Min Fey Chek, Sun-Yong Kim, Tomoyuki Mori, Keiji Matsumoto, Shunsuke Sato, Toshio Hakoshima
Polyhydroxyalkanoate (PHA) is a biodegradable polyester that can serve as a promising alternative to petrochemical plastics which present a serious source of pollution. PHA synthase (PhaC) is a key enzyme responsible for producing a wide variety of PHAs in microorganisms. Here we present crystal structures of full-length PhaC from Aeromonas caviae, a high-performance PhaC employed for industrial use. The structure reveals an N-terminal helical domain that mediates head-to-head dimerization and stabilizes the C-terminal α/β catalytic domain to form a tunnel that connects the catalytic center embedded inside the protein to the protein surface. We showed that this tunnel is a putative egress tunnel for the product PHA chain. Our results establish a fundamental understanding of the PhaC machinery that should lead to improvement of this enzyme in industrial applications.
{"title":"Structures of Polyhydroxyalkanoate Synthase PhaC from Aeromonas caviae, Producing Biodegradable Plastics","authors":"Min Fey Chek, Sun-Yong Kim, Tomoyuki Mori, Keiji Matsumoto, Shunsuke Sato, Toshio Hakoshima","doi":"10.1002/anie.202504626","DOIUrl":"https://doi.org/10.1002/anie.202504626","url":null,"abstract":"Polyhydroxyalkanoate (PHA) is a biodegradable polyester that can serve as a promising alternative to petrochemical plastics which present a serious source of pollution. PHA synthase (PhaC) is a key enzyme responsible for producing a wide variety of PHAs in microorganisms. Here we present crystal structures of full-length PhaC from Aeromonas caviae, a high-performance PhaC employed for industrial use. The structure reveals an N-terminal helical domain that mediates head-to-head dimerization and stabilizes the C-terminal α/β catalytic domain to form a tunnel that connects the catalytic center embedded inside the protein to the protein surface. We showed that this tunnel is a putative egress tunnel for the product PHA chain. Our results establish a fundamental understanding of the PhaC machinery that should lead to improvement of this enzyme in industrial applications.","PeriodicalId":125,"journal":{"name":"Angewandte Chemie International Edition","volume":"73 1","pages":""},"PeriodicalIF":16.6,"publicationDate":"2025-04-25","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143872495","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}
Jingyi Zhou, Chen Chen, Jinchi Sun, Thomas R. Fielitz, Weijun Zhou, David G. Cahill, Paul V. Braun
This study provides a rich database of structure–property relationships that will help guide future work in designing polymers with low intrinsic thermal conductivity. Fluorinated polymers are widely utilized in industry for their outstanding hydrophobicity, chemical resistance, and heat resistance. Our study provides insights that fluorinated polymers have generally lower thermal conductivity, offering benefits for industry where thermal insulation is desired. This study provides an important step in the validation of computational studies and advances the development of machine learning models for the thermal conductivity of polymers.
{"title":"Reduction of the Thermal Conductivity of Polyurethanes by Fluorination: Impact of Crystallinity, Atomic Density, and Sound Velocity","authors":"Jingyi Zhou, Chen Chen, Jinchi Sun, Thomas R. Fielitz, Weijun Zhou, David G. Cahill, Paul V. Braun","doi":"10.1002/anie.202503497","DOIUrl":"https://doi.org/10.1002/anie.202503497","url":null,"abstract":"This study provides a rich database of structure–property relationships that will help guide future work in designing polymers with low intrinsic thermal conductivity. Fluorinated polymers are widely utilized in industry for their outstanding hydrophobicity, chemical resistance, and heat resistance. Our study provides insights that fluorinated polymers have generally lower thermal conductivity, offering benefits for industry where thermal insulation is desired. This study provides an important step in the validation of computational studies and advances the development of machine learning models for the thermal conductivity of polymers.","PeriodicalId":125,"journal":{"name":"Angewandte Chemie International Edition","volume":"72 1","pages":""},"PeriodicalIF":16.6,"publicationDate":"2025-04-25","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143872594","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}
The controlled generation and utilization of singlet oxygen (1O2) are crucial for its diverse applications but remain challenging due to its high reactivity and short-lived nature. Here, we report a box-shaped metallacage prepared via multicomponent coordination-driven self-assembly using tetrapyridyl perylene diimide (PDI) and tetracarboxylate anthracene as building blocks. Upon photo-irradiation, the PDI faces act as photosensitizers to generate 1O2, which reacts with the anthracene pillars to form a peroxidized metallacage, where 1O2 is captured and stored as anthracene peroxides. Heating releases 1O2 quantitatively, restoring the original metallacage structure. Both states are stable at room temperature, as confirmed by X-ray diffraction. Additionally, photoinduced electron transfer (PET) from anthracene pillars to PDI faces quenches the emission of the metallacage, while oxidation of anthracene inhibits PET, yielding bright fluorescence for the peroxidized metallacage. This reversible emission change enables the metallacage to function as a “turn-on” fluorescence sensor for dissolved oxygen, with a detection limit of 1.1×10-3 mg/L. This study demonstrates a metallacage that can generate, capture, store, and release 1O2 for oxygen sensing, offering insights for designing stimuli-responsive smart materials.
{"title":"Generation, Capture, Storage and Release of Singlet Oxygen from A Perylene Diimide-Based Metallacage for Oxygen Sensing","authors":"Yali Hou, Yingjie Li, Dengke Han, Zeyuan Zhang, Jinping Zhang, Shijin Jian, Zixuan Li, Xianglong Duan, Haonan Peng, Yu Fang, Mingming Zhang","doi":"10.1002/anie.202507112","DOIUrl":"https://doi.org/10.1002/anie.202507112","url":null,"abstract":"The controlled generation and utilization of singlet oxygen (1O2) are crucial for its diverse applications but remain challenging due to its high reactivity and short-lived nature. Here, we report a box-shaped metallacage prepared via multicomponent coordination-driven self-assembly using tetrapyridyl perylene diimide (PDI) and tetracarboxylate anthracene as building blocks. Upon photo-irradiation, the PDI faces act as photosensitizers to generate 1O2, which reacts with the anthracene pillars to form a peroxidized metallacage, where 1O2 is captured and stored as anthracene peroxides. Heating releases 1O2 quantitatively, restoring the original metallacage structure. Both states are stable at room temperature, as confirmed by X-ray diffraction. Additionally, photoinduced electron transfer (PET) from anthracene pillars to PDI faces quenches the emission of the metallacage, while oxidation of anthracene inhibits PET, yielding bright fluorescence for the peroxidized metallacage. This reversible emission change enables the metallacage to function as a “turn-on” fluorescence sensor for dissolved oxygen, with a detection limit of 1.1×10-3 mg/L. This study demonstrates a metallacage that can generate, capture, store, and release 1O2 for oxygen sensing, offering insights for designing stimuli-responsive smart materials.","PeriodicalId":125,"journal":{"name":"Angewandte Chemie International Edition","volume":"17 1","pages":""},"PeriodicalIF":16.6,"publicationDate":"2025-04-25","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143872499","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}
The catalytic enantioselective synthesis of aza-sulfur(VI) compounds holds significant potential in pharmaceuticals owing to their broad spectrum of biological properties. Herein, we report the first N-heterocyclic carbene (NHC)-organocatalyzed enantioselective synthesis of cyclic sulfonimidamides (SIAs). The free N-H containing SIAs often exhibit configurational lability through tautomerization. We investigated this by demonstrating their non-symmetric nature in both solid state and solution. The in situ generated chiral acylazolium intermediates from easily accessible aldehydes in the presence of NHC and oxidant were trapped with the prochiral cyclic SIA anions allowing the enantioselective synthesis of configurationally stable N-acyl cyclic SIAs. Mechanistic studies reveal that the present strategy proceeds via the desymmetrization of the prochiral SIA anions. Moreover, the derivatization of the synthesized N-acyl SIAs highlights the practical utility of the present methodology.
{"title":"Control Over S(VI)-Stereogenic Center: NHC-Catalyzed Enantioselective Synthesis of N-Acyl Cyclic Sulfonimidamides","authors":"Soumen Barik, Fathima Dinsha Paravakkal, Priyanshu Gupta, Palash Roy, Akkattu T. Biju","doi":"10.1002/anie.202506929","DOIUrl":"https://doi.org/10.1002/anie.202506929","url":null,"abstract":"The catalytic enantioselective synthesis of aza-sulfur(VI) compounds holds significant potential in pharmaceuticals owing to their broad spectrum of biological properties. Herein, we report the first N-heterocyclic carbene (NHC)-organocatalyzed enantioselective synthesis of cyclic sulfonimidamides (SIAs). The free N-H containing SIAs often exhibit configurational lability through tautomerization. We investigated this by demonstrating their non-symmetric nature in both solid state and solution. The in situ generated chiral acylazolium intermediates from easily accessible aldehydes in the presence of NHC and oxidant were trapped with the prochiral cyclic SIA anions allowing the enantioselective synthesis of configurationally stable N-acyl cyclic SIAs. Mechanistic studies reveal that the present strategy proceeds via the desymmetrization of the prochiral SIA anions. Moreover, the derivatization of the synthesized N-acyl SIAs highlights the practical utility of the present methodology.","PeriodicalId":125,"journal":{"name":"Angewandte Chemie International Edition","volume":"7 1","pages":""},"PeriodicalIF":16.6,"publicationDate":"2025-04-25","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143872496","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}
Xingxing Gong, Lian-Wei Ye, Zong-Chang Han, Yue Zhao, Jin Xie, Han-Shi Hu, Jun Li, Congqing Zhu
Photocatalysis is a pivotal area in synthetic chemistry. Despite extensive application potential in nuclear industry, uranium-based photocatalysts are historically limited to uranyl(VI/V) redox cycle. Here, we report the discovery of the first tetravalent uranium [U(IV)] photocatalyst that enables efficient C(sp3)–C(sp3) bond cleavage and formation under ideal visible light. The U(IV) alkoxy species mediates C–C bond cleavage in a wide range of cycloalkanols and promotes their coupling with electron-deficient alkenes, providing access to previously unattainable molecular architectures. These U(IV) alkoxy complexes, fully characterized by X-ray diffraction and magnetic studies, exhibit exceptional photocatalytic efficiency. Quantum chemical studies reveal that the energy barrier for C–C bond cleavage and formation is reduced to below 10 kcal mol-1 under visible light excitation. This work introduces a new mechanistic paradigm for uranium-based photocatalysis and positions U(IV) alkoxy complexes as a versatile platform for bond activation and functionalization, expanding the potential applications of depleted uranium in synthetic chemistry.
{"title":"Unprecedented Tetravalent Uranium Photocatalysts for Efficient C(sp3)–C(sp3) Bond Cleavage and Formation","authors":"Xingxing Gong, Lian-Wei Ye, Zong-Chang Han, Yue Zhao, Jin Xie, Han-Shi Hu, Jun Li, Congqing Zhu","doi":"10.1002/anie.202502634","DOIUrl":"https://doi.org/10.1002/anie.202502634","url":null,"abstract":"Photocatalysis is a pivotal area in synthetic chemistry. Despite extensive application potential in nuclear industry, uranium-based photocatalysts are historically limited to uranyl(VI/V) redox cycle. Here, we report the discovery of the first tetravalent uranium [U(IV)] photocatalyst that enables efficient C(sp3)–C(sp3) bond cleavage and formation under ideal visible light. The U(IV) alkoxy species mediates C–C bond cleavage in a wide range of cycloalkanols and promotes their coupling with electron-deficient alkenes, providing access to previously unattainable molecular architectures. These U(IV) alkoxy complexes, fully characterized by X-ray diffraction and magnetic studies, exhibit exceptional photocatalytic efficiency. Quantum chemical studies reveal that the energy barrier for C–C bond cleavage and formation is reduced to below 10 kcal mol-1 under visible light excitation. This work introduces a new mechanistic paradigm for uranium-based photocatalysis and positions U(IV) alkoxy complexes as a versatile platform for bond activation and functionalization, expanding the potential applications of depleted uranium in synthetic chemistry.","PeriodicalId":125,"journal":{"name":"Angewandte Chemie International Edition","volume":"34 1","pages":""},"PeriodicalIF":16.6,"publicationDate":"2025-04-25","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143872502","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}
Zhongyue J. Yang, Ning Ding, Yaoyukun Jiang, Robbie Ge, Qianzhen Shao, Wook Shin, Xinchun Ran
Cold-adapted bidomain enzymes have the potential to foster industrial sustainability by reducing energy consumption and greenhouse gas emissions. Despite their allure, these benefits are unattainable as the molecular basis of cold adaptation remains elusive and there are no strategies to guide the acquisition of this behavior. To uncover principles of cold adaptation, we selected the cold-adapted Saccharophagus degradans amylase (sdA) and mesophilic Pseudomonas saccharophila amylase (psA) as model systems to study. Through molecular dynamics simulations and biochemical assays, we found that sdA exhibits significantly greater interdomain separation between its catalytic domain (CD) and carbohydrate-binding module (CBM) at low temperatures. Guided by this insight, we introduce the domain separation index (DSI) metric to guide in-silico screening of 120 psA variants using high-throughput enzyme modeling. The highest ranked variant, psA121, shows a 3-fold increase in relative activity over the wild type at 0°C. MD simulations suggest that psA121 achieves cold adaptation via helical linkers which induce interdomain separation and enhance flexibility of the active-site and binding loop via dynamic allostery, promoting substrate recruitment, binding, and catalysis at lower temperatures. This study highlights how domain separation contributes to cold adaptation in bidomain amylases and offers strategies for introducing such cold-adaption to other systems.
{"title":"Enhancing Cold Adaptation of Bidomain Amylases by High-Throughput Computational Engineering","authors":"Zhongyue J. Yang, Ning Ding, Yaoyukun Jiang, Robbie Ge, Qianzhen Shao, Wook Shin, Xinchun Ran","doi":"10.1002/anie.202505991","DOIUrl":"https://doi.org/10.1002/anie.202505991","url":null,"abstract":"Cold-adapted bidomain enzymes have the potential to foster industrial sustainability by reducing energy consumption and greenhouse gas emissions. Despite their allure, these benefits are unattainable as the molecular basis of cold adaptation remains elusive and there are no strategies to guide the acquisition of this behavior. To uncover principles of cold adaptation, we selected the cold-adapted Saccharophagus degradans amylase (sdA) and mesophilic Pseudomonas saccharophila amylase (psA) as model systems to study. Through molecular dynamics simulations and biochemical assays, we found that sdA exhibits significantly greater interdomain separation between its catalytic domain (CD) and carbohydrate-binding module (CBM) at low temperatures. Guided by this insight, we introduce the domain separation index (DSI) metric to guide in-silico screening of 120 psA variants using high-throughput enzyme modeling. The highest ranked variant, psA121, shows a 3-fold increase in relative activity over the wild type at 0°C. MD simulations suggest that psA121 achieves cold adaptation via helical linkers which induce interdomain separation and enhance flexibility of the active-site and binding loop via dynamic allostery, promoting substrate recruitment, binding, and catalysis at lower temperatures. This study highlights how domain separation contributes to cold adaptation in bidomain amylases and offers strategies for introducing such cold-adaption to other systems.","PeriodicalId":125,"journal":{"name":"Angewandte Chemie International Edition","volume":"7 1","pages":""},"PeriodicalIF":16.6,"publicationDate":"2025-04-24","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143867051","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}
Ryo Fukuoka, Yusuke Yano, Nozomi Hara, Chihiro Sadamoto, Andres D. Maturana, Masaki Kita
Mammalian secreted venoms mainly consist of peptides and proteases used for defense or predation. Blarina paralytic peptides (BPPs), mealworm-targeting neurotoxins from shrew, are very similar to human synenkephalin. This peptide is released from proenkephalin in the brain along with opioid peptides that mediate analgesic and antidepressant effects, though its physiological function is unclear. Here we synthesized and characterized human synenkephalin [1–53] (hSYN), and reveal its disulfide bond connectivity. Similar to BPP2, hSYN caused a hyperpolarizing shift in the human T-type voltage-gated calcium channel (hCav3.2) at 0.74 µM, but did not paralyze mealworms. Molecular docking and molecular dynamics simulations showed that hSYN and BPP2 interact with hCav3.2 channel differently, due to differences in polar residues. Since Cav3.2 channel regulates neuronal excitability and is implicated in conditions like autism and epilepsy, our findings on hSYN could provide insights into the channel gating and agonistic mechanisms, along with potential pathways for developing treatments for neurological disorders.
{"title":"Hyperpolarization Modulation of the T-type hCav3.2 Channel by Human Synenkephalin [1–53], a Shrew Neurotoxin Analogue without Paralytic Effects","authors":"Ryo Fukuoka, Yusuke Yano, Nozomi Hara, Chihiro Sadamoto, Andres D. Maturana, Masaki Kita","doi":"10.1002/anie.202503891","DOIUrl":"https://doi.org/10.1002/anie.202503891","url":null,"abstract":"Mammalian secreted venoms mainly consist of peptides and proteases used for defense or predation. Blarina paralytic peptides (BPPs), mealworm-targeting neurotoxins from shrew, are very similar to human synenkephalin. This peptide is released from proenkephalin in the brain along with opioid peptides that mediate analgesic and antidepressant effects, though its physiological function is unclear. Here we synthesized and characterized human synenkephalin [1–53] (hSYN), and reveal its disulfide bond connectivity. Similar to BPP2, hSYN caused a hyperpolarizing shift in the human T-type voltage-gated calcium channel (hCav3.2) at 0.74 µM, but did not paralyze mealworms. Molecular docking and molecular dynamics simulations showed that hSYN and BPP2 interact with hCav3.2 channel differently, due to differences in polar residues. Since Cav3.2 channel regulates neuronal excitability and is implicated in conditions like autism and epilepsy, our findings on hSYN could provide insights into the channel gating and agonistic mechanisms, along with potential pathways for developing treatments for neurological disorders.","PeriodicalId":125,"journal":{"name":"Angewandte Chemie International Edition","volume":"95 1","pages":""},"PeriodicalIF":16.6,"publicationDate":"2025-04-24","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143872509","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}
Jens Wöhnert, Konstantin Neissner, Elke Duchardt-Ferner, Christoph Wiedemann, Julian Kraus, Ute A. Hellmich
Phosphodiester groups occur ubiquitously in nature, e.g. in nucleic acids or in cyclic (di-)nucleotides important for signal transduction. Proteins often use polar or positively charged amino acids to interact with the negatively charged phosphodiester groups via hydrogen bonds and salt bridges. In contrast, the acidic amino acids aspartate and glutamate are generally not considered as important determinants for phosphodiester group recognition. Instead they are regarded as detrimental to such interactions due to the assumed charge repulsion between their deprotonated, negatively charged side chain carboxylate groups and the phosphodiester. Accordingly, acidic amino acids are often purposefully introduced into proteins to abrogate nucleic acid interactions in functional studies. Here, we show that in appropriate structural contexts glutamate side chains are readily protonated even at neutral pH and act as hydrogen bond donors to phosphodiester groups using a c-di-GMP binding protein – the GSPII-B domain of PilF from Thermus thermophilus – as an example. Surveying available RNA-protein and DNA-protein complex structures in the PDB, we found that hydrogen bonds between protonated carboxylate groups of glutamate and aspartate and phosphodiester groups occur frequently in different functional protein classes. Thus, the functional role of acidic amino acids in phosphodiester group recognition needs to be re-evaluated.
{"title":"Protonated Glutamate and Aspartate Side Chains Can Recognize Phosphodiester Groups via Strong and Short Hydrogen Bonds in Biomacromolecular Complexes","authors":"Jens Wöhnert, Konstantin Neissner, Elke Duchardt-Ferner, Christoph Wiedemann, Julian Kraus, Ute A. Hellmich","doi":"10.1002/anie.202501589","DOIUrl":"https://doi.org/10.1002/anie.202501589","url":null,"abstract":"Phosphodiester groups occur ubiquitously in nature, e.g. in nucleic acids or in cyclic (di-)nucleotides important for signal transduction. Proteins often use polar or positively charged amino acids to interact with the negatively charged phosphodiester groups via hydrogen bonds and salt bridges. In contrast, the acidic amino acids aspartate and glutamate are generally not considered as important determinants for phosphodiester group recognition. Instead they are regarded as detrimental to such interactions due to the assumed charge repulsion between their deprotonated, negatively charged side chain carboxylate groups and the phosphodiester. Accordingly, acidic amino acids are often purposefully introduced into proteins to abrogate nucleic acid interactions in functional studies. Here, we show that in appropriate structural contexts glutamate side chains are readily protonated even at neutral pH and act as hydrogen bond donors to phosphodiester groups using a c-di-GMP binding protein – the GSPII-B domain of PilF from Thermus thermophilus – as an example. Surveying available RNA-protein and DNA-protein complex structures in the PDB, we found that hydrogen bonds between protonated carboxylate groups of glutamate and aspartate and phosphodiester groups occur frequently in different functional protein classes. Thus, the functional role of acidic amino acids in phosphodiester group recognition needs to be re-evaluated.","PeriodicalId":125,"journal":{"name":"Angewandte Chemie International Edition","volume":"32 1","pages":""},"PeriodicalIF":16.6,"publicationDate":"2025-04-24","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143867043","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}
Haotian Qiu, Ran An, Chen Cui, Zhi Li, Jinfeng Yang, Xiaochuang Wang, Xueling Hou, Junjie Li, Juanjuan Lu, Jun Sun, Zhihua Yang, Shilie Pan, Miriding Mutailipu
The light polarization modulation involves the capacity to respond selectively to light-mater interaction and is dependent on the optical anisotropy of crystalline materials. The π-conjugated component is almost typically utilized to produce such materials in the short-wave ultraviolet region, however, the conflicting link between high optical anisotropy and strong layered habit is difficult to reconcile. As a result, many anisotropic crystals are limited to tiny crystals rather than processing optical devices. This study designs crystals with beneficial but easy-to-grow layered structure and strong optical anisotropy by bridging the interlayer binding to ordered π-conjugated units. To this end, two new hybrid crystals are reported by combining cationic regulation and π-conjugated units. This allows for the easy growth of centimeter-large, high optical quality 1Na single crystals, providing crystal assurance for all-around testing for a practical crystal. Using the most accurate minimal deviation angle method, the birefringence is measured to be 0.174-0.258@253-1013 nm, surpassing all reported crystals with the same components of [HCOO] or [C(NH2)3] in the applied short-wave ultraviolet region as well as the corresponding commercial crystals. This work will serve as a guide for future research on innovative short-wave ultraviolet birefringent crystals.
{"title":"Bridging the Interlayer Binding to Ordered π-Conjugated Units for Constructing High-Performing Light Polarization Crystals","authors":"Haotian Qiu, Ran An, Chen Cui, Zhi Li, Jinfeng Yang, Xiaochuang Wang, Xueling Hou, Junjie Li, Juanjuan Lu, Jun Sun, Zhihua Yang, Shilie Pan, Miriding Mutailipu","doi":"10.1002/anie.202507171","DOIUrl":"https://doi.org/10.1002/anie.202507171","url":null,"abstract":"The light polarization modulation involves the capacity to respond selectively to light-mater interaction and is dependent on the optical anisotropy of crystalline materials. The π-conjugated component is almost typically utilized to produce such materials in the short-wave ultraviolet region, however, the conflicting link between high optical anisotropy and strong layered habit is difficult to reconcile. As a result, many anisotropic crystals are limited to tiny crystals rather than processing optical devices. This study designs crystals with beneficial but easy-to-grow layered structure and strong optical anisotropy by bridging the interlayer binding to ordered π-conjugated units. To this end, two new hybrid crystals are reported by combining cationic regulation and π-conjugated units. This allows for the easy growth of centimeter-large, high optical quality 1Na single crystals, providing crystal assurance for all-around testing for a practical crystal. Using the most accurate minimal deviation angle method, the birefringence is measured to be 0.174-0.258@253-1013 nm, surpassing all reported crystals with the same components of [HCOO] or [C(NH2)3] in the applied short-wave ultraviolet region as well as the corresponding commercial crystals. This work will serve as a guide for future research on innovative short-wave ultraviolet birefringent crystals.","PeriodicalId":125,"journal":{"name":"Angewandte Chemie International Edition","volume":"23 1","pages":""},"PeriodicalIF":16.6,"publicationDate":"2025-04-24","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143872512","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}
Lennart Gerhard Holzapfel, Johanna Manegold, Stefan Florian Clewing, Hartmut Schubert, Klaus Eichele, Lars Wesemann
A one-pot synthesis for previously unknown heavy homologues of group 9 metal carbynes [(Me3P)3CoºGeAr*] (1), [(Me3P)3RhºGeAr*] (2), [(Me3P)3IrºGeAr*] (3), [(Me3P)3IrºSnAr*] (5), and [(Et3P)3IrºPbAr*] (7) is presented [Ar* = C6H3-2,6-(Trip)2, Trip = 2,4,6-C6H2iPr3]. During these preparations the tetrylidynes [(Me3P)3RhºSnAr*] (4), and [(Me3P)3RhºPbAr*] (6), were also prepared in a one-pot procedure. In a hitherto unknown metathetical exchange reaction the transition metal plumbylidynes were converted into the respective stannylidynes in reaction with terphenyl stannylene chloride, and the germylidynes were formed from the corresponding stannylidynes in reaction with terphenyl germylene chloride. This metathesis reaction was tracked by 31P{1H} NMR spectroscopy which shows complete exchange of the tetrel [EAr]-fragment and the formation of an intermediate in the rhodium plumbylidyne reaction with stannylene chloride (Ar = Ar*, Tbb). Reactions of the tetrylidynes (2-5) with carbon dioxide yield the products of a redox reaction [(Me3P)3(CO)M-E(η2-O2CO-κ2O)Ar*] [E = Ge, M= Rh (11); M = Ir (12); E = Sn, M = Rh (14), M = Ir (16)] with a carbon monoxide coordinated at the transition metal and a carbonate coordinated at the group 14 element. For tin the intermediates formed by mono CO2 addition [(Me3P)3M(µ,η2-CO2-κC:κO)SnAr*] [M = Rh (13), M = Ir (15)] have been isolated.
{"title":"Metathetical Exchange, Synthesis and Carbon Dioxide Addition of Higher Homologues of Group 9 Metal Carbynes","authors":"Lennart Gerhard Holzapfel, Johanna Manegold, Stefan Florian Clewing, Hartmut Schubert, Klaus Eichele, Lars Wesemann","doi":"10.1002/anie.202503930","DOIUrl":"https://doi.org/10.1002/anie.202503930","url":null,"abstract":"A one-pot synthesis for previously unknown heavy homologues of group 9 metal carbynes [(Me3P)3CoºGeAr*] (1), [(Me3P)3RhºGeAr*] (2), [(Me3P)3IrºGeAr*] (3), [(Me3P)3IrºSnAr*] (5), and [(Et3P)3IrºPbAr*] (7) is presented [Ar* = C6H3-2,6-(Trip)2, Trip = 2,4,6-C6H2iPr3]. During these preparations the tetrylidynes [(Me3P)3RhºSnAr*] (4), and [(Me3P)3RhºPbAr*] (6), were also prepared in a one-pot procedure. In a hitherto unknown metathetical exchange reaction the transition metal plumbylidynes were converted into the respective stannylidynes in reaction with terphenyl stannylene chloride, and the germylidynes were formed from the corresponding stannylidynes in reaction with terphenyl germylene chloride. This metathesis reaction was tracked by 31P{1H} NMR spectroscopy which shows complete exchange of the tetrel [EAr]-fragment and the formation of an intermediate in the rhodium plumbylidyne reaction with stannylene chloride (Ar = Ar*, Tbb). Reactions of the tetrylidynes (2-5) with carbon dioxide yield the products of a redox reaction [(Me3P)3(CO)M-E(η2-O2CO-κ2O)Ar*] [E = Ge, M= Rh (11); M = Ir (12); E = Sn, M = Rh (14), M = Ir (16)] with a carbon monoxide coordinated at the transition metal and a carbonate coordinated at the group 14 element. For tin the intermediates formed by mono CO2 addition [(Me3P)3M(µ,η2-CO2-κC:κO)SnAr*] [M = Rh (13), M = Ir (15)] have been isolated.","PeriodicalId":125,"journal":{"name":"Angewandte Chemie International Edition","volume":"24 1","pages":""},"PeriodicalIF":16.6,"publicationDate":"2025-04-24","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143866884","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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