Angewandte Chemie (International ed. in English)最新文献

Targeted Detection of Phospholipid Aldehydes in Living Cells by Oxime Ligation. 肟结扎法靶向检测活细胞中磷脂醛。

IF 16.9

Angewandte Chemie (International ed. in English) Pub Date : 2025-10-01 DOI: 10.1002/anie.202512578

Jacob A Vance, Wei-An Chen, Palina Nepachalovich, Caroline Knittel, Maria Fedorova, Neal K Devaraj

{"title":"Targeted Detection of Phospholipid Aldehydes in Living Cells by Oxime Ligation.","authors":"Jacob A Vance, Wei-An Chen, Palina Nepachalovich, Caroline Knittel, Maria Fedorova, Neal K Devaraj","doi":"10.1002/anie.202512578","DOIUrl":"https://doi.org/10.1002/anie.202512578","url":null,"abstract":"Oxidatively damaged lipids play critical roles in numerous human pathologies, yet methods to directly identify these species within living cells remain limited due to their transient and low-abundance nature. Among lipid oxidation products, aldehyde-containing lipids are significant due to their heightened reactivity and strong links to disease pathology. Here, we introduce OxiLox (oxime ligation to oxidized lipids), a method that leverages fluorescent hydroxylamine-based probes to enable direct, chemoselective tagging of aldehyde-containing lipids within living cells via rapid oxime ligation. Using confocal microscopy, we observe the subcellular localization of these oxidized lipids, highlighting prominent accumulation within perinuclear membranes, particularly under oxidative stress conditions induced by the ferroptosis activator RSL3. Coupled with high-resolution mass spectrometry, our method identifies aldehyde lipid species, notably revealing the abundance of oxidized plasmenyl phosphatidylethanolamines in ferroptotic cells. We demonstrate that cellular labeling by hydroxylamine probes can be modulated by altering the expression of antioxidant enzymes such as aldose reductase (AKR1B1), underscoring the relationship between enzymatic antioxidant defenses and lipid aldehyde metabolism. Our work establishes OxiLox as a robust approach for direct, sensitive, and chemically precise detection of lipid aldehydes in live cells, offering new insights into the role of lipid oxidation in health and disease.","PeriodicalId":520556,"journal":{"name":"Angewandte Chemie (International ed. in English)","volume":" ","pages":"e202512578"},"PeriodicalIF":16.9,"publicationDate":"2025-10-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145202869","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":0,"RegionCategory":"","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

引用次数: 0

Youwei Ma.

IF 16.9

Angewandte Chemie (International ed. in English) Pub Date : 2025-09-30 DOI: 10.1002/anie.202520832

Youwei Ma

引用次数: 0

Interplay of Polar Order and Positional Order in Liquid Crystals-Observation of Re-entrant Ferroelectric Nematic Phase. 液晶中极性序和位置序的相互作用——重入铁电向列相的观察。

IF 16.9

Angewandte Chemie (International ed. in English) Pub Date : 2025-09-30 DOI: 10.1002/anie.202516302

Grant J Strachan, Shona J Ramsay, Marijus Juodka, Damian Pociecha, Jadwiga Szydlowska, John M D Storey, Nataša Vaupotič, Rebecca Walker, Ewa Gorecka

引用次数: 0

N-Doped Nonalternant Molecular Bowl/Saddle Hybrids. n掺杂非交替分子碗/鞍杂化物。

IF 16.9

Angewandte Chemie (International ed. in English) Pub Date : 2025-09-30 DOI: 10.1002/anie.202516881

Shuhai Qiu, Kai Chen, Ziqi Deng, Xuan Jin, Zuoyu Li, Guogang Liu, Li Zhang, Wei Jiang, Teng-Teng Chen, Junzhi Liu, Zhaohui Wang

{"title":"N-Doped Nonalternant Molecular Bowl/Saddle Hybrids.","authors":"Shuhai Qiu, Kai Chen, Ziqi Deng, Xuan Jin, Zuoyu Li, Guogang Liu, Li Zhang, Wei Jiang, Teng-Teng Chen, Junzhi Liu, Zhaohui Wang","doi":"10.1002/anie.202516881","DOIUrl":"https://doi.org/10.1002/anie.202516881","url":null,"abstract":"Herein, we report the straightforward synthesis and properties of N-doped molecular bowl/saddle hybrids with nonalternant topologies via successive palladium-catalyzed annulations. Structural evolutions from twisted, bowl-shaped to bowl/saddle-hybridized structures are involved during the core-expansion process, as confirmed by X-ray crystallographic analyses. Notably, this resultant bowl/saddle-hybridized molecular carbon shows unique molecular dynamics, as revealed by 1H NMR, chiral HPLC analyses and theoretical calculations. These molecules exhibit interesting photophysical properties, including moderate fluorescence quantum yields and narrowband emissions. Steady-state and transient spectroscopy reveal the different photophysical properties in these molecular bowl and bowl/saddle hybrids. Moreover, the molecular bowl/saddle hybrid exhibits the shape-adaptive character, and allow for multiple bindings with fullerene guests in a stoichiometry ratio of 1:3, which is seldomly observed in most nonplanar molecular carbons. This study not only presents an efficient strategy to construct a new family of N-doped nonalternant molecular bowl/saddle hybrids, but also provides insights into molecular design of topological nanocarbons with potential applications of chiral materials and organic electronics.","PeriodicalId":520556,"journal":{"name":"Angewandte Chemie (International ed. in English)","volume":" ","pages":"e202516881"},"PeriodicalIF":16.9,"publicationDate":"2025-09-30","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145194269","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":0,"RegionCategory":"","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

引用次数: 0

Mn(I)-Complex Catalyzed Upcycling of Polyethylene Terephthalate to α-Hydroxy Carboxylic Acids. Mn(I)-配合物催化聚对苯二甲酸酯升级回收制α-羟基羧酸。

IF 16.9

Angewandte Chemie (International ed. in English) Pub Date : 2025-09-30 DOI: 10.1002/anie.202513145

Soham Das Adhikary, Sayan K Jana, Biplab Maji

{"title":"Mn(I)-Complex Catalyzed Upcycling of Polyethylene Terephthalate to α-Hydroxy Carboxylic Acids.","authors":"Soham Das Adhikary, Sayan K Jana, Biplab Maji","doi":"10.1002/anie.202513145","DOIUrl":"https://doi.org/10.1002/anie.202513145","url":null,"abstract":"The chemical upcycling of poly(ethylene terephthalate) (PET) waste into value-added products presents a promising strategy to address global plastic pollution. Here, we report a manganese-catalyzed, one-pot approach for tandem PET depolymerization and acceptorless dehydrogenative coupling (ADC) to selectively produce α-hydroxycarboxylic acids (α-HCAs), including glycolic, lactic, and higher-value derivatives, along with terephthalic acid (TPA) and H2 gas. Employing bench-stable (PNP)Mn(I)-pincer complexes, this cascade process operates under mild conditions (120-140 °C) and accommodates a broad range of primary alcohol coupling partners, enabling the synthesis of valuable biodegradable polymer precursors (glycolic and lactic acid) and higher α-HCAs. Notably, the system exhibits exceptional tolerance to common plastic additives and requires no energy-intensive pretreatment, achieving near-quantitative TPA recovery and significant H2 evolution. This work demonstrates how base-metal catalysis can bridge plastic waste remediation and sustainable chemical synthesis, offering a practical pathway toward circular polymer economies.","PeriodicalId":520556,"journal":{"name":"Angewandte Chemie (International ed. in English)","volume":" ","pages":"e202513145"},"PeriodicalIF":16.9,"publicationDate":"2025-09-30","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145194278","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":0,"RegionCategory":"","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

引用次数: 0

Hybrid of Indolizine and Merocyanine-A New Class of Organelle-Specific Dyes. 吲哚嘧啶和merocyanine的杂化——一类新的细胞器特异性染料。

IF 16.9

Angewandte Chemie (International ed. in English) Pub Date : 2025-09-29 DOI: 10.1002/anie.202508044

Jaqueline S A Badaro, Beata Koszarna, Maja Perkowska, Kristiana Kandere-Grzybowska, Diana V Kolygina, Olaf Morawski, Juhee Park, Bartosz Grzybowski, Irena Deperasińska, Daniel T Gryko

{"title":"Hybrid of Indolizine and Merocyanine-A New Class of Organelle-Specific Dyes.","authors":"Jaqueline S A Badaro, Beata Koszarna, Maja Perkowska, Kristiana Kandere-Grzybowska, Diana V Kolygina, Olaf Morawski, Juhee Park, Bartosz Grzybowski, Irena Deperasińska, Daniel T Gryko","doi":"10.1002/anie.202508044","DOIUrl":"https://doi.org/10.1002/anie.202508044","url":null,"abstract":"Unlocking the potential of electron-rich 2-hydroxyindolizines led to the discovery of a new class of dyes-indolizine-merocyanines (IndMer) and indolizine-cyanines. Tandem Friedel-Crafts alkylation followed by intramolecular nucleophilic aromatic substitution afforded structurally diverse dyes, as both the nucleophilic and electrophilic partners can be broadly modified. A convergent fragment coupling strategy allowed rapid access to these π-conjugated merocyanines in three steps from pyridines. Uniform distribution of the HOMO and LUMO combined with negligible change of dipole moment upon excitation is responsible for the intense orange or red emission of this new family of reasonably photostable dyes in a broad range of solvents. The new merocyanine dyes have the potential to target a variety of organelles-both uncharged and positively charged indolizine-merocyanines localize a subset of cellular lysosomes, positively charged indolizine-cyanine hybrid accumulates in mitochondria, while coumarin-merocyanine shows context-dependent localization to mitochondria and RNA-rich nucleoli of the living cells.","PeriodicalId":520556,"journal":{"name":"Angewandte Chemie (International ed. in English)","volume":" ","pages":"e202508044"},"PeriodicalIF":16.9,"publicationDate":"2025-09-29","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145194181","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":0,"RegionCategory":"","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

引用次数: 0

Discovery and Biosynthesis of Rare Fungal Terpenoid-Isonitrile Amino Acid Hybrid Natural Products. 稀有真菌萜类-异腈氨基酸杂化天然产物的发现与生物合成。

IF 16.9

Angewandte Chemie (International ed. in English) Pub Date : 2025-09-29 DOI: 10.1002/anie.202516403

Xing-Yue Chen, Qian Yang, Yi Zou

{"title":"Discovery and Biosynthesis of Rare Fungal Terpenoid-Isonitrile Amino Acid Hybrid Natural Products.","authors":"Xing-Yue Chen, Qian Yang, Yi Zou","doi":"10.1002/anie.202516403","DOIUrl":"https://doi.org/10.1002/anie.202516403","url":null,"abstract":"Terpenoid nonproteinogenic amino acid hybrid natural products usually have complex chemical structures and important biological functions. Herein, we discovered a group of conserved and widely distributed clusters of sesquiterpenoid-isonitrile isoleucine hybrid compounds from Fusarium through a two-step genome mining strategy. An investigation of the function of the isc cluster from Fusarium chlamydosporum revealed a variety of unusual enzymatic transformations, which importantly include 1) a single-module nonribosomal peptide synthase (NRPS) IscF featuring an unusual C-terminal transferase domain that catalyses the esterification reaction on C2─OH of a highly oxidised guaiane-type 5/7-bicyclic sesquiterpene precursor 4 with T domain-bound l-isonitrile isoleucine 11a to yield terpenoid-isonitrile isoleucine hybrid natural product 9a (chlamonitrile A) and 2) cytochrome P450 (CYP450) IscD, which unexpectedly catalyses the Cα-Cβ dehydrogenation of the isonitrile isoleucine moiety of 9a, resulting in the final products 13a/13b (chlamonitriles E/F). In addition, phytotoxic evaluation experiments revealed that 9a and its structural analogues are new phytotoxins of Fusarium. Our work provides the first example of the discovery of terpenoid-isonitrile amino acid hybrid compounds from fungi, expands our knowledge of the new functions of NRPS domains and fungal CYP450s, and uncovers the possible biological functions of these compounds in Fusarium.","PeriodicalId":520556,"journal":{"name":"Angewandte Chemie (International ed. in English)","volume":" ","pages":"e202516403"},"PeriodicalIF":16.9,"publicationDate":"2025-09-29","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145194186","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":0,"RegionCategory":"","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

引用次数: 0

Bismuth-Selenopeptides Combine Potent Bioactivity with Exceptional Kinetic Inertness. 铋-硒肽结合了强大的生物活性和特殊的动力学惰性。

IF 16.9

Angewandte Chemie (International ed. in English) Pub Date : 2025-09-29 DOI: 10.1002/anie.202517700

Pritha Ghosh, Minghao Shang, Katarina Trajković, Lani J Davies, Upamali Somathilake, Toshiki Takei, Hironobu Hojo, Christoph Nitsche

{"title":"Bismuth-Selenopeptides Combine Potent Bioactivity with Exceptional Kinetic Inertness.","authors":"Pritha Ghosh, Minghao Shang, Katarina Trajković, Lani J Davies, Upamali Somathilake, Toshiki Takei, Hironobu Hojo, Christoph Nitsche","doi":"10.1002/anie.202517700","DOIUrl":"https://doi.org/10.1002/anie.202517700","url":null,"abstract":"Bismuth peptides and proteins are emerging as versatile tools for medicinal chemistry and chemical biology. Bismuth(III) binds three cysteine residues in peptides and proteins with remarkable selectivity. While the thermodynamic stability of these bismuth complexes is outstanding, their kinetic lability imposes limitations. Introducing bismuth selenopeptides, we demonstrate that selenocysteine binds bismuth with substantially higher kinetic stability than cysteine. This effect was quantified by directly comparing a peptide containing three cysteine residues with an identical peptide containing three selenocysteines. Bismuth selenopeptides are not only inert to strong chelators such as ethylenediaminetetraacetic acid (EDTA) and diethylenetriaminepentaacetic acid (DTPA) but also to the natural metal-binding protein transferrin present in human plasma. We further demonstrate biological utility by developing bismuth selenopeptides that selectively bind and inhibit unrelated target proteins. To extend this concept to a more complex system, we investigated the human epidermal growth factor (EGF), a small protein comprising three disulfide bonds. We established that precisely two bismuth atoms bind to the six cysteine or selenocysteine residues in EGF and seleno-EGF, respectively. In the presence of EDTA, bismuth seleno-EGF remains fully intact, unlike its cysteine-based analog, consistent with observations from smaller peptides. Structural models confirm full preservation of the native EGF fold.","PeriodicalId":520556,"journal":{"name":"Angewandte Chemie (International ed. in English)","volume":" ","pages":"e202517700"},"PeriodicalIF":16.9,"publicationDate":"2025-09-29","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145194429","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":0,"RegionCategory":"","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

引用次数: 0

Ligand Effects in Regio- and Enantioselective Cobalt-Catalyzed Intramolecular [4+2]- and [2+2]-Cycloaddition Reactions of Unactivated 1,3-Diene-8-ynes and 1,3-Diene-8-enes. 钴催化非活化1,3-二烯-8-炔和1,3-二烯-8-炔分子内[4+2]-和[2+2]-环加成反应中的配体效应

IF 16.9

Angewandte Chemie (International ed. in English) Pub Date : 2025-09-29 DOI: 10.1002/anie.202515154

Kiron Kumar Ghosh, Rajdip Chowdhury, Jonathan P Gordon, T V RajanBabu

{"title":"Ligand Effects in Regio- and Enantioselective Cobalt-Catalyzed Intramolecular [4+2]- and [2+2]-Cycloaddition Reactions of Unactivated 1,3-Diene-8-ynes and 1,3-Diene-8-enes.","authors":"Kiron Kumar Ghosh, Rajdip Chowdhury, Jonathan P Gordon, T V RajanBabu","doi":"10.1002/anie.202515154","DOIUrl":"https://doi.org/10.1002/anie.202515154","url":null,"abstract":"Intramolecular Diels-Alder reactions have been extensively used for the syntheses of biologically active compounds including natural products. We have identified Co(I) complexes and optimal reaction conditions to accomplish highly diastereo- and enantioselective intramolecular [4+2]-cycloaddition reactions of 1,3-diene-ynes and 1,3-diene-enes. These catalysts, readily prepared from an earth-abundant metal and tunable ligands, serve as practical replacements for the prohibitively expensive Rh-complexes previously used for similar reactions. The cationic complexes are readily prepared by the reaction of LCoX2 with Zn in the presence of NaBARF. Both neutral and cationic Co(I)-complexes of (S)-BINAP and (S)-H8-BINAP ligands effect the cyclization of 1,3-diene-ynes giving the expected [4+2]-addition products in excellent selectivities. The [4+2]-cycloadditions of the less reactive 1,3-diene-enes proceed only with the cationic complexes and 1,2-bis-[(2S,5S)-2,5-diphenylphospholan-1-yl]ethane (PhBPE) and appropriately substituted phosphinooxazoline (PHOX) are the most optimal ligands for these reactions. Depending on the ligands, 1,3-diene-enes bearing an aromatic substituent at the terminal position undergo an intramolecular [2+2]-cycloaddition, giving cyclobutane products in very good yields and enantioselectivities. The absence of the corresponding [2+2]-cycloaddition in the 1,3-diene-yne substates may be related to the enhanced strain in the expected bicyclo[3.2.0]heptene products. A unified mechanism involving Co(I)/Co(III)-redox cycle, consistent with all available evidence, is proposed for these reactions.","PeriodicalId":520556,"journal":{"name":"Angewandte Chemie (International ed. in English)","volume":" ","pages":"e202515154"},"PeriodicalIF":16.9,"publicationDate":"2025-09-29","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145194211","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":0,"RegionCategory":"","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

引用次数: 0

Ultrasmall Chemogenetic Tags with Group-Transfer Ligands. 基团转移配体的超小化学发生标签。

IF 16.9

Angewandte Chemie (International ed. in English) Pub Date : 2025-09-27 DOI: 10.1002/anie.202506997

Vedagopuram Sreekanth, Shaimaa H Sindi, Santosh K Chaudhary, Rajaiah Pergu, Prashant Singh, Endri Karaj, Surached Siriwongsup, Jeffrey E Fung, Arghya Deb, Stephan J DeCarlo, Jaron A M Mercer, Kei Yamada, Diego Rodriguez, David R Liu, Amit Choudhary

{"title":"Ultrasmall Chemogenetic Tags with Group-Transfer Ligands.","authors":"Vedagopuram Sreekanth, Shaimaa H Sindi, Santosh K Chaudhary, Rajaiah Pergu, Prashant Singh, Endri Karaj, Surached Siriwongsup, Jeffrey E Fung, Arghya Deb, Stephan J DeCarlo, Jaron A M Mercer, Kei Yamada, Diego Rodriguez, David R Liu, Amit Choudhary","doi":"10.1002/anie.202506997","DOIUrl":"10.1002/anie.202506997","url":null,"abstract":"Chemogenetic tags facilitate exploration of activities of a protein-of-interest (POI) that lacks small-molecule ligands; however, most tags are too large for several POIs. Here, we report two ultrasmall chemogenetic tags (mgTag and cTag) of 36 and 50 amino acids (aa) that, to the best of our knowledge, are the smallest. These tags exhibit transferase-type reactivity with their ligands, allowing the attachment of any moiety-of-interest to the tag. cTag utilizes an engineered C1 domain-bearing cysteine that undergoes a group-transfer reaction with its ligand. Likewise, mgTag utilizes an engineered zinc-finger domain-bearing cysteine that undergoes a group-transfer reaction with its molecular glue ligand in the presence of cereblon (CRBN). While the fusion of HaloTag (297 aa) or SNAPTag (182 aa) to the KRASG12D (188 aa) disrupted its growth-signaling pathway, fusion of mgTag or cTag did not, pointing to the importance of tag size. Group-transfer of BRD4 binder to tags appended to Abelson kinase (ABL) induced proximity between ABL and BRD4, resulting in the latter's phosphorylation. Deletion of the transferase-type reactivity reduced phosphorylation levels, suggesting that proximity-inducing chimeras with group-transfer design may be more efficacious. We envision these ultrasmall tags to have wide-ranging applications, including in basic science, biotechnology, and medicine.","PeriodicalId":520556,"journal":{"name":"Angewandte Chemie (International ed. in English)","volume":" ","pages":"e202506997"},"PeriodicalIF":16.9,"publicationDate":"2025-09-27","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145180864","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":0,"RegionCategory":"","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

引用次数: 0