ</em> irradiation and could pave new ways for sustainable solar energy utilization as well as biomanufacturing in space, where solar energy might be limited.","PeriodicalId":268,"journal":{"name":"Chem","volume":"32 1","pages":""},"PeriodicalIF":23.5,"publicationDate":"2025-01-03","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142917917","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}
引用次数: 0
Fine-tuned coordination environment of Pt-Fe-Pt active site for selective heterogeneous hydrogenation of crotonaldehyde 巴豆醛选择性非均相加氢Pt-Fe-Pt活性位点配位环境的微调
IF 23.5 1区 化学 Q1 CHEMISTRY, MULTIDISCIPLINARY Pub Date : 2025-01-03 DOI: 10.1016/j.chempr.2024.11.018
Di Zhou, Junjun Wang, Minzhen Jian, Yong Li, Zheng Jiang, Shuang Liu, Yan Zhou, Jiake Wei, Christof Wöll, Wei-Xue Li, Yuemin Wang, Wenjie Shen
Dispersing the catalytically more active noble metal at the single-site scale ensures maximum atom efficiency for selective heterogeneous hydrogenation over bimetallic particles. However, the low density and random location of the noble-metal atoms compromise the intrinsic activity and/or selectivity because of the resulting altered electronic structure. Here, we report that densely populating and precisely arranging Pt atoms in the form of a Pt-Fe-Pt heterotrimer not only catalyzes preferential hydrogenation of the C=O bond in crotonaldehyde (CAL) but also increases the reaction rate by 35-fold, circumventing the activity-selectivity trade-off. The Pt-Fe-Pt active site is fabricated by H2 reduction at 673 K of a Pt-Fe2O3 particle pair, wherein a 3.3 nm Pt particle sits on a 9.8 nm Fe2O3 particle. It interacts with the CAL molecule in a site-bond recognition manner: the left-end Pt atom anchors the C=C bond, whereas the central Fe atom activates the C=O bond, which is further hydrogenated by H atoms adsorbed on the right-end Pt atom.
将催化活性更高的贵金属分散在单位点尺度上,可确保在双金属颗粒上进行选择性非均相氢化的最大原子效率。然而,由于贵金属原子的低密度和随机位置,导致电子结构改变,从而损害了其固有活性和/或选择性。在这里,我们报道了密集填充和精确排列Pt原子以Pt- fe -Pt异质三聚体的形式不仅催化巴丁醛(CAL)中C=O键的优先氢化,而且还将反应速率提高了35倍,绕过了活性-选择性权衡。在673 K下H2还原Pt-Fe2O3粒子对制备了Pt- fe -Pt活性位点,其中3.3 nm的Pt粒子位于9.8 nm的Fe2O3粒子上。它以位点键识别的方式与CAL分子相互作用:左端Pt原子锚定C=C键,而中心Fe原子激活C=O键,C=O键被吸附在右端Pt原子上的H原子进一步氢化。
{"title":"Fine-tuned coordination environment of Pt-Fe-Pt active site for selective heterogeneous hydrogenation of crotonaldehyde","authors":"Di Zhou, Junjun Wang, Minzhen Jian, Yong Li, Zheng Jiang, Shuang Liu, Yan Zhou, Jiake Wei, Christof Wöll, Wei-Xue Li, Yuemin Wang, Wenjie Shen","doi":"10.1016/j.chempr.2024.11.018","DOIUrl":"https://doi.org/10.1016/j.chempr.2024.11.018","url":null,"abstract":"Dispersing the catalytically more active noble metal at the single-site scale ensures maximum atom efficiency for selective heterogeneous hydrogenation over bimetallic particles. However, the low density and random location of the noble-metal atoms compromise the intrinsic activity and/or selectivity because of the resulting altered electronic structure. Here, we report that densely populating and precisely arranging Pt atoms in the form of a Pt-Fe-Pt heterotrimer not only catalyzes preferential hydrogenation of the C=O bond in crotonaldehyde (CAL) but also increases the reaction rate by 35-fold, circumventing the activity-selectivity trade-off. The Pt-Fe-Pt active site is fabricated by H<sub>2</sub> reduction at 673 K of a Pt-Fe<sub>2</sub>O<sub>3</sub> particle pair, wherein a 3.3 nm Pt particle sits on a 9.8 nm Fe<sub>2</sub>O<sub>3</sub> particle. It interacts with the CAL molecule in a site-bond recognition manner: the left-end Pt atom anchors the C=C bond, whereas the central Fe atom activates the C=O bond, which is further hydrogenated by H atoms adsorbed on the right-end Pt atom.","PeriodicalId":268,"journal":{"name":"Chem","volume":"75 1","pages":""},"PeriodicalIF":23.5,"publicationDate":"2025-01-03","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142917848","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}
引用次数: 0
期刊
Chem
全部 Acc. Chem. Res. ACS Applied Bio Materials ACS Appl. Electron. Mater. ACS Appl. Energy Mater. ACS Appl. Mater. Interfaces ACS Appl. Nano Mater. ACS Appl. Polym. Mater. ACS BIOMATER-SCI ENG ACS Catal. ACS Cent. Sci. ACS Chem. Biol. ACS Chemical Health & Safety ACS Chem. Neurosci. ACS Comb. Sci. ACS Earth Space Chem. ACS Energy Lett. ACS Infect. Dis. ACS Macro Lett. ACS Mater. Lett. ACS Med. Chem. Lett. ACS Nano ACS Omega ACS Photonics ACS Sens. ACS Sustainable Chem. Eng. ACS Synth. Biol. Anal. Chem. BIOCHEMISTRY-US Bioconjugate Chem. BIOMACROMOLECULES Chem. Res. Toxicol. Chem. Rev. Chem. Mater. CRYST GROWTH DES ENERG FUEL Environ. Sci. Technol. Environ. Sci. Technol. Lett. Eur. J. Inorg. Chem. IND ENG CHEM RES Inorg. Chem. J. Agric. Food. Chem. J. Chem. Eng. Data J. Chem. Educ. J. Chem. Inf. Model. J. Chem. Theory Comput. J. Med. Chem. J. Nat. Prod. J PROTEOME RES J. Am. Chem. Soc. LANGMUIR MACROMOLECULES Mol. Pharmaceutics Nano Lett. Org. Lett. ORG PROCESS RES DEV ORGANOMETALLICS J. Org. Chem. J. Phys. Chem. J. Phys. Chem. A J. Phys. Chem. B J. Phys. Chem. C J. Phys. Chem. Lett. Analyst Anal. Methods Biomater. Sci. Catal. Sci. Technol. Chem. Commun. Chem. Soc. Rev. CHEM EDUC RES PRACT CRYSTENGCOMM Dalton Trans. Energy Environ. Sci. ENVIRON SCI-NANO ENVIRON SCI-PROC IMP ENVIRON SCI-WAT RES Faraday Discuss. Food Funct. Green Chem. Inorg. Chem. Front. Integr. Biol. J. Anal. At. Spectrom. J. Mater. Chem. A J. Mater. Chem. B J. Mater. Chem. C Lab Chip Mater. Chem. Front. Mater. Horiz. MEDCHEMCOMM Metallomics Mol. Biosyst. Mol. Syst. Des. Eng. Nanoscale Nanoscale Horiz. Nat. Prod. Rep. New J. Chem. Org. Biomol. Chem. Org. Chem. Front. PHOTOCH PHOTOBIO SCI PCCP Polym. Chem.
×
引用
GB/T 7714-2015
复制
MLA
复制
APA
复制
导出至
BibTeX EndNote RefMan NoteFirst NoteExpress
×
0
微信
客服QQ
Book学术公众号 扫码关注我们
反馈
×
意见反馈
请填写您的意见或建议
请填写您的手机或邮箱
×
提示
您的信息不完整,为了账户安全,请先补充。
现在去补充
×
提示
您因"违规操作"
具体请查看互助需知
我知道了
×
提示
现在去查看 取消
×
提示
确定
Book学术官方微信
Book学术文献互助
Book学术文献互助群
群 号:481959085
Book学术
文献互助 智能选刊 最新文献 互助须知 联系我们:info@booksci.cn
Book学术提供免费学术资源搜索服务,方便国内外学者检索中英文文献。致力于提供最便捷和优质的服务体验。
Copyright © 2023 Book学术 All rights reserved.
ghs 京公网安备 11010802042870号 京ICP备2023020795号-1