Pub Date : 2025-02-07DOI: 10.1016/j.chempr.2024.102409
Joshua Krehan, Chuen-Ru Li, Marcos Masukawa, Esther Amstad, Andreas Walther
Prototissues made from artificial cells (ACs) aim to replicate the behaviors of living tissues, such as communication, collective behavior, and homeostasis. Despite progress in developing diverse AC types, building prototissues and achieving effective communication as well as collective behavior in such prototissues remain challenging. We introduce ACs with an intrinsic homeostatic pH control mechanism that can be organized into prototissues to collectively maintain a stable microenvironment and protect cargo from environmental pH fluctuations. These ACs contain pH-modulating enzymes within a pH-sensitive membrane, allowing for self-regulation through chemo-structural feedback. They adjust pH by importing substrates within a specific pH range and self-regulate to control substrate influx. This enables them to modulate local pH, manage cargo release, and facilitate interactive communication in organized spheroids. Our findings demonstrate the potential of homeostatic ACs to create advanced synthetic tissue mimics, replicating protective and communicative functions of living tissues for biomedical and tissue engineering applications.
{"title":"Homeostatic artificial cells enable self-protection in prototissue spheroids","authors":"Joshua Krehan, Chuen-Ru Li, Marcos Masukawa, Esther Amstad, Andreas Walther","doi":"10.1016/j.chempr.2024.102409","DOIUrl":"https://doi.org/10.1016/j.chempr.2024.102409","url":null,"abstract":"Prototissues made from artificial cells (ACs) aim to replicate the behaviors of living tissues, such as communication, collective behavior, and homeostasis. Despite progress in developing diverse AC types, building prototissues and achieving effective communication as well as collective behavior in such prototissues remain challenging. We introduce ACs with an intrinsic homeostatic pH control mechanism that can be organized into prototissues to collectively maintain a stable microenvironment and protect cargo from environmental pH fluctuations. These ACs contain pH-modulating enzymes within a pH-sensitive membrane, allowing for self-regulation through chemo-structural feedback. They adjust pH by importing substrates within a specific pH range and self-regulate to control substrate influx. This enables them to modulate local pH, manage cargo release, and facilitate interactive communication in organized spheroids. Our findings demonstrate the potential of homeostatic ACs to create advanced synthetic tissue mimics, replicating protective and communicative functions of living tissues for biomedical and tissue engineering applications.","PeriodicalId":268,"journal":{"name":"Chem","volume":"13 1","pages":""},"PeriodicalIF":23.5,"publicationDate":"2025-02-07","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143258282","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 : 2025-02-07DOI: 10.1016/j.chempr.2024.102402
Yeji Lee, Hyerin Woo, Jieun Kang, Soomin Hwang, Soojin Park, Sarah S. Park
Dual-ion batteries (DIBs) are promising for efficient energy storage, yet they encounter challenges in cycling stability due to solvent co-intercalation and electrolyte decomposition at high voltages during anion intercalation. Herein, we propose integrating metal-organic frameworks (MOFs) with intertwined zwitterionic polymers as a quasi-solid-state electrolyte (QSSE). This design exploits the synergistic effect of the mesoporous structure of MOFs and zwitterionic polymers synthesized within the pores, thereby enhancing ion transport kinetics and weakening solvent-ion interactions. The PVIPS@MIL-101 QSSE exhibits an improved ionic conductivity of 0.902 mS cm−1 at 25°C and wide electrochemical stability up to ∼5.1 V vs. Li/Li+. Notably, the DIBs with PVIPS@MIL-101 QSSE demonstrate impressive high-rate capabilities and extended cycle life without additives, retaining 93.3% capacity after 4,000 cycles at 10 C, surpassing conventional battery systems.
{"title":"Zwitterionic polymer intertwined metal-organic framework-based quasi-solid-state electrolyte for long cycle life dual-ion batteries","authors":"Yeji Lee, Hyerin Woo, Jieun Kang, Soomin Hwang, Soojin Park, Sarah S. Park","doi":"10.1016/j.chempr.2024.102402","DOIUrl":"https://doi.org/10.1016/j.chempr.2024.102402","url":null,"abstract":"Dual-ion batteries (DIBs) are promising for efficient energy storage, yet they encounter challenges in cycling stability due to solvent co-intercalation and electrolyte decomposition at high voltages during anion intercalation. Herein, we propose integrating metal-organic frameworks (MOFs) with intertwined zwitterionic polymers as a quasi-solid-state electrolyte (QSSE). This design exploits the synergistic effect of the mesoporous structure of MOFs and zwitterionic polymers synthesized within the pores, thereby enhancing ion transport kinetics and weakening solvent-ion interactions. The PVIPS@MIL-101 QSSE exhibits an improved ionic conductivity of 0.902 mS cm<sup>−1</sup> at 25°C and wide electrochemical stability up to ∼5.1 V vs. Li/Li<sup>+</sup>. Notably, the DIBs with PVIPS@MIL-101 QSSE demonstrate impressive high-rate capabilities and extended cycle life without additives, retaining 93.3% capacity after 4,000 cycles at 10 C, surpassing conventional battery systems.","PeriodicalId":268,"journal":{"name":"Chem","volume":"28 1","pages":""},"PeriodicalIF":23.5,"publicationDate":"2025-02-07","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143258283","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 : 2025-02-06DOI: 10.1016/j.chempr.2024.102398
Wenqiang Zhang, Yuting Zhang, Weili Ma, Xing Han, Wei Gong, Yan Liu, Yong Cui
Covalent organic frameworks (COFs) and metal-organic frameworks (MOFs) are sought for their tunable porous structures and potential utility. Whereas the coordination bonds in MOFs enable the generation of single crystals, facilitating insight into structure-function relationships, this is not typically the case for COFs. Here, we present a simple and rapid synthetic method that exploits coordination-directed imine formation to prepare families of highly crystalline porous materials that are MOF-COF (MOCOF) hybrids. This synthetic approach consistently provides 14 high-quality single crystals formed using various combinations of imine (COF) and N-donor linker ligand (MOF) within 1 to 2 days, with sizes ranging from 50 to 500 μm, allowing determination of the single-crystal X-ray structures. These crystal structures provide insight into architectures, structural evolution, and host-guest interactions (including chirality recognition) with atomic resolution. Moreover, these MOCOF hybrids can be deconstructed through linker ligand removal and exfoliated to form ultrathin COF nanosheets.
{"title":"Coordination-templated construction of single-crystal covalent organic frameworks","authors":"Wenqiang Zhang, Yuting Zhang, Weili Ma, Xing Han, Wei Gong, Yan Liu, Yong Cui","doi":"10.1016/j.chempr.2024.102398","DOIUrl":"https://doi.org/10.1016/j.chempr.2024.102398","url":null,"abstract":"Covalent organic frameworks (COFs) and metal-organic frameworks (MOFs) are sought for their tunable porous structures and potential utility. Whereas the coordination bonds in MOFs enable the generation of single crystals, facilitating insight into structure-function relationships, this is not typically the case for COFs. Here, we present a simple and rapid synthetic method that exploits coordination-directed imine formation to prepare families of highly crystalline porous materials that are MOF-COF (MOCOF) hybrids. This synthetic approach consistently provides 14 high-quality single crystals formed using various combinations of imine (COF) and N-donor linker ligand (MOF) within 1 to 2 days, with sizes ranging from 50 to 500 μm, allowing determination of the single-crystal X-ray structures. These crystal structures provide insight into architectures, structural evolution, and host-guest interactions (including chirality recognition) with atomic resolution. Moreover, these MOCOF hybrids can be deconstructed through linker ligand removal and exfoliated to form ultrathin COF nanosheets.","PeriodicalId":268,"journal":{"name":"Chem","volume":"26 1","pages":""},"PeriodicalIF":23.5,"publicationDate":"2025-02-06","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143192478","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 : 2025-02-06DOI: 10.1016/j.chempr.2024.102399
Christine M.E. Kriebisch, Olga Bantysh, Lorena Baranda Pellejero, Andrea Belluati, Eva Bertosin, Kun Dai, Maria de Roy, Hailin Fu, Nicola Galvanetto, Julianne M. Gibbs, Samuel Santhosh Gomez, Gaetano Granatelli, Alessandra Griffo, Maria Guix, Cenk Onur Gurdap, Johannes Harth-Kitzerow, Ivar S. Haugerud, Gregor Häfner, Pranay Jaiswal, Sadaf Javed, Job Boekhoven
The synthesis of life from non-living matter has captivated and divided scientists for centuries. This bold goal aims at unraveling the fundamental principles of life and leveraging its unique features, such as its resilience, sustainability, and ability to evolve. Synthetic life represents more than an academic milestone—it has the potential to revolutionize biotechnology, medicine, and materials science. Although the fields of synthetic biology, systems chemistry, and biophysics have made great strides toward synthetic life, progress has been hindered by social, philosophical, and technical challenges, such as vague goals, misaligned interdisciplinary efforts, and incompletely addressing public and ethical concerns. Our perspective offers a roadmap toward the synthesis of life based on discussions during a 2-week workshop with scientists from around the globe.
{"title":"A roadmap toward the synthesis of life","authors":"Christine M.E. Kriebisch, Olga Bantysh, Lorena Baranda Pellejero, Andrea Belluati, Eva Bertosin, Kun Dai, Maria de Roy, Hailin Fu, Nicola Galvanetto, Julianne M. Gibbs, Samuel Santhosh Gomez, Gaetano Granatelli, Alessandra Griffo, Maria Guix, Cenk Onur Gurdap, Johannes Harth-Kitzerow, Ivar S. Haugerud, Gregor Häfner, Pranay Jaiswal, Sadaf Javed, Job Boekhoven","doi":"10.1016/j.chempr.2024.102399","DOIUrl":"https://doi.org/10.1016/j.chempr.2024.102399","url":null,"abstract":"The synthesis of life from non-living matter has captivated and divided scientists for centuries. This bold goal aims at unraveling the fundamental principles of life and leveraging its unique features, such as its resilience, sustainability, and ability to evolve. Synthetic life represents more than an academic milestone—it has the potential to revolutionize biotechnology, medicine, and materials science. Although the fields of synthetic biology, systems chemistry, and biophysics have made great strides toward synthetic life, progress has been hindered by social, philosophical, and technical challenges, such as vague goals, misaligned interdisciplinary efforts, and incompletely addressing public and ethical concerns. Our perspective offers a roadmap toward the synthesis of life based on discussions during a 2-week workshop with scientists from around the globe.","PeriodicalId":268,"journal":{"name":"Chem","volume":"11 1","pages":""},"PeriodicalIF":23.5,"publicationDate":"2025-02-06","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143192477","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 : 2025-02-05DOI: 10.1016/j.chempr.2024.102401
Wentao Wu, Shuyi Lin, Jian-Xin Wang, Yafeng Xu, Tengyue He, Yang Zhou, Peng Yuan, Partha Maity, Issatay Nadinov, Simil Thomas, Renwu Huang, Catherine S.P. De Castro, Jun Yin, Husam N. Alshareef, Osman M. Bakr, Omar F. Mohammed
Cu(I) halide-based scintillators are emerging as eco-friendly alternatives to traditional X-ray imaging scintillators because of their high luminescence efficiency and solution processability. Although much progress has been made in zero-dimensional (0D) Cu–I cluster scintillators, there has been limited focus on one-dimensional (1D) Cu–I coordination polymers because of their lower luminescence efficiencies. This study presents a ligand halogen engineering strategy for significantly enhancing the photoluminescence efficiency of 1D Cu–I coordination polymers by utilizing halogen-based chemical modifications. The chlorine-modified ligands increase structural rigidity, reducing electronic repulsion between copper and iodine atoms and minimizing photon loss through non-radiative recombination pathways, resulting in an impressive photoluminescence quantum yield of nearly 100%. The designed scintillators demonstrate improved radioluminescence intensity, low detection limits, and exceptional spatial resolution (16 lp/mm). This research offers an approach for creating highly emissive 1D Cu–I coordination polymers and highlights their potential in X-ray imaging applications in medical diagnosis and security checks.
{"title":"Enhanced X-ray luminescence in one-dimensional Cu–I coordination polymers via ligand halogen engineering","authors":"Wentao Wu, Shuyi Lin, Jian-Xin Wang, Yafeng Xu, Tengyue He, Yang Zhou, Peng Yuan, Partha Maity, Issatay Nadinov, Simil Thomas, Renwu Huang, Catherine S.P. De Castro, Jun Yin, Husam N. Alshareef, Osman M. Bakr, Omar F. Mohammed","doi":"10.1016/j.chempr.2024.102401","DOIUrl":"https://doi.org/10.1016/j.chempr.2024.102401","url":null,"abstract":"Cu(I) halide-based scintillators are emerging as eco-friendly alternatives to traditional X-ray imaging scintillators because of their high luminescence efficiency and solution processability. Although much progress has been made in zero-dimensional (0D) Cu–I cluster scintillators, there has been limited focus on one-dimensional (1D) Cu–I coordination polymers because of their lower luminescence efficiencies. This study presents a ligand halogen engineering strategy for significantly enhancing the photoluminescence efficiency of 1D Cu–I coordination polymers by utilizing halogen-based chemical modifications. The chlorine-modified ligands increase structural rigidity, reducing electronic repulsion between copper and iodine atoms and minimizing photon loss through non-radiative recombination pathways, resulting in an impressive photoluminescence quantum yield of nearly 100%. The designed scintillators demonstrate improved radioluminescence intensity, low detection limits, and exceptional spatial resolution (16 lp/mm). This research offers an approach for creating highly emissive 1D Cu–I coordination polymers and highlights their potential in X-ray imaging applications in medical diagnosis and security checks.","PeriodicalId":268,"journal":{"name":"Chem","volume":"28 1","pages":""},"PeriodicalIF":23.5,"publicationDate":"2025-02-05","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143124916","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}
Targeted protein degradation (TPD) technologies leveraging the ubiquitin-proteasome system address “undruggable” proteins but struggle with optimizing targeting warheads and linkers. This study introduces a systematic platform for creating aptamer-based TPD molecules on demand. We developed a microbead-displayed oligonucleotide-E3 ligand chimera library and applied in vitro ubiquitination systems by using a fluorescent assay with bead sorting to identify high-affinity aptamer-chimera degraders that bind to target proteins and recruit E3 ligase for ubiquitination. This approach, tested with CRBN and VHL E3 ligases, successfully degraded BRD4 and IRAK4 proteins. Additionally, we evolved a bispecific RNA aptamer degrader, demonstrating the versatility of our platform. The selected aptamer chimeras achieved degradation rates of up to 87% for BRD4. Functional assays showed effective inhibition of cancer cell proliferation, induction of apoptosis, and significant tumor growth suppression in a subcutaneous tumor model. These findings highlight the potential of aptamer-based TPD technologies as powerful tools for cancer treatment.
{"title":"Systematic evolution of functional oligonucleotides for targeted protein degradation","authors":"Huang Su, Yifan Chen, Xuyang Zhao, Zengyi Lu, Tongxuan Wei, Qinguo Liu, Xiyang Liu, Qinhao Zhang, Siqi Bian, Qianwei Qiu, Panzhu Yao, Wenlang Liu, Zheng Zheng, Da Xu, Liqin Zhang","doi":"10.1016/j.chempr.2024.102408","DOIUrl":"https://doi.org/10.1016/j.chempr.2024.102408","url":null,"abstract":"Targeted protein degradation (TPD) technologies leveraging the ubiquitin-proteasome system address “undruggable” proteins but struggle with optimizing targeting warheads and linkers. This study introduces a systematic platform for creating aptamer-based TPD molecules on demand. We developed a microbead-displayed oligonucleotide-E3 ligand chimera library and applied <em>in vitro</em> ubiquitination systems by using a fluorescent assay with bead sorting to identify high-affinity aptamer-chimera degraders that bind to target proteins and recruit E3 ligase for ubiquitination. This approach, tested with CRBN and VHL E3 ligases, successfully degraded BRD4 and IRAK4 proteins. Additionally, we evolved a bispecific RNA aptamer degrader, demonstrating the versatility of our platform. The selected aptamer chimeras achieved degradation rates of up to 87% for BRD4. Functional assays showed effective inhibition of cancer cell proliferation, induction of apoptosis, and significant tumor growth suppression in a subcutaneous tumor model. These findings highlight the potential of aptamer-based TPD technologies as powerful tools for cancer treatment.","PeriodicalId":268,"journal":{"name":"Chem","volume":"40 1","pages":""},"PeriodicalIF":23.5,"publicationDate":"2025-02-04","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143083605","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 : 2025-02-04DOI: 10.1016/j.chempr.2024.102396
Andreas Bonde, Joakim Bøgelund Jakobsen, Alexander Ahrens, Weiheng Huang, Ralf Jackstell, Matthias Beller, Troels Skrydstrup
Commodity chemical production is heavily dependent on fossil feedstocks. Transitioning to renewable resources is a pressing necessity, with green methanol being a promising candidate for rethinking chemical platforms. Here, we report how interlocking methanol-to-syngas reforming and hydroformylation of olefins may integrate methanol as a platform for accessing renewable oxo-products. This study demonstrates the importance of interlocking kinetics and selectivity of a ruthenium-catalyzed acceptorless dehydrogenation and a rhodium-catalyzed hydroformylation. Notably, coal- or natural gas-derived syngas can be substituted with fuel-grade e-methanol obtained from captured CO2 and green hydrogen. Although these conditions do not replicate large-scale industrial settings, we consider this dual-catalysis approach a proof of concept illustrating the potential to synthesize oxo-products entirely from CO2-derived methanol. We envision that redesigning chemical value chains to extend from renewable platforms like methanol could play a pivotal role toward establishing a more sustainable chemical industry.
{"title":"Integrating hydroformylations with methanol-to-syngas reforming","authors":"Andreas Bonde, Joakim Bøgelund Jakobsen, Alexander Ahrens, Weiheng Huang, Ralf Jackstell, Matthias Beller, Troels Skrydstrup","doi":"10.1016/j.chempr.2024.102396","DOIUrl":"https://doi.org/10.1016/j.chempr.2024.102396","url":null,"abstract":"Commodity chemical production is heavily dependent on fossil feedstocks. Transitioning to renewable resources is a pressing necessity, with green methanol being a promising candidate for rethinking chemical platforms. Here, we report how interlocking methanol-to-syngas reforming and hydroformylation of olefins may integrate methanol as a platform for accessing renewable oxo-products. This study demonstrates the importance of interlocking kinetics and selectivity of a ruthenium-catalyzed acceptorless dehydrogenation and a rhodium-catalyzed hydroformylation. Notably, coal- or natural gas-derived syngas can be substituted with fuel-grade e-methanol obtained from captured CO<sub>2</sub> and green hydrogen. Although these conditions do not replicate large-scale industrial settings, we consider this dual-catalysis approach a proof of concept illustrating the potential to synthesize oxo-products entirely from CO<sub>2</sub>-derived methanol. We envision that redesigning chemical value chains to extend from renewable platforms like methanol could play a pivotal role toward establishing a more sustainable chemical industry.","PeriodicalId":268,"journal":{"name":"Chem","volume":"47 1","pages":""},"PeriodicalIF":23.5,"publicationDate":"2025-02-04","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143083606","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 : 2025-01-30DOI: 10.1016/j.chempr.2024.102395
Yi Lu, Florian Bourdeaux, Binbin Nian, Pirathiha Manimaran, Bhupesh Verma, Max Rommerskirchen, Sebastian Bold, Leilei Zhu, Yu Ji, Johannes Henrich Schleifenbaum, Ulrich Schwaneberg
Biocatalysis in stainless steel flow reactors is limited by inefficient enzyme immobilization on stainless steel surfaces. Herein, we report a universal and generally applicable strategy to achieve efficient enzyme immobilization in stainless steel flow reactors by utilizing an engineered material-binding peptide (MBP) with improved binding toward stainless steel. Through this method, phytase from Yersinia mollaretii (YmPh) was immobilized and showed high activity in hydrolyzing phytic acid to produce phosphate over multiple cycles. The MBP liquid chromatography peak I (LCI) was selected and engineered for improved stainless steel binding. The variant LCISS4 (LCI A14K/Y30R/D45R) showed an 8.2-fold improved binding to stainless steel compared with the LCI wild type. YmPh-LCISS4 immobilized in additively manufactured stainless steel flow reactors exhibited strong washing resistance and high reusability. The immobilization strategy presented here, based on LCISS4, enables robust and oriented enzyme immobilization on stainless steel, making it an appealing tool for industrial biocatalysis.
{"title":"Engineered material-binding peptide empowers biocatalysis in stainless steel flow reactors for phosphate recovery","authors":"Yi Lu, Florian Bourdeaux, Binbin Nian, Pirathiha Manimaran, Bhupesh Verma, Max Rommerskirchen, Sebastian Bold, Leilei Zhu, Yu Ji, Johannes Henrich Schleifenbaum, Ulrich Schwaneberg","doi":"10.1016/j.chempr.2024.102395","DOIUrl":"https://doi.org/10.1016/j.chempr.2024.102395","url":null,"abstract":"Biocatalysis in stainless steel flow reactors is limited by inefficient enzyme immobilization on stainless steel surfaces. Herein, we report a universal and generally applicable strategy to achieve efficient enzyme immobilization in stainless steel flow reactors by utilizing an engineered material-binding peptide (MBP) with improved binding toward stainless steel. Through this method, phytase from <em>Yersinia mollaretii</em> (YmPh) was immobilized and showed high activity in hydrolyzing phytic acid to produce phosphate over multiple cycles. The MBP liquid chromatography peak I (LCI) was selected and engineered for improved stainless steel binding. The variant LCI<sub>SS</sub>4 (LCI A14K/Y30R/D45R) showed an 8.2-fold improved binding to stainless steel compared with the LCI wild type. YmPh-LCI<sub>SS</sub>4 immobilized in additively manufactured stainless steel flow reactors exhibited strong washing resistance and high reusability. The immobilization strategy presented here, based on LCI<sub>SS</sub>4, enables robust and oriented enzyme immobilization on stainless steel, making it an appealing tool for industrial biocatalysis.","PeriodicalId":268,"journal":{"name":"Chem","volume":"23 1","pages":""},"PeriodicalIF":23.5,"publicationDate":"2025-01-30","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143057302","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 : 2025-01-29DOI: 10.1016/j.chempr.2024.102392
Dongmin Wang, Wang Chen, Rong Sun, Jun-Liang Liu, Bingwu Wang, Shengfa Ye, Gengwen Tan, Song Gao
Telluryl radicals are elusive species that have been characterized spectroscopically in the gas phase or under matrix isolation conditions. In this study, we present the synthesis, structural, and spectroscopic characterization of a stable telluryl radical supported by a sterically congested hydrindacene ligand. Structural characterization unveiled that it bears a one-coordinate tellurium atom. Electron paramagnetic resonance spectroscopy coupled with wavefunction-based ab initio calculations substantiated that it possesses an orbitally doubly degenerate ground state and thereby strong magnetic anisotropy as manifested by the large difference of its three g components. Consequently, this telluryl radical exhibits a field-induced slow magnetic relaxation behavior, which is unprecedented for purely main-group radicals. This work not only provides structural and spectroscopic information on a long-sought-after telluryl radical, but also demonstrates the potential application of main-group radicals as a new class of magnetic materials.
{"title":"Synthesis and magnetic property of a telluryl radical","authors":"Dongmin Wang, Wang Chen, Rong Sun, Jun-Liang Liu, Bingwu Wang, Shengfa Ye, Gengwen Tan, Song Gao","doi":"10.1016/j.chempr.2024.102392","DOIUrl":"https://doi.org/10.1016/j.chempr.2024.102392","url":null,"abstract":"Telluryl radicals are elusive species that have been characterized spectroscopically in the gas phase or under matrix isolation conditions. In this study, we present the synthesis, structural, and spectroscopic characterization of a stable telluryl radical supported by a sterically congested hydrindacene ligand. Structural characterization unveiled that it bears a one-coordinate tellurium atom. Electron paramagnetic resonance spectroscopy coupled with wavefunction-based <em>ab initio</em> calculations substantiated that it possesses an orbitally doubly degenerate ground state and thereby strong magnetic anisotropy as manifested by the large difference of its three <em>g</em> components. Consequently, this telluryl radical exhibits a field-induced slow magnetic relaxation behavior, which is unprecedented for purely main-group radicals. This work not only provides structural and spectroscopic information on a long-sought-after telluryl radical, but also demonstrates the potential application of main-group radicals as a new class of magnetic materials.","PeriodicalId":268,"journal":{"name":"Chem","volume":"120 1","pages":""},"PeriodicalIF":23.5,"publicationDate":"2025-01-29","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143055273","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 : 2025-01-29DOI: 10.1016/j.chempr.2024.102393
Yingjun Sun, Zhengyi Qian, Mingzi Sun, Yingjie Li, Qinghua Zhang, Yan Nie, Lin Gu, Mingchuan Luo, Jianguo Liu, Bolong Huang, Shaojun Guo
Electrocatalytic hydrogen peroxide (H2O2) production from O2 reduction is attractive because of its wide applications; however, the lack of efficient and selective electrocatalysts hinders its further development. Herein, we have created a class of electrocatalysts by anchoring osmium (Os) single atomic sites on ultrathin copper sulfide nanoplates (Os1-CuS NPs) to greatly boost the electroreduction of O2 into H2O2 via a two-electron pathway. The Os single-atomic-site catalyst with sulfur coordination achieved a record-high Os loading (25.9 wt %) and an exceptional H2O2 production rate (8.2 mol gcat−1 h−1) with near-perfect selectivity (∼98%), making it a top performer among metal-based electrocatalysts. In situ attenuated total reflectance surface-enhanced infrared absorption spectroscopy (ATR-SEIRAS) and density functional theory (DFT) calculations revealed that the introduced Os sites promote a selective 2e− oxygen reduction pathway by strengthening OOH binding and thus suppressing the undesired 4e− pathway. This study advances the design of high-performance single-atomic-site electrocatalysts for selective H2O2 generation.
{"title":"Osmium atomic sites on CuS nanoplates for efficient two-electron oxygen reduction into H2O2","authors":"Yingjun Sun, Zhengyi Qian, Mingzi Sun, Yingjie Li, Qinghua Zhang, Yan Nie, Lin Gu, Mingchuan Luo, Jianguo Liu, Bolong Huang, Shaojun Guo","doi":"10.1016/j.chempr.2024.102393","DOIUrl":"https://doi.org/10.1016/j.chempr.2024.102393","url":null,"abstract":"Electrocatalytic hydrogen peroxide (H<sub>2</sub>O<sub>2</sub>) production from O<sub>2</sub> reduction is attractive because of its wide applications; however, the lack of efficient and selective electrocatalysts hinders its further development. Herein, we have created a class of electrocatalysts by anchoring osmium (Os) single atomic sites on ultrathin copper sulfide nanoplates (Os<sub>1</sub>-CuS NPs) to greatly boost the electroreduction of O<sub>2</sub> into H<sub>2</sub>O<sub>2</sub> via a two-electron pathway. The Os single-atomic-site catalyst with sulfur coordination achieved a record-high Os loading (25.9 wt %) and an exceptional H<sub>2</sub>O<sub>2</sub> production rate (8.2 mol g<sub>cat</sub><sup>−1</sup> h<sup>−1</sup>) with near-perfect selectivity (∼98%), making it a top performer among metal-based electrocatalysts. <em>In situ</em> attenuated total reflectance surface-enhanced infrared absorption spectroscopy (ATR-SEIRAS) and density functional theory (DFT) calculations revealed that the introduced Os sites promote a selective 2e<sup>−</sup> oxygen reduction pathway by strengthening OOH binding and thus suppressing the undesired 4e<sup>−</sup> pathway. This study advances the design of high-performance single-atomic-site electrocatalysts for selective H<sub>2</sub>O<sub>2</sub> generation.","PeriodicalId":268,"journal":{"name":"Chem","volume":"59 1","pages":""},"PeriodicalIF":23.5,"publicationDate":"2025-01-29","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143055272","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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