Pub Date : 2025-01-09DOI: 10.1016/j.chempr.2024.07.009
William G. Ryder , Aviva Levina , Marcus E. Graziotto , Bryson A. Hawkins , David E. Hibbs , Elizabeth J. New , Philip A. Gale
Synthetic anion transporters that mediate electroneutral (H+/Cl−) transport have demonstrated anti-cancer activity due to their ability to disrupt subcellular homeostatic environments. Elucidation of the cell death mechanism revealed the transporters’ ability to neutralize lysosomal pH gradients and inhibit autophagy. However, their effects on other subcellular compartments are unknown. Herein, we disclose the first subcellular targeted anionophores that accumulate in various membrane-bound organelles to bias their natural propensity to depolarize lysosomes. Confocal microscopy revealed that the naphthalimide-based transporters effectively localized within their intended organelles. Analogs containing endoplasmic reticulum (ER) and lysosomal targeting motifs showed an enhanced H+/Cl− transport ability and greater cytotoxicity compared with non-targeted analogs. Moreover, lysosomal accumulation improved cancer cell selectivity, while ER and mitochondrial localization enhanced apoptosis in cancer cells. Our work provides an alternative approach to the design of therapeutically focused synthetic anion transporters and an insight into possible subcellular compartment-specific effects on homeostasis.
介导电中性（H+/Cl-）转运的合成阴离子转运体具有破坏亚细胞平衡环境的能力，因而具有抗癌活性。对细胞死亡机制的阐明表明，转运体能够中和溶酶体的 pH 梯度并抑制自噬。然而，它们对其他亚细胞区室的影响尚不清楚。在此，我们首次揭示了亚细胞靶向阴离子载体，这种载体在各种膜结合细胞器中积聚，使溶酶体的自然去极化倾向发生偏移。共聚焦显微镜显示，基于萘二甲酰亚胺的转运体有效地定位在其目标细胞器内。与非靶向类似物相比，含有内质网（ER）和溶酶体靶向基团的类似物显示出更强的 H+/Cl- 转运能力和更大的细胞毒性。此外，溶酶体积聚提高了癌细胞的选择性，而 ER 和线粒体定位则增强了癌细胞的凋亡。我们的工作为设计具有治疗作用的合成阴离子转运体提供了另一种方法，并使我们深入了解了亚细胞区室对稳态的特异性影响。
{"title":"Subcellular targeted anion transporters","authors":"William G. Ryder , Aviva Levina , Marcus E. Graziotto , Bryson A. Hawkins , David E. Hibbs , Elizabeth J. New , Philip A. Gale","doi":"10.1016/j.chempr.2024.07.009","DOIUrl":"10.1016/j.chempr.2024.07.009","url":null,"abstract":"<div><div>Synthetic anion transporters that mediate electroneutral (H<sup>+</sup>/Cl<sup>−</sup>) transport have demonstrated anti-cancer activity due to their ability to disrupt subcellular homeostatic environments. Elucidation of the cell death mechanism revealed the transporters’ ability to neutralize lysosomal pH gradients and inhibit autophagy. However, their effects on other subcellular compartments are unknown. Herein, we disclose the first subcellular targeted anionophores that accumulate in various membrane-bound organelles to bias their natural propensity to depolarize lysosomes. Confocal microscopy revealed that the naphthalimide-based transporters effectively localized within their intended organelles. Analogs containing endoplasmic reticulum (ER) and lysosomal targeting motifs showed an enhanced H<sup>+</sup>/Cl<sup>−</sup> transport ability and greater cytotoxicity compared with non-targeted analogs. Moreover, lysosomal accumulation improved cancer cell selectivity, while ER and mitochondrial localization enhanced apoptosis in cancer cells. Our work provides an alternative approach to the design of therapeutically focused synthetic anion transporters and an insight into possible subcellular compartment-specific effects on homeostasis.</div></div>","PeriodicalId":268,"journal":{"name":"Chem","volume":"11 1","pages":"Article 102247"},"PeriodicalIF":19.1,"publicationDate":"2025-01-09","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142023141","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Pub Date : 2025-01-09DOI: 10.1016/j.chempr.2024.08.017
Xin Chang , Zhenpu Lu , Ran Luo , Xianhui Wang , Guodong Sun , Donglong Fu , Zhi-Jian Zhao , Jinlong Gong
Although non-noble metal catalysts are appealing for propane dehydrogenation, achieving high propylene selectivity remains a persistent challenge, which necessitates the regulation of catalytic microenvironment. In this study, we comparatively investigate three commonly used active metals (Pt, Pd, and non-noble metal Ni) using both theoretical and experimental approaches. We find that the low selectivity of Ni-based catalysts is intrinsically attributed to a narrow interatomic distance (Δd) between Ni atoms, which promotes side reactions. Thus, Ni-based intermetallic alloys are employed to modulate Δd, whose surface microenvironment is quantified with a descriptor called degree-of-isolation. The established volcano-shaped isolation-selectivity plot provides a direct avenue for predicting propylene selectivity, which is determined by two competing variables: desorption and further dehydrogenation of propylene. The optimal catalyst, NiIn, manifests moderate Ni–C repulsion, obtaining >91% experimental propylene selectivity. This reveals the Sabatier principle over Ni-based catalysts for selective propane dehydrogenation and underscores the significance of microenvironment engineering.
尽管非贵金属催化剂在丙烷脱氢中很有吸引力，但实现高丙烯选择性仍是一个长期挑战，这就需要对催化微环境进行调节。在本研究中，我们采用理论和实验方法对三种常用活性金属（铂、钯和非贵金属镍）进行了比较研究。我们发现，镍基催化剂选择性低的内在原因是镍原子间的原子间距（Δd）较窄，这会促进副反应。因此，我们采用镍基金属间合金来调节 Δd，其表面微环境可通过一种称为隔离度的描述符来量化。已建立的火山状分离选择性曲线图为预测丙烯选择性提供了直接途径，丙烯选择性由两个竞争变量决定：丙烯的解吸和进一步脱氢。最佳催化剂 NiIn 表现出适度的 Ni-C 排斥，获得了 91% 的实验丙烯选择性。这揭示了用于选择性丙烷脱氢的镍基催化剂的萨巴蒂尔原理，并强调了微环境工程的重要性。
{"title":"Microenvironment engineering of non-noble metal alloy for selective propane dehydrogenation","authors":"Xin Chang , Zhenpu Lu , Ran Luo , Xianhui Wang , Guodong Sun , Donglong Fu , Zhi-Jian Zhao , Jinlong Gong","doi":"10.1016/j.chempr.2024.08.017","DOIUrl":"10.1016/j.chempr.2024.08.017","url":null,"abstract":"<div><div>Although non-noble metal catalysts are appealing for propane dehydrogenation, achieving high propylene selectivity remains a persistent challenge, which necessitates the regulation of catalytic microenvironment. In this study, we comparatively investigate three commonly used active metals (Pt, Pd, and non-noble metal Ni) using both theoretical and experimental approaches. We find that the low selectivity of Ni-based catalysts is intrinsically attributed to a narrow interatomic distance (Δ<em>d</em>) between Ni atoms, which promotes side reactions. Thus, Ni-based intermetallic alloys are employed to modulate Δ<em>d</em>, whose surface microenvironment is quantified with a descriptor called degree-of-isolation. The established volcano-shaped isolation-selectivity plot provides a direct avenue for predicting propylene selectivity, which is determined by two competing variables: desorption and further dehydrogenation of propylene. The optimal catalyst, NiIn, manifests moderate Ni–C repulsion, obtaining >91% experimental propylene selectivity. This reveals the Sabatier principle over Ni-based catalysts for selective propane dehydrogenation and underscores the significance of microenvironment engineering.</div></div>","PeriodicalId":268,"journal":{"name":"Chem","volume":"11 1","pages":"Article 102294"},"PeriodicalIF":19.1,"publicationDate":"2025-01-09","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142235468","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Pub Date : 2025-01-09DOI: 10.1016/j.chempr.2024.07.017
Zhongtao Feng , Rei Kinjo
Coulomb repulsion in multiply charged ions (MCIs) is mitigated by long-range electrostatic interaction with the distant charge separation and delocalized systems. Meanwhile, MCIs featuring the charged centers located at two directly connected atoms (E+/−–E+/−) bear a strong repulsive force, which leads to electron detachment or molecular fragmentation, namely, Coulomb explosion. Here, we describe the synthesis of a trianionic triangular triboron species (B3R63−) through the reductive dealumination from a Cp∗AlB3R6 anion (Cp∗, 1,2,3,4,5-pentamethylcyclopentadienyl). X-ray crystallographic and spectroscopic analyses with the aid of quantum chemical calculations reveal that despite the triply negatively charged skeleton, the B3 core is tightly held by electron-precise B–B bonds, overcoming Coulomb repulsion. In contrast to the extant electron-deficient triborate rings, this molecule exhibits reducing ability and nucleophilicity; thus, it undergoes not only electron transfer but also cyclization and salt metathesis reactions, demonstrating its trait as elusive (R2B−) and ([R2B]22−) surrogates.
多电荷离子（MCIs）中的库仑斥力可通过与远距离电荷分离和脱局域系统的长程静电相互作用得到缓解。同时，带电中心位于两个直接相连原子（E+/--E+/-）的多电荷离子（MCIs）会产生强大的斥力，导致电子脱离或分子破碎，即库仑爆炸。在这里，我们介绍了通过还原脱铝法从 Cp∗AlB3R6 阴离子（Cp∗，1,2,3,4,5-五甲基环戊二烯）合成三阴离子三角三硼化物（B3R63-）的过程。借助量子化学计算进行的 X 射线晶体学和光谱分析显示，尽管 B3 核心的骨架带三重负电荷，但它被电子精确的 B-B 键紧紧固定，克服了库仑排斥。与现存的缺电子三硼酸环不同，这种分子具有还原能力和亲核性；因此，它不仅能进行电子转移反应，还能进行环化反应和盐代合成反应，显示了其作为难以捉摸的（R2B-）和（[R2B]22-）代用品的特性。
{"title":"A crystalline trianionic triangular triboron species","authors":"Zhongtao Feng , Rei Kinjo","doi":"10.1016/j.chempr.2024.07.017","DOIUrl":"10.1016/j.chempr.2024.07.017","url":null,"abstract":"<div><div>Coulomb repulsion in multiply charged ions (MCIs) is mitigated by long-range electrostatic interaction with the distant charge separation and delocalized systems. Meanwhile, MCIs featuring the charged centers located at two directly connected atoms (E<sup>+/−</sup>–E<sup>+/−</sup>) bear a strong repulsive force, which leads to electron detachment or molecular fragmentation, namely, Coulomb explosion. Here, we describe the synthesis of a trianionic triangular triboron species (B<sub>3</sub>R<sub>6</sub><sup>3−</sup>) through the reductive dealumination from a Cp∗AlB<sub>3</sub>R<sub>6</sub> anion (Cp∗, 1,2,3,4,5-pentamethylcyclopentadienyl). X-ray crystallographic and spectroscopic analyses with the aid of quantum chemical calculations reveal that despite the triply negatively charged skeleton, the B<sub>3</sub> core is tightly held by electron-precise B–B bonds, overcoming Coulomb repulsion. In contrast to the extant electron-deficient triborate rings, this molecule exhibits reducing ability and nucleophilicity; thus, it undergoes not only electron transfer but also cyclization and salt metathesis reactions, demonstrating its trait as elusive (R<sub>2</sub>B<sup>−</sup>) and ([R<sub>2</sub>B]<sub>2</sub><sup>2−</sup>) surrogates.</div></div>","PeriodicalId":268,"journal":{"name":"Chem","volume":"11 1","pages":"Article 102255"},"PeriodicalIF":19.1,"publicationDate":"2025-01-09","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142023142","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Pub Date : 2025-01-09DOI: 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.
{"title":"Electrocatalytic grafting of polyvinyl chloride plastics","authors":"Jordan L.S. Zackasee , Valmuri Srivardhan , Blaise L. Truesdell , Elizabeth J. Vrana , 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}
Pub Date : 2025-01-09DOI: 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.
{"title":"In-depth understanding and precise modulation of surface reconstruction during heterogeneous electrocatalysis: From model to practical catalyst","authors":"Weidong Dai , Kaiwei Wan , Kanglei Pang , Jun Guo , Siyuan Liu , Keying Wu , Chiyao Tang , Yanjuan Sun , Xinghua Shi , Zhiyong Tang , Chang Long , 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}
Pub Date : 2025-01-09DOI: 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.
{"title":"Guest binding is governed by multiple stimuli in low-symmetry metal-organic cages containing bis-pyridyl(imine) vertices","authors":"Yuchong Yang , Tanya K. Ronson , Paula C.P. Teeuwen , Yuyin Du , Jieyu Zheng , David J. Wales , 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}
Pub Date : 2025-01-09DOI: 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).
{"title":"Bridging gaps between lab- and fab-oriented anode design for proton exchange membrane water electrolyzers","authors":"Jun Xu , Yuting Yang , Huanyu Jin , Yao Zheng , 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}
Pub Date : 2025-01-09DOI: 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 , Osama Shekhah , Osman M. Bakr , Mohamed Eddaoudi , 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}
Pub Date : 2025-01-09DOI: 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.
{"title":"The cyclotriborate trianion","authors":"Manjur O. Akram , 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}
Pub Date : 2025-01-08DOI: 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.
{"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}
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