Journal of the American Chemical Society最新文献

Understanding the behavior of water molecules at solid-liquid interfaces is crucial for various applications such as photocatalytic water splitting, a key technology for sustainable fuel production and chemical transformations. Despite extensive studies conducted in the past, the impact of the microscopic structure of interfacial water molecules on photocatalytic reactivity has not been directly examined. In this study, using real-time mass spectrometry and Fourier-transform infrared spectroscopy, we demonstrated the crucial role of hydrogen bond (H-bond) networks on the photocatalytic hydrogen evolution in thickness-controlled water adsorption layers on various TiO₂ photocatalysts. Under controlled water vapor environments with relative humidity (RH) below 70%, we observed a monotonic increase in the H₂ formation rate with increasing RH, indicating that reactive water molecules were present not only in the first adsorbed layer but also in several overlying layers. In contrast, at RH > 70%, when more than three water layers covered the catalyst surface, the H₂ formation rate turned to decrease dramatically because of the structural rearrangement and hardening of the interfacial H-bond network induced during further water adsorption. This unique many-body effect of interfacial water was consistently observed for various TiO₂ particles with different crystalline structures, including brookite, anatase, and a mixture of anatase and rutile. Our results demonstrated that depositing several water layers in a water vapor environment with RH ∼ 70% is optimal for photocatalytic hydrogen evolution rather than liquid-phase reaction conditions in aqueous solutions. This study provides molecular-level insights into designing interfacial water conditions to enhance photocatalytic performance.

Chiral secondary alkyl amines with a vicinal quaternary stereocenter are undoubtedly important and ubiquitous subunits in natural products and pharmaceuticals. However, their asymmetric synthesis remains a formidable challenge. Herein, we merge the ring-opening 1,2-metallate shift with iridium-catalyzed enantioselective C(sp³)-H borylation of aziridines to deliver these frameworks with high enantioselectivities. We also demonstrated the synthetic application by downstream transformations, including the total synthesis of two Amaryllidaceae alkaloids, (-)-crinane and (+)-mesmebrane.

Hydrogen sulfide (H₂S) is an endogenously produced gasotransmitter involved in many physiological processes that are integral to proper cellular functioning. Due to its profound anti-inflammatory and antioxidant properties, H₂S plays important roles in preventing inflammatory skin disorders and improving wound healing. Transdermal H₂S delivery is a therapeutically viable option for the management of such disorders. However, current small-molecule H₂S donors are not optimally suited for transdermal delivery and typically generate electrophilic byproducts that may lead to undesired toxicity. Here, we demonstrate that H₂S release from metal-organic frameworks (MOFs) bearing coordinatively unsaturated metal centers is a promising alternative for controlled transdermal delivery of H₂S. Gas sorption measurements and powder X-ray diffraction (PXRD) studies of 11 MOFs support that the Mg-based framework Mg₂(dobdc) (dobdc^4- = 2,5-dioxidobenzene-1,4-dicarboxylate) is uniquely well-suited for transdermal H₂S delivery due to its strong yet reversible binding of H₂S, high capacity (14.7 mmol/g at 1 bar and 25 °C), and lack of toxicity. In addition, Rietveld refinement of synchrotron PXRD data from H₂S-dosed Mg₂(dobdc) supports that the high H₂S capacity of this framework arises due to the presence of three distinct binding sites. Last, we demonstrate that transdermal delivery of H₂S from Mg₂(dobdc) is sustained over a 24 h period through porcine skin. Not only is this significantly longer than sodium sulfide but this represents the first example of controlled transdermal delivery of pure H₂S gas. Overall, H₂S-loaded Mg₂(dobdc) is an easily accessible, solid-state source of H₂S, enabling safe storage and transdermal delivery of this therapeutically relevant gas.

Preserving vanadium in a high oxidation state during chemical transformations can be challenging due to the oxidizing nature of V(+5) species. Oxo and similar isoelectronic ligands have been utilized to stabilize V(+5) by extensive π-donation. However, decreasing the bond order between V and the oxo ligand often results in a reduction of the metal center. Herein, we report a unique transformation involving anionic V(+5) alkylidene that converts a V(+5) oxo complex to a V(+5) alkylidyne in three steps without altering the oxidation state of the metal center. This method has been used to obtain rare 3d Schrock carbynes, which provide easy and scalable access to V(+5) alkylidynes.

Photocatalysis has emerged as an effective tool for addressing the contemporary challenges in organic synthesis. However, the trial-and-error-based screening of feasible substrates and optimal reaction conditions remains time-consuming and potentially expensive in industrial practice. Here, we demonstrate an electrochemical-based data-acquisition approach that derives a simple set of redox-relevant electro-descriptors for effective mechanistic analysis and performance evaluation through machine learning (ML) in photocatalytic synthesis. These electro-descriptors correlate to the quantification of shifted charge transfer processes in response to the photoirradiation and enabled construction of reactivity diagram where high-yield reactive "hot zones" can reflect subtle changes of the reaction system. For the model reaction of photocatalytic deoxygenation reaction, the influence of varying carboxylic acids (substrate A, oxidation-intended) and alkenes (substrate B, reduction-intended) and varying reaction conditions on the reaction yield can be visualized, while mathematical analysis of the electro-descriptor patterns further revealed distinct mechanistic/kinetic impacts from different substrates and conditions. Additionally, in the application of ML algorithms, the experimentally derived electro-descriptors reflect an overall redox kinetic outcome contributed from vast reaction parameters, serving as a capable means to reduce the dimensionality in the case of complex multiparameter chemical space. As a result, utilization of electro-descriptors enabled efficient and robust quantitative evaluation of chemical reactivity, demonstrating promising potential of introducing operando-relevant experimental insights in the data-driven chemistry.

Converting dilute CO₂ source into value-added chemicals and fuels is a promising route to reduce fossil fuel consumption and greenhouse gas emission, but integrating electrocatalysis with CO₂ capture still faced marked challenges. Herein, we show that a self-healing metal-organic macrocycle functionalized as an electrochemical catalyst to selectively produce methane from flue gas and air with the lowest applied potential so far (0.06 V vs reversible hydrogen electrode, RHE) through an enzymatic activation fashion. The capsule emulates the enzyme' pocket to abstract one in situ-formed CO₂-adduct molecule with the commercial amino alcohols, forming an easy-to-reduce substrate-involving clathrate to combine the CO₂ capture with electroreduction for a thorough CO₂ reduction. We find that the self-healing system exhibited enzymatic kinetics for the first time with the Michaelis-Menten mechanism in the electrochemical reduction of CO₂ and maintained a methane Faraday efficiency (FE) of 74.24% with a selectivity of over 99% for continuous operation over 200 h. A consecutive working lab at 50 mA·cm^-2, in an eleven-for-one (10 h working and 1 h healing) electrolysis manner, gives a methane turnover number (TON) of more than 10,000 within 100 h. The integrated electrolysis with CO₂ capture facilitates the thorough reduction of flue gas (ca. 13.0% of CO₂) and first time of air (ca. 400 ppm of CO₂ to 42.7 mL CH₄ from 1.0 m³ air). The new self-healing strategy of molecular electrocatalyst with an enzymatic activation manner and anodic shifting of the applied potentials provided a departure from the existing electrochemical catalytic techniques.

Amid the escalating integration of renewable energy sources, the demand for grid energy storage solutions, including non-aqueous organic redox flow batteries (oRFBs), has become ever more pronounced. oRFBs face a primary challenge of irreversible capacity loss attributed to the crossover of redox-active materials between half-cells. A possible solution for the crossover challenge involves utilization of bipolar electrolytes that act as both the catholyte and anolyte. Identifying such molecules poses several challenges as it requires a delicate balance between the stability of both oxidation states and energy density, which is influenced by the separation between the two redox events. We report the development of a diaminotriazolium redox-active core capable of producing two electronically distinct persistent radical species with typically extreme reduction potentials (E_1/2^red < -2 V, E_1/2^ox > +1 V, vs Fc^0/+) and up to 3.55 V separation between the two redox events. Structure-property optimization studies allowed us to identify factors responsible for fine-tuning of potentials for both redox events, as well as separation between them. Mechanistic studies revealed two primary decomposition pathways for the neutral radical charged species and one for the radical biscation. Additionally, statistical modeling provided evidence for the molecular descriptors to allow identification of the structural features responsible for stability of radical species and to propose more stable analogues.

The solution-state fluxional behavior of bullvalene has fascinated physical organic and supramolecular chemists alike. Little effort, however, has been put into investigating bullvalene applications in bulk, partially due to difficulties in characterizing such dynamic systems. To address this knowledge gap, we herein probe whether bullvalene Hardy-Cope rearrangements can be mechanically perturbed in bulk polymer networks. We use dynamic mechanical analysis to demonstrate that the activation barrier to the glass transition process is significantly elevated for bullvalene-containing materials relative to "static" control networks. Furthermore, bullvalene rearrangements can be mechanically perturbed at low temperatures in the glassy region; such behavior facilitates energy dissipation (i.e., increased hysteresis energy) and polymer chain alignment to stiffen the material (i.e., increased Young's modulus) under load. Computational simulations corroborate our work that showcases bullvalene as a reversible "low-force" covalent mechanophore in the modulation of viscoelastic behavior.

Glycans cover the cell surface to form the glycocalyx, which governs a myriad of biological phenomena. However, understanding and regulating glycan functions is extremely challenging due to the large number of heterogeneous glycans that engage in intricate interaction networks with diverse biomolecules. Glycocalyx-editing techniques offer potent tools to probe their functions. In this study, we devised a HaloTag-based technique for glycan manipulation, which enables the introduction of chemically synthesized glycans onto a specific protein (protein of interest, POI) and concurrently incorporates fluorescent units to attach homogeneous, well-defined glycans to the fluorescence-labeled POIs. Leveraging this HaloTag-based glycan-display system, we investigated the influence of the interactions between Gal-3 and various N-glycans on protein dynamics. Our analyses revealed that glycosylation modulates the lateral diffusion of the membrane proteins in a structure-dependent manner through interaction with Gal-3, particularly in the context of the Gal-3-induced formation of the glycan network (galectin lattice). Furthermore, N-glycan attachment was also revealed to have a significant impact on the extracellular vesicle-loading of membrane proteins. Notably, our POI-specific glycan introduction does not disrupt intact glycan structures, thereby enabling a functional analysis of glycans in the presence of native glycan networks. This approach complements conventional glycan-editing methods and provides a means for uncovering the molecular underpinnings of glycan functions on the cell surface.

Self-assembly of conjugated polymers offers a powerful method to prepare semiconducting two-dimensional (2D) nanosheets for optoelectronic applications. However, due to the typical biaxial growth behavior of the polymer self-assembly, independent control of the width and length of 2D sheets has been challenging. Herein, we present a greatly accelerated crystallization-driven self-assembly (CDSA) system of polyacetylene-based conjugated polymer to produce 2D semiconducting nanorectangles with precisely controllable dimensions. In detail, rectangular 2D seeds with tunable widths of 0.2-1.3 μm were produced by changing the cosolvent% and grown in the length direction by uniaxial living CDSA up to 11.8 μm. The growth rate was effectively enhanced by tuning the cosolvent%, seed concentration, and temperature, achieving up to 27-fold increase. Additionally, systematic kinetic investigation yielded empirical rate equations, elucidating the relationship between growth rate constant, cosolvent%, seed concentration, and seed width. Finally, the living CDSA allowed us to prepare penta-block comicelles with tunable width, length, and height.