Tonk K, Sun S, Bamidele OH
… +9 more, Niu M, Zuo X, Lamb JV, Kropf AJ, Delferro M, Lee B, Heyden A, Huang W, Sadow AD
J Am Chem Soc
· 2026 Jun · PMID 42359561
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A catalyst architecture with mesoporous silica coating Ru nanoparticles on reduced graphene oxide (mSiO/Ru/rGO) localizes the 2 nm Ru solely at the closed bottoms of 2.9 nm diameter mesopores. mSiO/Ru/rGO catalyzes the r...A catalyst architecture with mesoporous silica coating Ru nanoparticles on reduced graphene oxide (mSiO/Ru/rGO) localizes the 2 nm Ru solely at the closed bottoms of 2.9 nm diameter mesopores. mSiO/Ru/rGO catalyzes the rapid, selective hydrogenolysis of polyolefins at wax formation rates (ν) up to 1700 g·g·h and a turnover frequency (TOF) for C-C bond cleavage of 130 ± 8 min. The ν and TOF for mSiO/Ru/rGO are 23× and 16× those of nonporous Ru/rGO, respectively, indicating that faster chain cleavage is also more selective inside mesopores. The methane yield from mSiO/Ru/rGO is ca. 30% of the value obtained from Ru/rGO. Methane decreases, and wax selectivity improves with narrow-pore (2.3 nm) mSiO/Ru/rGO. The reaction rate decreases at lower and higher H pressures from its maximum at 37 bar. Log(TOF)-log() plots reveal rates ∝ [] or [] in the lower or higher pressure ranges, respectively. Corresponding plots for Ru/C give rates ∝ [] or []. Ru is hydrocarbon-covered at low pressure; thus, the higher H order for mSiO/Ru/rGO indicates that mesopores increase the density of cleavable unsaturated moieties on the Ru surface. The lower H order on Ru/C implies a lower density of cleavable groups because saturated segments occupy a larger fraction of the Ru surface. Higher surface occupancy by the hydrocarbon reactant correlates with more methane formation. Therefore, pore confinement, narrower pore diameter in mSiO/Ru/rGO, or higher H pressure leads to lower methane yields. Ru nanoparticles in mSiO/Ru/rGO maintain equivalent activity and selectivity over five recycling tests.
Kim JH, Mills CE, Kozicka Z
… +19 more, Scott DC, Jin C, Jiang Z, Dwyer BG, Geng Q, Toenjes ST, Byun WS, ElHarouni D, Li H, Ligon KL, Thornhill AM, Jones HM, Romero BA, Hinshaw SM, Ebert BL, Schulman BA, Donovan KA, Fischer ES, Gray NS
J Am Chem Soc
· 2026 Jun · PMID 42358219
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PROTACs are commonly developed by linking E3 ligase-recruiting ligands to established inhibitors of a protein target, often resulting in degraders that retain enzymatic inhibition. Type II inhibition of cyclin-dependent...PROTACs are commonly developed by linking E3 ligase-recruiting ligands to established inhibitors of a protein target, often resulting in degraders that retain enzymatic inhibition. Type II inhibition of cyclin-dependent kinases (CDKs) has been challenging, as reported compounds generally exhibit weak biochemical potency and limited cellular activity. Consistent with these limitations, most reported CDK degraders have been derived from type I ATP-competitive inhibitors. Here, we explored whether targeted protein degradation could enable functional CDK targeting from a type II kinase scaffold. Using the multikinase inhibitor regorafenib as a starting scaffold, we generated a focused library of CRL4-recruiting bifunctional molecules and profiled their degradation activity using quantitative mass spectrometry-based proteomics. This analysis unexpectedly revealed CDK5 and CDK6, kinases not inhibited by the parent scaffold, as degradation targets. Optimization of this series led to , a selective CDK6 degrader that does not display a hook effect and promotes potent CDK6 degradation despite weak CDK6 binding and negligible CDK6 inhibition. In cellular models of acute myeloid leukemia (AML) and glioblastoma, induced sustained G1 arrest and reduced phosphorylation of the retinoblastoma protein. Interestingly, subtle modifications in PROTAC architecture redirected degradation selectivity, yielding as a selective type II CDK5 degrader derived from the same scaffold. Together, these findings establish the first type II inhibitor-derived selective CDK6 degrader and demonstrate that targeted protein degradation can enable functional CDK targeting from type II kinase scaffolds.
Fu W, Hu W, Jing H
… +7 more, Wang T, Wang C, Liu F, Gao D, Yuan H, Pang R, Zhang N
J Am Chem Soc
· 2026 Jun · PMID 42358070
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The generation of RNA-DNA hybrid G-quadruplexes (RDQs) through heteromeric association between individual DNA and RNA G-rich strands has been proposed as an important mechanism in the regulation of genome transcription,...The generation of RNA-DNA hybrid G-quadruplexes (RDQs) through heteromeric association between individual DNA and RNA G-rich strands has been proposed as an important mechanism in the regulation of genome transcription, replication, and telomere capping. Based on low-global-structure-resolution circular dichroism spectra, numerous RDQs have been routinely detected almost exclusively in a parallel topology because of the inherent preference of riboguanosine (rG) to adopt an glycosidic torsion angle. However, high atomic-resolution structures of RDQs resolved using nuclear magnetic resonance (NMR) spectroscopy, X-ray crystallography, or cryogenic electron microscopy (CryoEM) remain unavailable in the PDB database at present. To the best of our knowledge, this study is the first to present an NMR structure of a human telomeric RDQ (Htel-RDQ) assembled between a three-repeat human telomeric DNA strand of d(GGGTTAGGGTTAGGG) and a single-repeat TERRA RNA strand of r(UAGGGU). Interestingly, this Htel-RDQ uncommonly adopts a (3 + 1) hybrid topology featuring three parallel and one antiparallel strand orientations, with one rG atypically in the glycosidic torsion angle and a sugar pucker conformation. The findings of this study confirm that the inherent rG preference in RNA G-quadruplexes can be adaptively unrestricted in an RDQ assembly and disclose a latent structural complexity previously unanticipated in RDQs.
Zhang R, Yu X, Du S
… +5 more, Hu R, Chen R, An L, Liu Z, Wang C
J Am Chem Soc
· 2026 Jun · PMID 42357943
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Rheumatoid arthritis is a systemic autoimmune disorder with a markedly unmet clinical need for highly effective and well-tolerated therapeutic agents with minimal toxicity. Herein, 15 C20-diterpenoid alkaloids, including...Rheumatoid arthritis is a systemic autoimmune disorder with a markedly unmet clinical need for highly effective and well-tolerated therapeutic agents with minimal toxicity. Herein, 15 C20-diterpenoid alkaloids, including nine novel compounds, delphyuanines A-I (-), were isolated from Chen. Notably, delphyuanine A () represents an exceptionally rare vakognavine-type C20-diterpenoid alkaloid with only 22 congeners of this subclass reported to date. Furthermore, in an LPS-induced macrophage inflammation model, nitric oxide production was substantially inhibited by Compound , and its inhibitory effect was markedly stronger than that of the other isolated compounds. Moreover, Compound exhibits potent antiarthritic efficacy in an adjuvant-induced arthritis rat model. Using a probe-affinity labeling assay, the transcription factor FoxO1 was confirmed to be the direct molecular target of Compound . Further molecular mechanistic studies demonstrated that Compound exerts antirheumatoid arthritis activity by directly targeting FoxO1, thereby inhibiting its nuclear translocation, promoting M2 macrophage polarization, and suppressing the NF-κB signaling pathway. Collectively, these findings provide valuable guidance for the rational design of anti-RA drugs and identifies Compound as a promising lead compound for the treatment of autoimmune diseases.
Song W, Zhang Y, Wang Y
… +8 more, Xu H, Chai X, Zhao W, Zhao H, Ding S, Gao G, Zeng L, Xiao C
J Am Chem Soc
· 2026 Jun · PMID 42357872
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Achieving durable oxygen evolution reaction (OER) under industrial alkaline water electrolysis (AWE) conditions remains a formidable challenge, arising from dynamic Fe dissolution and segregation in NiFe layered double h...Achieving durable oxygen evolution reaction (OER) under industrial alkaline water electrolysis (AWE) conditions remains a formidable challenge, arising from dynamic Fe dissolution and segregation in NiFe layered double hydroxides (LDH) and further aggravated by sluggish ion transport and bubble release at the gas-liquid-solid interface. Herein, we report a design concept of using an ultrathin sodium polyacrylate (PANa) hydrogel layer on NiFe LDH as a spatially confining, transport-permissive interphase to dynamically stabilize Fe sites and enhance multiphase interfacial transport for boosting OER durability in hectowatt-scale AWE. We demonstrate that the PANa interphase converts uncontrolled Fe dissolution-segregation into an interfacially confined and self-regulated dissolution-redeposition process, in which carboxylate-mediated Fe-O-C coordination thermodynamically stabilizes lattice Fe by suppressing overoxidation, while the hydrated polymer network kinetically retains transiently dissolved Fe within the interfacial region and favors its reincorporation toward homogeneous active-phase regeneration. Meanwhile, the carboxylate-rich framework reorganizes the interfacial hydrogen-bond network to accelerate OH transport and promote rapid O disengagement through its porous superaerophobic architecture. In an industrial 600 W-scale alkaline electrolyzer (679 cm total anode area), the PANa/NiFe LDH anode sustains stable operation for over 2500 h at 0.5 A cm, with an energy consumption as low as 4.25 kWh Nm H and a competitively low projected hydrogen production cost of US$ 2.38 kg.
J Am Chem Soc
· 2026 Jun · PMID 42357865
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Carbon-based metal-free catalysts have attracted considerable interest for the electrochemical nitrogen reduction reaction (eNRR) under ambient conditions, but their activity origin is often attributed to heteroatoms or...Carbon-based metal-free catalysts have attracted considerable interest for the electrochemical nitrogen reduction reaction (eNRR) under ambient conditions, but their activity origin is often attributed to heteroatoms or defects, while this work demonstrates the activity of pure carbon without doping or defects. Herein, we unveil a spin mechanism induced at / carbon interfaces that triggers nitrogen reduction, based on a combination of grand-canonical first-principles calculations, constant-potential AIMD simulations, and rigorous experiments. With the presence of / carbon interfaces in our model, it emerges isolated bands adjacent to the Fermi level and extended spin distribution originating from electronic redundancy. Through a spin-mediated activation mechanism, N is highly activated with chemisorption on the dual-spins of / carbon interfaces. Thermodynamic results show that N adsorption is the single uphill step of eNRR with 1.26 eV, while the following steps proceed downhill with the spontaneous NH desorption at -0.65 V vs RHE. Kinetic barriers, evaluated through constant-potential enhanced sampling, confirm the high activity under typical operating conditions (pH = 7, -0.65 V): with Li, N adsorption needs to overcome a kinetic barrier of 1.22 eV (further to 0.94 eV with a graphene substrate), followed by facile hydrogenation steps to form NH─all featuring kinetic barriers below 0.65 eV. Guided by theory, we synthesized a carbon nanosheet-nanotube composite, experimentally verified / carbon interfaces and spin signatures, and achieved an NH yield rate of 86.3 μg·h·mg, ranking among the best carbon-based metal-free eNRR catalysts. This work highlights the atomic-level insights and interfacial spin engineering for intrinsic reactivity in pure carbon electrocatalysts.
Zhao F, Xiao T, Wang Y
… +8 more, Qi Z, Kang L, Zhang J, Mu C, Guo D, Wan T, Wang S, Ma X
J Am Chem Soc
· 2026 Jun · PMID 42350926
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CeO-supported metal catalysts are highly efficient and widely employed in the ethane-CO coconversion reaction, offering a promising approach to natural gas utilization and greenhouse gas valorization. However, this kind...CeO-supported metal catalysts are highly efficient and widely employed in the ethane-CO coconversion reaction, offering a promising approach to natural gas utilization and greenhouse gas valorization. However, this kind of catalyst with metal-CeO interfaces predominantly favors dry reforming of ethane (DRE) to syngas, while achieving selective dehydrogenation to ethylene remains challenging. Here, a crystal-facet engineering strategy was adopted to fabricate nanoporous CeO (np-CeO) with exposed high-index facets (HIFs). The relatively low-coordinated O atoms on HIFs render a stronger bonding with transition metals (e.g., Co), thereby forming more electron-deficient Co species. Consequently, the unique Co-O-Ce interfaces deliver superior selectivity to ethylene (88% on the basis of ethane) for the ethane-CO coconversion, whereas Co on CeO samples with low-index facets (LIFs) mainly undergoes DRE with only 2% ethylene selectivity. Through combining multiple in situ characterizations and theoretical calculations, it was found that more electron-deficient Co moderates the adsorption and activation of C-H bonds, suppresses the formation of key DRE intermediates (CHO*), and weakens the hybridization with the π orbital of ethylene, thereby promoting product desorption and inhibiting C-C cleavage. This work provides new insights for designing catalysts that achieve high olefin selectivity and CO utilization in alkane-CO coconversion reactions.
J Am Chem Soc
· 2026 Jun · PMID 42350302
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Two-dimensional (2D) nanocomposite membranes have gained significant research interest owing to their high designability, excellent strength, and optimal balance between ion selectivity and flux. However, their character...Two-dimensional (2D) nanocomposite membranes have gained significant research interest owing to their high designability, excellent strength, and optimal balance between ion selectivity and flux. However, their characteristically large interlayer spacing introduces a fundamental trade-off, typically at the expense of ion selectivity. Bioinspired asymmetry, combined with accelerated ion transport dynamics, presents a promising avenue for advancing 2D nanocomposite membranes. Herein, we report an asymmetric heterogeneous 2D composite membrane for efficient osmotic energy conversion, that integrates a gradient architecture with an SA-enabled transport-promoting microenvironment, consistent with hopping-assisted Na transport. The heterogeneous membrane features a dual-layer architecture: a substrate of sulfonated large-sized graphene oxide (GO) nanosheets and bacterial cellulose (BC) for high ion selectivity, and a functional layer of sulfonated small-sized GO nanosheets, BC, and sodium alginate (SA) for enhanced ion flux. This rationally designed structure delivers a power density of approximately 11 W m under a river water/seawater mixture, comparing favorably with representative GO-based membranes under matched artificial-salinity conditions. Temperature-dependent transport measurements, together with continuum and molecular dynamics simulations, support the beneficial roles of the asymmetric structure and SA-containing functional layer, including a lower apparent transport barrier and reduced concentration-polarization-related losses relative to the corresponding controls. This work establishes an asymmetric membrane design strategy for improving the balance between ion selectivity and ion flux in osmotic energy conversion.
Chang L, Shao Y, You X
… +9 more, Luo X, Cui Y, Zhang Z, Wu X, Wang Z, Kang F, Ledendecker M, Li J, Gan L
J Am Chem Soc
· 2026 Jun · PMID 42350151
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The durability of platinum (Pt) electrocatalysts in electrochemical energy conversion is fundamentally challenged by surface oxidation and dissolution during electrochemical operation. Although Pt surface oxidation has c...The durability of platinum (Pt) electrocatalysts in electrochemical energy conversion is fundamentally challenged by surface oxidation and dissolution during electrochemical operation. Although Pt surface oxidation has commonly been discussed in terms of a "place exchange" mechanism between Pt and oxygen, atomic-scale insight into its potential-dependent progression has remained limited. Herein, we directly visualize atomic electrooxidation and dissolution of {111}-terminated surfaces of octahedral Pt nanoparticles by employing differential-phase-contrast scanning transmission electron microscopy combined with online inductively coupled-plasma mass spectroscopy and density functional theory calculations. We reveal the atomistic structural evolution of the {111} nanoparticle surface with progressively increasing electrode potentials (0.8-1.5 V), from the initial lattice expansion induced by adsorbed oxygen, to vacancy-induced formation of two-dimensional, lattice-contracted PtO monolayers, and finally to a dimensional transition to three-dimensional PtO growth. Furthermore, we demonstrate how the potential cycling protocols (triangular versus square wave cycling) decisively control the final oxide's dimensionality (multilayer versus single layer) and stability. These atomic-scale insights establish how electrochemical conditions dictate Pt oxidation pathways and atomistic structural evolution, providing a mechanistic basis for understanding and improving the durability of Pt-based electrocatalysts.
Wilson QD, Mobley EB, Lin EY
… +5 more, Li BY, Hua AS, Liu D, Caram JR, Sletten EM
J Am Chem Soc
· 2026 Jun · PMID 42349864
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The shortwave infrared (SWIR, 1000-2000 nm) region offers significant advantages for fluorescence imaging, including reduced scattering, minimal autofluorescence, and deep-tissue penetration. However, the development of...The shortwave infrared (SWIR, 1000-2000 nm) region offers significant advantages for fluorescence imaging, including reduced scattering, minimal autofluorescence, and deep-tissue penetration. However, the development of small-molecule fluorophores with high brightness and maximum emission above 1100 nm remains a key challenge. Here, we report a new class of silicon-containing flavylium (SiliFlav) polymethine dyes that address this limitation. By incorporating a silicon heteroatom into the established Flav scaffold, we achieve unprecedented bathochromic shifts in emission up to 200 nm, while maintaining respectable fluorescence quantum yields (up to 0.30%). A modular synthetic route enables diverse functionalization at the 1-, 2-, and 7-positions of the heterocycle, allowing for systematic tuning of photophysical properties and improved dye performance. The lead fluorophore, SiliFlav5, formulated into canola oil nanoemulsions, enables bright SWIR emission above 1300 nm. imaging in mice demonstrates high-resolution visualization of the vasculature and spleen, confirming the utility of SiliFlav polymethine dyes as a new platform for deep-tissue SWIR imaging.
Sabbarwal S, Kaswan RR, Galvan J
… +3 more, Willard A, Yahagh A, D'Souza F
J Am Chem Soc
· 2026 Jun · PMID 42348854
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BODIPY chromophores have attracted significant attention due to their various applications in optoelectronics. Notably, symmetry-breaking charge separation (SB-CS) in BODIPYs has been studied to imitate natural photosynt...BODIPY chromophores have attracted significant attention due to their various applications in optoelectronics. Notably, symmetry-breaking charge separation (SB-CS) in BODIPYs has been studied to imitate natural photosynthesis, enabling the efficient production of radical ion pairs upon light absorption. However, most of the chromophores, including the BODIPY derivatives investigated for SB-CS, primarily absorb visible light, unlike natural chlorophylls, which absorb in the far-red and near-infrared (NIR) regions. This results in partial utilization of solar energy, leaving the useful far-red and near-infrared light energy untapped. To overcome the visible-light constraint of conventional artificial chromophores, we introduce NIR-absorbing bisstyryltriphenylamine-BODIPY dimers that bridge the long-standing gap with natural photosynthetic absorbers. Steady-state spectroscopy combined with femtosecond transient absorption studies revealed the ultrafast formation of the charge-separated (CS) state upon photoexcitation. Electrochemical measurements confirm that this process is thermodynamically feasible, as the redox gap is lower than the excited-state energy. The presence of a low-lying charge-transfer state and strong communication between the two monomer units─especially in dimer ─is further supported by quantum-computational calculations, given their coplanarity. These findings demonstrate that these dimers provide a useful platform for SB-CS and NIR light harvesting, offering guidelines for designing next-generation molecular systems with efficient photoinduced energy capture and conversion.
Zhao J, Dong X, Wan W
… +3 more, Qiao L, Yang K, Xia Y
J Am Chem Soc
· 2026 Jun · PMID 42348831
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Annular lipids, which constitute the lipid layer directly interacting with protein transmembrane domains, are essential for maintaining protein structure and function. Nevertheless, the analysis of the dynamic and weak n...Annular lipids, which constitute the lipid layer directly interacting with protein transmembrane domains, are essential for maintaining protein structure and function. Nevertheless, the analysis of the dynamic and weak noncovalent interactions between annular lipids and proteins remains challenging, leaving their interaction details largely underexplored. To address this challenge, we have developed novel phototagging probes, NHS-c-Bpa and IAM-c-Bpa, to capture these weak interactions in peptide-liposome models. The probes feature an NHS moiety for lysine derivatization or an iodoacetamidyl group for cysteine conjugation, a basic pH-cleavable linker, and a -benzoyl-l-phenylalanine (Bpa) group for tagging annular lipids upon UV irradiation. The cross-linked peptide-lipid products are subjected to saponification, followed by liquid chromatography-tandem mass spectrometry (MS/MS) analysis. Importantly, MS/MS analysis resolves product isomers that differ only in the tagging positions along the fatty acyl chains, enabling the construction of tagging profiles and the determination of the penetration depth of the targeted amino acid residues within the lipid bilayer. Combined with all-atom molecular dynamics simulations, we reveal the structural details of hydrophobic mismatches induced by model transmembrane peptides and determine the identity and stoichiometry of annular lipids surrounding individual peptides. Although currently demonstrated with peptide models, our method can be further developed to investigate annular lipid-protein interactions, providing critical experimental insights that are not attainable through existing structural biology techniques.
Wang BY, Peng SR, You W
… +12 more, Gao F, Chen G, Tang LQ, Zhang Z, Nie X, Huang WQ, Wang LH, Hong CY, Hao ZY, Wang F, Liu WY, You YZ
J Am Chem Soc
· 2026 Jun · PMID 42348767
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Intracellular proton-coupled electron transfer (PCET) governs cellular metabolism and fate, and its dysregulation is closely associated with disease progression. In normal cells, PCET into the electron transport chain su...Intracellular proton-coupled electron transfer (PCET) governs cellular metabolism and fate, and its dysregulation is closely associated with disease progression. In normal cells, PCET into the electron transport chain supports ATP production and cellular growth. In cancer cells, however, overexpressed lactate dehydrogenase (LDH) redirects PCET to pyruvate, producing lactate and thereby sustaining tumor growth, proliferation, and metastasis. Reprogramming LDH-driven PCET in living tumors therefore represents an attractive antitumor strategy, yet no artificial catalyst has been shown to outcompete LDH and reprogram PCET in living cells. Here, we report an organoiridium catalyst, Ir(Cp*)-CN, that captures proton-coupled electrons from NADH and transfers them to protons to generate H under ultrasound irradiation at physiological pH. In living cancer cells, Ir(Cp*)-CN outcompetes LDH and redirects LDH-driven pyruvate reduction and lactate production toward proton reduction and H generation. This PCET-reprogramming process converts a tumor-promoting, lactate-producing reaction into a tumor-suppressive, H-generating reaction, suppressing lactate and ATP production and markedly inhibiting tumor growth with minimal toxicity to normal cells and tissues. These findings establish a framework for reprogramming intracellular PCET via artificial catalysts that outcompete endogenous enzymes, offering a strategy for treating diseases associated with dysregulated cellular redox metabolism.
J Am Chem Soc
· 2026 Jun · PMID 42348753
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Unsaturated main-group compounds containing heteroleptic double bonds of bismuth remain exceedingly rare due to inherent p-p bond weakness. Here we report the synthesis and characterization of the first isolable silylide...Unsaturated main-group compounds containing heteroleptic double bonds of bismuth remain exceedingly rare due to inherent p-p bond weakness. Here we report the synthesis and characterization of the first isolable silylidenebismuthane complexes, L(MeSi)Si═Bi(SiMe) and L(MeSi)Si═Bi(SiPr) (()-,) (L = PhC(NBu)), containing a neutral but strongly polarized silicon-bismuth double bond. The complexes were obtained as the isomers in 55% and 60% yield through the salt metathesis reaction of LSiCl with the corresponding potassium bis(silyl)bismuthanide complexes. Remarkably, LSi-Bi(SiMe) and LSi-Bi(SiMe)(SiPr) could not be observed but undergo a trimethylsilyl group migration from the Bi atom to the Si atom to form a Si═Bi moiety containing σλ-coordinate Si and σλ-coordinate Bi atoms. The reactions of ()-, with [W(CO)(thf)] cause the () → () isomerization with respect to the silyl groups attached to furnish the corresponding terminal Bi→W(CO) complexes ()-, in which the Si═Bi π bonding interaction is significantly weakened. This and the nature of the Si═Bi bonds are corroborated by DFT calculations.
Zhang X, Sigal M, Fujimura N
… +2 more, Aikawa H, Suga H
J Am Chem Soc
· 2026 Jun · PMID 42348749
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Glycan-mediated molecular recognition is central to many diseases, yet designing selective synthetic glycan binders is difficult due to the limited functional group diversity of carbohydrates. Boronic acids can form reve...Glycan-mediated molecular recognition is central to many diseases, yet designing selective synthetic glycan binders is difficult due to the limited functional group diversity of carbohydrates. Boronic acids can form reversible covalent bonds with -diols but typically lack selectivity. To address this, we developed conformationally constrained macrocyclic peptides incorporating boronic acid-containing amino acids using genetic code reprogramming and the RaPID system. Screening against the -linked biantennary sialylated glycan -A2G2S2 yielded macrocycles with single-digit micromolar affinities. The lead peptide, A2-17, showed remarkable selectivity for -A2G2S2 and formed a reversible boronate ester with the glycan, as confirmed by competition assays and mass spectrometry. Fluorescence microscopy and flow cytometry demonstrated that A2-17 recognizes cell-surface glycans containing -A2G2S2, highlighting the potential of this platform for discovering selective glycan-binding peptides.
Sun Y, Wang B, Li W
… +5 more, Jiang Z, Li T, Xi H, Yan Y, Li Q
J Am Chem Soc
· 2026 Jun · PMID 42347770
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Lithium-sulfur (Li-S) batteries are promising next-generation energy storage systems, yet critical challenges including severe sulfur volume expansion, uncontrolled lithium polysulfide (LiPS) shuttling, and sluggish sulf...Lithium-sulfur (Li-S) batteries are promising next-generation energy storage systems, yet critical challenges including severe sulfur volume expansion, uncontrolled lithium polysulfide (LiPS) shuttling, and sluggish sulfur redox kinetics impede their practical application. Herein, we develop a metal-organic framework (MOF) functionalization strategy across three distinct structural modules (MOF backbone, grafted modulators, and engineered pore space) to tackle these issues. Specifically, in the newly synthesized Zr-based topology FDM-221, its high surface area (1956 m g) and large pore volume (1.35 cm g) provide ample pore space to accommodate sulfur volume expansion even after high sulfur encapsulation. Furthermore, sulfiphilic sites (coordinatively unsaturated Zr(IV) in the framework backbone) and lithiophilic moieties (S atoms from the benzotrithiophene-based linker and F atoms from the dangling modulators) work in tandem to furnish robust binding sites for LiPS adsorption while concurrently accelerating the redox catalysis of sulfur species. Li-S batteries based on this trinity structure deliver a high capacity of 1164 mAh g at 0.1C and excellent cycling stability over 1000 cycles at 2C, demonstrating the great potential of this MOF design strategy for next-generation batteries.
J Am Chem Soc
· 2026 Jun · PMID 42347763
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Niduenes A and B, two tetraquinane sesterterpenoids, possess a complex and intriguing 5/5/5/5/6 pentacyclic skeleton with eight contiguous stereocenters. We have achieved the first total synthesis of niduenes A and B in...Niduenes A and B, two tetraquinane sesterterpenoids, possess a complex and intriguing 5/5/5/5/6 pentacyclic skeleton with eight contiguous stereocenters. We have achieved the first total synthesis of niduenes A and B in 16 and 14 steps, respectively. The synthesis features a Pauson-Khand reaction to generate the 5/5 bicycle, a Pd-catalyzed oxidative cyclization to construct the congested triquinane framework, and a radical cyclization to assemble the tetraquinane skeleton.
Ye K, Li QK, Hu M
… +2 more, Zhang G, Ahlquist MSG
J Am Chem Soc
· 2026 Jun · PMID 42347741
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The promotional effect of cations on the CO reduction reaction (CORR) on Cu is well-established experimentally, yet the underlying mechanism remains debated. This is further complicated by an underexplored factor: in aci...The promotional effect of cations on the CO reduction reaction (CORR) on Cu is well-established experimentally, yet the underlying mechanism remains debated. This is further complicated by an underexplored factor: in acidic solution, the Cu surface may be covered by a H adlayer rather than being pristine. We employ a multiscale modeling approach to investigate how the H adlayer and electric double layer environment affect CORR activity on Cu(100). GC-DFT calculations demonstrate that the H adlayer on Cu lowers the d-band center of Cu, attenuating CORR activity and correctly identifying CO chemisorption as the rate-limiting step. This H-passivated surface provides a novel lens through which to view the cation effects. Molecular dynamics simulations reveal that the direct Cs stabilization of intermediates is a minor effect. More importantly, Cs thermodynamically favors the transition to lower H coverage and suppresses HO adsorption on the Cu surface. We thus propose a dual-role mechanism: alkali cations promote CORR also by acting as depassivants that reduce H coverage, restoring the catalytic activity of the Cu surface for the CORR.
Siriwongsup S, Lee S, Guo Y
… +2 more, Wahl C, Kim J
J Am Chem Soc
· 2026 Jun · PMID 42347692
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A bioorthogonal click-to-release reaction employing cyclooctynes and ,-dialkylhydroxylamines is described. The reaction is characterized by a tandem retro-Cope/Cope elimination reaction sequence in which strain-promoted...A bioorthogonal click-to-release reaction employing cyclooctynes and ,-dialkylhydroxylamines is described. The reaction is characterized by a tandem retro-Cope/Cope elimination reaction sequence in which strain-promoted hydroamination of a cyclooctyne by a ,-dialkylhydroxylamine reagent is relayed into Cope elimination of the resulting enamine -oxide. β-Elimination of the -hydroxyenamine product then results in bond cleavage. The reaction is regioselective, and the cleavage is directional. The primary hydroamination reaction exhibits second order rate constants up to 2 Ms, and the ensuing elimination steps are not rate limiting up to millimolar levels of hydroxylamine. The transformation enables the rapid and complete cleavage of a chemical bond in biologically relevant settings using reagents with a small molecular footprint. We demonstrate the importance of reagent size in an application involving the chemical activation of protein function using hydroxylamines that are tuned for either rapid kinetics or constrained spaces. Access limitations to enzyme active sites are a major determinant of reagent choice in bioorthogonal cleavage reaction applications.
Geue N, Greis K, Newnham HR
… +3 more, Timco GA, Winpenny REP, Barran PE
J Am Chem Soc
· 2026 Jun · PMID 42347689
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Metallosupramolecular assemblies are promising platforms for selective extraction, catalysis, and molecular recognition, yet their solution-phase synthesis often relies on complex self-assembly pathways that can be diffi...Metallosupramolecular assemblies are promising platforms for selective extraction, catalysis, and molecular recognition, yet their solution-phase synthesis often relies on complex self-assembly pathways that can be difficult to control. Here, using ion mobility mass spectrometry supported by density functional theory calculations, we introduce a gas-phase approach for directing topology in polymetallic complexes based on the encapsulation of coordination metal cations within a homometallic {Cr} ring. Upon inclusion, the resulting host-guest complexes undergo collision-induced dissociation to produce distinct polymetallic fragments whose topologies, ring, host-guest complex or open chain, depend on the identity of the guest cation. This topology switching enables the targeted synthesis of new polymetallic rings, host-guest complexes and open chains in vacuo and provides insight into the stoichiometric and conformational preferences of such assemblies.