Zhu T, Chan SKS, Gerritz L
… +4 more, Nizkorodov SA, Shiraiwa M, Chan MN, Tse YS
J Am Chem Soc
· 2026 Jun · PMID 42339664
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Organosulfates are major reservoirs of sulfur in atmospheric aerosols, yet the molecular steps by which hydroxyl radicals (OH) convert organosulfates into inorganic sulfate in aqueous particles remain poorly constrained....Organosulfates are major reservoirs of sulfur in atmospheric aerosols, yet the molecular steps by which hydroxyl radicals (OH) convert organosulfates into inorganic sulfate in aqueous particles remain poorly constrained. This uncertainty limits the mechanistic interpretation of organosulfate chemical aging and its representation in atmospheric models. Here, we use methyl sulfate, CHOSO, the simplest organosulfate, as a model system to elucidate OH-initiated aqueous oxidation chemistry through integrated quantum-chemical calculations, electron paramagnetic resonance spin trapping, and high-resolution mass spectrometry. Calculations show that OH oxidation is initiated predominantly by methyl H-abstraction rather than direct attack at the sulfate ester, producing a carbon-centered radical that rapidly adds O to form a peroxy radical. Subsequent peroxy-peroxy chemistry forms a tetroxide intermediate whose decomposition favors stepwise O-O bond scission to alkoxy sulfate radicals, while classical Russell and Bennett-Summers pathways are kinetically inaccessible. The key sulfate-forming step is a water-assisted, proton-coupled C-O bond cleavage of the alkoxy sulfate radical. Extended hydrogen-bond networks markedly lower the barrier for this fragmentation, enabling direct formation of bisulfate/sulfate and a formyl radical without requiring sulfite or sulfate radical anions as obligatory intermediates. Experimentally, mass spectrometry detects a BMPO-trapped methyl sulfate radical and an adduct consistent with formyl-radical formation, whereas sulfur-centered radical adducts are minor under our conditions. These combined results reveal a non-sulfur radical pathway for inorganic sulfate formation from organosulfates and highlight the central role of explicit solvation and proton transfer in aqueous aerosol sulfur chemistry.
J Am Chem Soc
· 2026 Jun · PMID 42339617
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Recent advances in mechanochemistry have shown that the deliberate incorporation of mechanically weak bonds, specifically scissile mechanophores, can improve the fracture resistance of polymer networks. In pendant cross-...Recent advances in mechanochemistry have shown that the deliberate incorporation of mechanically weak bonds, specifically scissile mechanophores, can improve the fracture resistance of polymer networks. In pendant cross-linked elastomers (e.g., side-chain cross-linked or vulcanized elastomers), bifunctional mechanophores incorporated into cross-links produce substantial toughening. By contrast, utilizing the same motifs for toughening in end-linked or step-growth networks, which are ubiquitous in industrial thermosets, has remained a challenge. Here, by establishing a topological correspondence between pendant cross-linked and end-linked architectures, we identify a design strategy that enables bifunctional scissile motifs to successfully toughen end-linked networks. We validate this approach using model thermoset polyurethanes and show that the resulting mechanophore-driven toughening is substantial, yielding a 16-fold enhancement in tensile toughness and an 8-fold enhancement in tearing energy. We further show that this strategy can be combined with conventional polyurethane toughening approaches to produce materials with outstanding properties. More broadly, this work establishes strand continuity as a mechanochemical design principle for fracture resistant materials across diverse polymer architectures.
Chatterjee A, Roy R, Sarkar S
… +9 more, Sarkar S, Chaini A, Roy AN, Jana B, Ethirajan A, Pal U, Barman S, Ghosh S, Das A
J Am Chem Soc
· 2026 Jun · PMID 42339607
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Amyloid-β 42 () misfolding and self-assembly drive proteostatic collapse in Alzheimer's disease, but chemically programmable systems enabling sequence-selective recognition and remodeling of the aggregation pathway rema...Amyloid-β 42 () misfolding and self-assembly drive proteostatic collapse in Alzheimer's disease, but chemically programmable systems enabling sequence-selective recognition and remodeling of the aggregation pathway remain elusive. We report a rationally engineered supramolecular composite, , that integrates benzo-18-crown-6 () to form a supramolecular inclusion complex with the ε-NH group on lysine, a short peptide sequence targeting the motif of , and a PEG appendage to enhance pharmacokinetics and blood-brain barrier permeability. Cooperative multivalent engagement of this motif, confirmed by H-N HSQC NMR, confers markedly enhanced affinity (K ∼ 7.4 × 10 M toward monomeric ) relative to individual components (≤10 M), demonstrating synergistic binding. Importantly, not only blocks nucleation-dependent aggregation but also effectively destabilizes soluble oligomers, as well as mature aggregates, revealing a mechanistically distinct supramolecular modulation of the aggregation pathway relative to conventional inhibitors. The nontoxic conjugate mitigates oxidative stress, restores mitochondrial function, reinstates glial-neuronal connectivity, and improves cognition in an Alzheimer's model. More broadly, this work introduces a conceptual design principle that integrates precision Lys-clamp by with targeting of the aggregation-prone motif to enable chemically programmable, multivalent intervention in pathogenic protein assemblies.
Schuler M, Koca E, Driehaus-Ortiz L
… +7 more, Braun MG, Lahu A, Holtmannspötter AL, Nguyen HC, Boekhoven J, Ng DYW, Weil T
J Am Chem Soc
· 2026 Jun · PMID 42339573
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Biomolecular condensates formed through liquid-liquid phase separation play central roles in intracellular organization and regulation. Replicating such dynamic compartmentalization using minimal synthetic components rem...Biomolecular condensates formed through liquid-liquid phase separation play central roles in intracellular organization and regulation. Replicating such dynamic compartmentalization using minimal synthetic components remains exceptionally challenging inside living cells. Here, we report short cationic peptides that undergo directed complex coacervation in living cells through preferential interactions with endogenous polyanionic biomolecules. Although the peptides were designed to contain a mitochondrial targeting motif, the Arg residues and cellular RNA guide the supramolecular interactions toward selective enrichment of liquid-like coacervates in nucleolar regions. In vitro studies reveal that polymeric RNA mimics promote coacervation far more efficiently than ATP, establishing RNA-peptide interactions as the principal driving force. In cells, nucleolar complex coacervates form rapidly and exhibit liquid-like behavior with fast molecular exchange. Importantly, the assemblies are transient and reversible: sustained peptide supply maintains the condensed state, whereas substrate depletion triggers droplet dissolution and recovery of cellular function. These findings demonstrate that endogenous biopolymer distributions can guide and participate in the formation of synthetic coacervates with minimalistic peptides, achieving reversible reorganization of intracellular components. More broadly, this work provides a framework for engineering synthetic coacervates with nonequilibrium, life-like features that operate in direct exchange with living cellular environments.
J Am Chem Soc
· 2026 Jun · PMID 42339568
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A short and diastereoselective synthesis of stephadiamine is presented. The carbocyclic framework of the alkaloid was built in the opening step through a homoconjugate addition-Wittig olefination cascade with a modified...A short and diastereoselective synthesis of stephadiamine is presented. The carbocyclic framework of the alkaloid was built in the opening step through a homoconjugate addition-Wittig olefination cascade with a modified Schweizer-Fuchs cyclopropyl phosphonium salt. The challenging [4.3.3]propellane was subsequently installed through a vinylogous substitution of an allylic hydroxy group with a primary amine that was developed for the purposes of the synthesis. After a series of oxidations, a second α-tertiary amine was introduced through a diastereoselective Strecker reaction, thus establishing the -diamine motif. Finally, an undesired -Strecker pathway was circumvented by using an azide functionality to mask the primary amine during a late-stage lactonization, thus enabling the completion of the synthesis in 12 steps.
Ghosh S, Kothari M, Kalita S
… +6 more, Kushwaha V, Sarkar S, Nandy T, Agasti SS, Chowdhury A, George SJ
J Am Chem Soc
· 2026 Jun · PMID 42339529
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Supramolecular polymerization has entered a vibrant new stage in which precise control over self-assembly pathways enables hierarchical topologies that emulate covalent polymer systems in structure and function, while al...Supramolecular polymerization has entered a vibrant new stage in which precise control over self-assembly pathways enables hierarchical topologies that emulate covalent polymer systems in structure and function, while also providing access to complex organic heterostructures previously inaccessible through bottom-up self-assembly strategies. In this context, the present work delivers the first precision-designed light-harvesting supramolecular donor-acceptor double-cable polymers with orthogonal heterojunctions, constructed through a surface-catalyzed heterogeneous nucleation pathway that mirrors well-defined covalent analogues. As a proof of concept, core substituted naphthalene diimide (cNDI) chromophores bearing tripeptide side chains and diverse optoelectronic characteristics are used as modular monomers, where the peptide units simultaneously (i) exploit their chirality to regulate the balance between elongation and surface catalyzed nucleation during seeding and (ii) provide a templated interface that stabilizes a secondary cable growing in parallel on top of a primary stack. Detailed kinetic analysis, guided by spectroscopic studies and concepts adapted from surface-catalyzed protein aggregation, reveals that chirality and seeding conditions selectively channel growth through heterogeneous surface nucleation while suppressing competing pathways. This level of control further enables programmable modulation of heterojunction length through sequential seeding. Furthermore, spectral and time-resolved fluorescence microscopy of individual supramolecular double-cable heterostructures demonstrate efficient resonance energy transfer between the parallel donor and acceptor cables, establishing light-harvesting functionality at the single-chain level. Overall, this study presents a unique manifestation of hierarchical supramolecular polymerization that pushes the limits of precision and complexity in supramolecular polymers, an advance that is crucial for the continued expansion of this exciting field.
Yurdusen A, Malik P, Mansouri A
… +16 more, Dovgaliuk I, Garvin M, Song AY, Pourghaderi A, Jin X, Stuart L, Chakraborty D, Nandi S, Fernando LA, Beauvois A, Briois V, Reimer JA, Garcia S, Smit B, Mouchaham G, Serre C
J Am Chem Soc
· 2026 Jun · PMID 42338394
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Herein, we report two heterometallic ultramicroporous metal-organic frameworks, MIP-212(Al/Cu) and MIP-212(Al/Zn) (MIP stands for Materials from Institute of Porous Materials of Paris), synthesized via a hard-soft acid-b...Herein, we report two heterometallic ultramicroporous metal-organic frameworks, MIP-212(Al/Cu) and MIP-212(Al/Zn) (MIP stands for Materials from Institute of Porous Materials of Paris), synthesized via a hard-soft acid-base design strategy. In these robust pyrazolate-carboxylate architectures, pyrazolates selectively coordinate Cu or Zn, while carboxylates bind Al, generating chain-based inorganic building units built up from connected M-pyrazolate polyhedra and μ-OH-corner-shared AlO octahedra, respectively. The resulting structures feature dual ultranarrow tunnel-like pores, one decorated with μ-OH groups. MIP-212(Al/Cu) combines pore confinement with Cu open metal sites (OMS) to deliver benchmark-level CO uptake at low pressure (2.30 mmol g at 0.15 bar, 298 K) and a CO/N Ideal Adsorbed Solution Theory (IAST) selectivity of ∼30. However, the OMS also imparts marked hydrophilicity, diminishing CO uptake under humid conditions. Markedly, replacing octahedral Cu with tetrahedral Zn centers in MIP-212(Al/Zn) suppresses OMS while preserving framework topology, resulting in significantly lower water affinity (up to ca. 4-fold reduction at 0.2 bar of HO) and superior CO breakthrough performance at 50% RH. These findings demonstrate that metal coordination geometry is a powerful lever to modulate hydrophilicity and sorption behavior in MOFs, enabling the rational design of sorbents for efficient CO capture under realistic, moisture-rich environments.
Hao R, Zhai Z, Li S
… +9 more, Sha Y, Chu S, Wang R, Yin K, Wang F, Zhang L, Ma X, Zhong H, Zhao D
J Am Chem Soc
· 2026 Jun · PMID 42338378
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The pursuit of high-performance wide-bandgap polymer (WBG) donors remains a pivotal challenge for advancing nonfullerene organic solar cells (OSCs). Herein, we address this challenge via creating a novel electron-deficie...The pursuit of high-performance wide-bandgap polymer (WBG) donors remains a pivotal challenge for advancing nonfullerene organic solar cells (OSCs). Herein, we address this challenge via creating a novel electron-deficient building block, difuranylphthalimide (DFI), via a strategic sulfur-to-oxygen atom swap in dithienophthalimide (DTI). This atomic substitution engenders a polymer, PDFI, with distinctly advantageous properties derived from the furan moieties: a deeper highest occupied molecular orbital (HOMO) energy level, enhanced backbone planarity and crystallinity, and superior miscibility with state-of-the-art nonfullerene acceptors. These characteristics collectively foster optimized blend morphology with tighter π-π stacking, more efficient charge transport, and significantly suppressed nonradiative energy loss. Consequently, binary OSCs based on PDFI and the acceptor BTP-eC9 achieve an impressive power conversion efficiency (PCE) of 19.17%, which is the highest value achieved by furan-containing donor materials in OSCs to date. Furthermore, incorporating PDFI as a third component into the PM6:L8-BO system yields a ternary device with a PCE exceeding 20%. This work not only introduces PDFI as a top-performing nonhalogenated polymer donor but also establishes the incorporation of furan into electron-deficient units as a transformative strategy for developing high-efficiency, sustainable organic photovoltaic materials.
Chen Z, Liu X, Sang W
… +16 more, Li L, Xiao J, Hu G, Zhou L, Qi Q, Peng C, Huang J, Xiong W, Li Z, Chen N, Zhang E, Yu L, Jiang H, Tian T, Zhou X, Deng H
J Am Chem Soc
· 2026 Jun · PMID 42338353
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We report the use of reticular design to construct metal-organic frameworks (MOFs) with molecularly defined catalytic pores for bioorthogonal RNA manipulation in living cells. A library of crystalline MOFs with systemati...We report the use of reticular design to construct metal-organic frameworks (MOFs) with molecularly defined catalytic pores for bioorthogonal RNA manipulation in living cells. A library of crystalline MOFs with systematically varied Cu cluster geometries, pore dimensions, and chemical environments was assembled to interrogate how structural precision influences RNA recognition and conversion within confined spaces. By integration of redox-stable Cu(I) clusters with dimensionally matched mesopores, selected MOFs were capable of catalyzing efficient and quantitative RNA bond cleavage and formation reactions in living systems without external reducing agents. Small-angle X-ray scattering reveals that pore chemistry governs substrate positioning relative to catalytic centers, enabling preferential engagement of protected RNA and facilitated release of original RNA as products, thereby driving complete conversion. Synchrotron soft X-ray microscopy was used to visualize intracellular localization and integrity of MOF in cells, further validating MOF as a bioorthogonal catalyst. An amine-functionalized framework, MOF-248-NH, enabled controlled sgRNA activation for CRISPR/Cas9 gene editing regulation in cells and treatment of cardiac disease in a canine model. These results establish reticular pore engineering as a powerful strategy to make MOFs programmable bioorthogonal catalysts.
J Am Chem Soc
· 2026 Jun · PMID 42338066
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Display technologies discover high-affinity peptides from vast combinatorial libraries. In mRNA display, flexizyme-enabled genetic code reprogramming has become the dominant approach to extend building block diversity an...Display technologies discover high-affinity peptides from vast combinatorial libraries. In mRNA display, flexizyme-enabled genetic code reprogramming has become the dominant approach to extend building block diversity and improve drug-relevant properties, yet post-translational modifications (PTMs) capable of installing more uniquely constrained backbone topologies remain underexplored. Here, we introduce a PTM strategy that broadens this scope by installing an aspartyl aldehyde (X), which undergoes spontaneous Pictet-Spengler-type cyclization with proximal nucleophilic side chains to yield polycyclic α-amino-γ-lactam (pcAgl) motifs. Systematic studies define the equilibria, stereochemistry, and side-chain requirements governing pcAgl formation under biocompatible conditions. Incorporation of this chemistry into reprogrammed peptide libraries enabled direct in vitro selection of pcAgl-containing ligands against the oncology target MAT2A. The selected peptides contained structurally critical pcAgl motifs, inhibited the enzyme (best IC = 9 μM), and showed improved stability in human serum. This work establishes aldehyde-mediated peptide backbone alkylation in mRNA display and showcases the value of applying chemistries traditionally not considered biocompatible to expand the chemical space of genetically encoded libraries.
Zhang D, Tang R, Ma Y
… +6 more, Zhao Q, Zheng Q, Wei Y, Long DL, Cronin L, Xuan W
J Am Chem Soc
· 2026 Jun · PMID 42336797
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The controlled assembly of giant molybdenum-red polyoxometalates (POMs) into high-order architectures and elucidating their structure-property relationships remain a formidable challenge. We report an unprecedented 204-n...The controlled assembly of giant molybdenum-red polyoxometalates (POMs) into high-order architectures and elucidating their structure-property relationships remain a formidable challenge. We report an unprecedented 204-nuclearity hollow nanocage, {Mo}@{Mo} (), featuring a host-guest architecture where a {Mo} shell encapsulates a -{Mo} guest, together with its one-dimensional chain derivative, [{Mo}@{Mo}{Mo}] (), in which the -{Mo} clusters further act as linkers. The drum-shaped {Mo} shell in is constructed from classical {Mo} and {Mo} units, complemented by phenylphosphonate(L)-induced novel V-shaped {MoL} and {MoL}* building blocks. Featuring highly reduced molybdenum centers and localized reducing electrons on Mo-Mo bonds, it forms a massive internal cavity (∼2.2 nm × 1.5 nm). The discovery of significantly expands the structural library of rare giant molybdenum-red clusters. Intriguingly, its assembly triggers a symmetry breaking from pseudo- to , shifting the architecture further away from an ideal fullerene-like topology. To accommodate the directional assembly of -{Mo} linkers, two equatorial {MoL}* units in each detach a {Mo} tail, converting the {Mo} cage into a {Mo} entity with open connection sites to ultimately form the 1D polymeric chain . Benefiting from dense proton-conductive sites and large open windows, exhibits a high conductivity of 8.28 × 10 S cm (80 °C, 98% RH). More impressively, continuous 1D pathways in boost this value to an ultrahigh 1.28 × 10 S cm, ranking among the best POM-based proton conductors. This work demonstrates rare dimensional evolution in giant POMs and establishes a new paradigm for designing high-performance solid-state proton conductors.
Cool LM, Pawar J, Sonam S
… +7 more, Kumari S, Zhao SL, Hu X, Lin Z, Wu M, Hu S, Peterson BR
J Am Chem Soc
· 2026 Jun · PMID 42336767
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Precise measurements of small molecule-protein interactions are critical for drug discovery. However, most biochemical profiling platforms measure binding using recombinant kinase domains or proteins in cell lysates, whi...Precise measurements of small molecule-protein interactions are critical for drug discovery. However, most biochemical profiling platforms measure binding using recombinant kinase domains or proteins in cell lysates, which can miss conformational regulation present in intact living cells. Here, we used flow cytometry-based fluorescent probe cellular binding assays (FPCBA) to demonstrate that the anticancer drug dasatinib binds native, untagged ABL1 kinase with 3-6-fold higher affinity than NanoLuc- or mVenus-tagged constructs in living cells. We further used this method for in-cell profiling of 25 native kinases, revealing conformational regulatory mechanisms, including SRC autoinhibition and membrane-dependent conformational states of DDR1, DDR2, and EPHA4 that are absent or attenuated in biochemical assays. For these studies, coumarin-dasatinib probes spanning a range of fluorophore acidity (p 4.1-7.3) were optimized for intracellular target engagement. To enhance sensitivity of detection, we found that uptake of acidic probes can be promoted by expression of the organic anion transporter OATP1B3. Quantitative flow cytometry with NIST-standardized beads established that intracellular concentrations of an intermediate-acidity 6FC-dasatinib probe approximated extracellular concentrations in HEK293T cells at equilibrium. Cellular values of dasatinib and imatinib for 25 kinases by FPCBA were broadly concordant with kinobead LC/MS measurements in cancer cell lysates but diverged substantially from recombinant KINOMEscan values, with divergences attributable to competition with ATP, autoinhibition, and membrane-dependent conformational states in living cells. FPCBA enables profiling of native protein-small molecule interactions in a physiologically relevant cellular context.
Jiang J, Chen Y, Wan R
… +8 more, Huang C, Xiang T, Luo C, Deng J, Zhang Z, Liu T, Tan Y, Li Z
J Am Chem Soc
· 2026 Jun · PMID 42336393
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Targeted protein degradation (TPD) is a promising therapeutic strategy, yet its application remains constrained by the limited repertoire of available E3 ubiquitin ligases, primarily CRBN and VHL. Here, we identify RNF21...Targeted protein degradation (TPD) is a promising therapeutic strategy, yet its application remains constrained by the limited repertoire of available E3 ubiquitin ligases, primarily CRBN and VHL. Here, we identify RNF213 as a recruitable E3 ligase that mediates protein degradation induced by molecular glue degraders. We developed by equipping the pan-FGFR inhibitor Infigratinib with a minimal dibromoacetamide covalent warhead. This covalent molecular glue recruits RNF213 to potently degrade FGFR1-4, with the strongest effect on FGFR2 (DC = 27 nM, = 96%). outperforms parent inhibitors in vitro (IC = 3.8 nM) and shows comparable antitumor efficacy in vivo (TGI = 94.6%), with sustained target suppression and no apparent hook effects under the tested conditions. Notably, the dibromoacetamide warhead is transplantable, enabling selective degradation of other challenging targets such as WEE1 and CDK12, which regulate cell-cycle progression and transcription. This offers a rational strategy for creating molecular glues. Our work identifies RNF213 as an exploitable ligase for TPD and establishes covalent molecular glues as a modular platform. This strategy expands the scope of degrader design beyond conventional E3 ligases, offering an avenue for developing potent and selective therapeutics.
Martins L, Zhu Y, Misselwitz E
… +7 more, Horn Y, Wald SR, Rominger F, Wei Z, Zaumseil J, Petrukhina MA, Kivala M
J Am Chem Soc
· 2026 Jun · PMID 42335470
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Two tetrasubstituted pyracylene derivatives were synthesized and chemically reduced using alkali metals. X-ray crystallographic evidence of the neutral, monoanionic, and dianionic states was obtained for both the -propyl...Two tetrasubstituted pyracylene derivatives were synthesized and chemically reduced using alkali metals. X-ray crystallographic evidence of the neutral, monoanionic, and dianionic states was obtained for both the -propyl and 4--butylphenyl-substituted derivatives, which were further characterized by NMR, EPR, and UV-vis spectroscopy studies. The aromaticity of each state was comprehensively examined using both experimental and computational methods. Both compounds feature an antiaromatic [12]annulene carbocycle in the neutral state, which turns aromatic upon 2-fold reduction to a 14 π-electron system. -Propyl substitution enhances the localized negative charge density and aromaticity within the five-membered rings in the dianionic state. In contrast, aryl substitution stabilizes the aromatic annulene character of the dianion, triggers photoluminescence, and enables further reduction coupled with enhanced reactivity. The use of potassium metal gives a highly reactive third reduction state of 4--butylphenyl derivative, which transforms the carbon scaffold into a phenanthrene-pyracylene hybrid via 2-fold reductive cyclodehydrogenation.
Cha L, Qian C, Padhi C
… +2 more, Zhu L, van der Donk WA
J Am Chem Soc
· 2026 Jun · PMID 42335466
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Nitrile-containing natural products are produced in all kingdoms of life. Despite the wide application of nitrile-containing peptide scaffolds in medicinal chemistry, the presence of the nitrile group is unprecedented in...Nitrile-containing natural products are produced in all kingdoms of life. Despite the wide application of nitrile-containing peptide scaffolds in medicinal chemistry, the presence of the nitrile group is unprecedented in ribosomally synthesized and post-translationally modified peptides (RiPPs). In this work, we report the identification and characterization of a RiPP biosynthetic gene cluster (BGC), where an asparagine synthetase-like (AS-like) protein encoded in the BGC converts the C-terminal carboxylate of the precursor peptide to a nitrile. Furthermore, a multinuclear nonheme iron-dependent oxidative enzyme (MNIO) and an α-ketoglutarate-dependent HExxH motif-containing enzyme (αKG-HExxH) perform stereoselective β-hydroxylation of aspartate and proline residues, respectively. Structure prediction-guided mechanistic evaluation of the nitrile synthetase provided insights into the possible mechanism of catalysis. These findings extend our understanding of the structural diversity of RiPPs and demonstrate the catalytic versatility of AS-like enzymes in natural product biosynthesis.
J Am Chem Soc
· 2026 Jun · PMID 42335279
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6-sulfo Lewis x-related glycan epitopes, including 6-sulfo Lewis x and its sialylated form, sialyl 6-sulfo Lewis x, constitute an important class of carbohydrate determinants that are widely expressed in human cells. Elu...6-sulfo Lewis x-related glycan epitopes, including 6-sulfo Lewis x and its sialylated form, sialyl 6-sulfo Lewis x, constitute an important class of carbohydrate determinants that are widely expressed in human cells. Elucidating the biological roles and structure-function relationships of these glycans has attracted considerable attention, as a substantial body of literatures suggest that 6-sulfo Lewis x-related glycans regulate numerous physiological and pathological processes through interactions with their glycan-binding proteins. However, the synthesis of intact complex glycans processing 6-sulfo Lewis x or sialyl 6-sulfo Lewis x glycan epitopes is much more difficult, as the incorporation of the sulfate group and sialic acid residue introduces additional complexity to the oligosaccharide synthesis. Here, we present a chemoenzymatic synthetic strategy for the efficient synthesis of complex N-glycans and O-glycans bearing 6-sulfo Lewis x-related epitopes. By screening a microarray prepared with this glycan library, we systematically probed their binding specificities with many important human glycan-binding proteins. The results provide an insightful understanding of the structure-function relationships of this important class of glycan structures.
J Am Chem Soc
· 2026 Jun · PMID 42335201
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Altermagnetism has recently emerged as a new class of spin compensated magnetic materials that exhibit momentum dependent spin splitting despite having zero net magnetization. The origin of these electronic signatures li...Altermagnetism has recently emerged as a new class of spin compensated magnetic materials that exhibit momentum dependent spin splitting despite having zero net magnetization. The origin of these electronic signatures lies in symmetry operations that connect opposite spin sublattices while allowing spin splitting in momentum space. While most candidate materials identified so far belong to inorganic crystals with fixed lattice symmetries, the realization of altermagnetism ultimately requires platforms in which magnetic symmetry can be deliberately engineered. In this Perspective, we discuss how metal-organic frameworks (MOFs) provide a unique chemical platform to address this challenge. We first place altermagnetism in the broader context of magnetic and electronically active metal-organic networks, highlighting how reticular chemistry enables precise control over lattice geometry, dimensionality and electronic structure. We then discuss how these features position framework materials as promising candidates for realizing altermagnetism and highlight the key challenges that must be addressed to translate theoretical proposals into experimentally accessible systems. Finally, we outline emerging directions for realizing and controlling altermagnetism in coordination framework materials, which emerge as a versatile and powerful platform for exploring new paradigms in spintronics.
Li J, Li Q, Zhao Z
… +4 more, Mi R, Li XX, Wang F, Li X
J Am Chem Soc
· 2026 Jun · PMID 42335189
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The insertion of arene C-H bonds to alkenes (the Murai reaction) has been established as a strategic protocol to access value-added aromatics, but the regioselectivity is predominantly to 1,2-selectivity. On the other ha...The insertion of arene C-H bonds to alkenes (the Murai reaction) has been established as a strategic protocol to access value-added aromatics, but the regioselectivity is predominantly to 1,2-selectivity. On the other hand, terminal alkenes may undergo remote functionalization via chain-walking that is predominantly initiated by an exogenous hydride source. It remains a daunting challenge to integrate asymmetric Murai reaction and olefin chain-walking to expand the boundary of this reaction in terms of regio- and stereoselectivity. Reported herein is rhodium-catalyzed Murai reaction between arenes bearing an diarylphosphino directing group and two categories of amide-functionalized terminal alkenes. In the case of long-chained terminal olefin-amides, the hydroarylation gives branched products via rapid chain-walking of metal alkyl species to the chelation-stabilized β position, affording proximally disposed axial and central chirality with Markovnikov selectivity. The 1,2-hydroarylation of α-substituted acrylamides afforded distally disposed axial and central chirality with -Markovnikov selectivity. The coupling system proceeds with high enantioselectivity, excellent diastereoselectivity (>20:1 d.r.), and 100% atom-economy. The catalytic reactivity has been enabled by judicious choice of additives and a chiral phosphoramidite, which overrides the inhibitive effect of the coupled product. Selected products proved to be effective chiral ligands in metal-catalyzed asymmetric C-C coupling reactions.