Journal of the American Chemical Society

Abstract Sialic acid (Neu5Ac) is a monosaccharide terminating glycoconjugates, serving as ligands for lectins in health and disease. Tools to target sialyltransferases (STs) and neuraminidases (NEUs) are important in the study of sialoglycans. 3FaxNeu5Ac is a common ST inhibitor, while 2,3diFNeu5Ac is a covalent mechanism-based NEU inactivator. Here, we demonstrate the advantages of having two fl…

Abstract Chiral allenes and alkynes are privileged scaffolds in natural products and pharmaceuticals. Although significant advances have been achieved in catalytic asymmetric synthesis from diazo compounds, selectively achieving high levels of both enantioselectivity and regioselectivity from the same starting materials remains challenging. Herein, we report a tunable organocatalytic strategy for…

Abstract High-entropy alloys (HEAs) provide compositionally diverse surfaces for electrocatalysis, yet how their surface atomic arrangements dictate active-site ensembles and catalytic activity remains unclear. Here, we develop a dropwise deposition strategy to synthesize Pd@Pd0.2Pt0.2Ir0.2Ru0.2Rh0.2 core–shell nanocrystals with comparable shell compositions but distinct surface atomic arrangemen…

Abstract We report a core-regenerating atom pair exchange strategy for skeletal carbon isotope incorporation into pyridines. The two-step sequence proceeds through pyridine dearomatization followed by a [4 + 2]/retro-[4 + 2] cycloaddition cascade with an isotope-labeled sulfonyl cyanide reagent, enabling selective replacement of a pyridine carbon atom with an isotopically labeled counterpart. Thi…

Abstract There has been recent interest in the physics of evaporating alcohol droplets under humid conditions. These studies focus on delineating time scales for different physical processes, but what about the chemistry? Given the novel reactivity of aqueous microdroplets, we surmise that there will also be interesting chemistry. Here we focus on the oxidation chemistry of single evaporating cha…

Abstract The spin ladder model is an important platform bridging one-dimensional and two-dimensional magnetic systems, with its physical properties modulated by geometric configuration. As such, the S = 1/2 two-leg antiferromagnetic spin ladder has attracted attention due to its potential connection to unconventional superconductivity. Here, we combine on-surface synthesis with scanning probe mic…

Abstract A mild supramolecular template strategy is reported for the selective synthesis of medium- to macrocyclic disulfides via aerobic oxidative cyclization of α,ω-dithiols in aqueous media. The water-soluble deep cavitand CV-1 serves as a multifunctional platform that synergistically addresses challenges of aqueous-phase macrocyclization, including poor substrate solubility, low cyclization s…

Abstract Protein-based recovery, detection, and separation of rare earth elements (REs) have accelerated since the discovery of the lanmodulin (LanM) proteins. While exceptional at total RE recovery, prior proteins, like most ligands, exhibited limited ability to differentiate REs, whether in detection or separations. Here we report two dimerizing LanMs (Al-LanM and Xan-LanM) that address these c…

Abstract Primary amines are among the most abundant and readily available functional groups, yet their direct use as alkyl cross-coupling partners remains underdeveloped. We report a general platform for C(sp3)–C(sp3) cross-coupling enabled by the in situ formation and visible-light-induced denitrogenation of unsymmetric diazenes. Central to this approach is the development of N-benzoyloxysulfami…

Abstract Tau filaments are a hallmark of neurodegenerative tauopathies, such as Alzheimer’s disease (AD). Structural studies have revealed that patient-derived tau fibrils adopt distinct folds in different tauopathies; however, it is unclear what forces guide this process. To explore this question, we investigated the assembly of a tau fragment containing four disease-associated phospho-mimetics …

Abstract Predicting the phosphorescent emission gaps of heavy-metal complexes is crucial for organic light-emitting diode materials design, yet challenged by the highly entangled nature of their triplet states. Traditional projective single-reference methods like coupled cluster break down for these systems due to severe spin contamination, physically misidentifying the electronic character and y…

Abstract Directing photogenerated carriers toward productive coupled redox chemistry is central to solar-to-chemical energy conversion, yet the interfacial chemical basis governing carrier routing remains elusive. Here, we establish a hydroxyl-defined Lewis base interface as a chemically programmed platform for coupling hole-selective extraction with cooperative photoredox catalysis. By in situ c…

Abstract Current research on separators for lithium metal batteries lacks unified theoretical frameworks and essential quantitative parameters, limiting reversibility, interfacial stability, and lifespan. Herein, we reveal a pronounced nonlinear correlation between the separator dielectric constant and ion transport kinetics. Specifically, an organic-aqueous interfacial reaction is employed to dr…

Abstract Rationally switching reaction pathways to selectively produce diverse value-added chemicals is crucial for electrochemical CO2 reduction reactions (CO2RRs). However, such a goal is usually achieved by catalyst design, and it remains a challenge for electrolyte engineering. Herein, two structurally similar ionic liquids (ILs) differing only in the C2 substituent (H or –CH3) of the imidazo…

Abstract Deciphering ultrafast relaxation pathways following the excitation of specific vibrational modes can inform our understanding of mode-selective chemistry; however, direct spectroscopic signatures of the underlying nuclear dynamics remain elusive. Here, we show that X-ray transient absorption spectroscopy at the carbon K-edge can resolve how vibrational pre-excitation biases the ultrafast…

Abstract The rational design of framework adsorbents for structurally diverse contaminants requires pore environments that can accommodate different molecular scales while preserving strong host–guest interactions. Here, we report a heteroporous covalent organic framework (COF) in which hierarchical pore architecture and local chemical functionality are jointly tuned through multicomponent reticu…

Abstract Reconciling molecular mobility with structural rigidity remains a fundamental thermodynamic paradox in soft matter mechanics, as traditional static nanoconfinement typically restricts chain dynamics and inevitably leads to brittle failure. Here, we demonstrate an ion-regulated dynamic confinement strategy within 1.5 nm 2D silicate galleries that overcomes this classical trade-off. We rev…

Abstract Ionization of hydrogen-bonded molecular clusters can initiate reaction pathways that are inaccessible in isolated molecules, yet the role of local solvation in directing this chemistry remains poorly understood. Here, we employ weakly bound CO2–H2O clusters as experimentally tractable model systems to investigate how microsolvation influences ionization-driven molecular growth and bond f…

Abstract Thiols on gold are the quintessential self-assembled monolayer, providing molecule-level interfacial control to solid surfaces. The Au–S bond is reasonably strong but labile. The Au–C bonds from N-heterocyclic carbene (NHC) ligands on gold surfaces are stronger and generally more inert than Au–S bonds, and it is known that NHCs can displace thiol ligands on gold, suggesting that NHCs mig…

Abstract Cyclohexynes are highly strained intermediates that are largely underexplored compared with benzynes, their aromatic counterparts. Known strategies toward generating cyclohexynes include accessing precursors with specific functionalities such as silyl alkenyl triflates, alkenyl halides, alkenyl pseudohalides, diazirines, carbene precursors, or diacyl peroxides, among others. Ultimately, …