This is a functionally adaptive response of the chemistry that may be partly responsible for the great success of this redox couple for dye-sensitized solar cells. The simulation results provide predictions that can be tested experimentally.A recent phenomenal study discovered that the extension domain of secreted amyloid-β precursor protein (sAPP) can bind to the intrinsically disordered sushi 1 domain of the γ-aminobutyric acid type B receptor subunit 1a (GABABR1a) and modulate its synaptic transmission. The work provided an important structural foundation for the modulation of GABABR1a; however, the detailed molecular interaction mechanism, crucial for future drug design, remains elusive. Here, we further investigated the dynamical interactions between sAPP peptides and the natively unstructured sushi 1 domain using all-atom molecular dynamics simulations, for both the 17-residue sAPP peptide (APP 17-mer) and its minimally active 9 residue segment (APP 9-mer). We then explored mutations of the APP 9-mer with rigorous free energy perturbation (FEP) calculations. Our in silico mutagenesis studies revealed key residues (D4, W6, and W7) responsible for the binding with the sushi 1 domain. More importantly, one double mutation based on different vertebrate APP sequences from evolution exhibited a stronger binding (ΔΔG = -1.91 ± 0.66 kcal mol-1), indicating a potentially enhanced GABABR1a modulator. These large-scale simulations may provide new insights into the binding mechanism between sAPP and the sushi 1 domain, which could open new avenues in the development of future GABABR1a-specific therapeutics.Single-atom catalysts provide a pathway to elucidate the nature of catalytically active sites. However, keeping them stabilized during operation proves to be challenging. Herein, we employ cryptomelane-type octahedral molecular sieve nanorods featuring abundant manganese vacancy defects as a support, to periodically anchor single-atom Ag. The doped Ag atoms with tetrahedral coordination are found to locate at cation substitution sites rather than being supported on the catalyst surface, thus effectively tuning the electronic structure of adjacent manganese atoms. The resulting unique Ag-O-MnO x unit functions as the active site. Its turnover frequency reaches 1038 h-1, one order of magnitude higher than for previously reported catalysts, with 90% selectivity for anti-Markovnikov phenylacetaldehyde. Mechanistic studies reveal that the activation of styrene on the ensemble site of Ag-O-MnO x is significantly promoted, which can accelerate the oxidation of styrene and, in particular, the rate-determining step of forming the epoxide intermediate. Such an extraordinary electronic promotion can be extended to other single-atom catalysts and paves the way for their practical applications.We here report a new approach to develop self-healing shape memory supramolecular liquid-crystalline (LC) networks through self-assembly of molecular building blocks via combination of hydrogen bonding and coordination bonding. We have designed and synthesized supramolecular LC polymers and networks based on the complexation of a forklike mesogenic ligand with Ag+ ions and carboxylic acids. Unidirectionally aligned fibers and free-standing films forming layered LC nanostructures have been obtained for the supramolecular LC networks. We have found that hybrid supramolecular LC networks formed through metal-ligand interactions and hydrogen bonding exhibit both self-healing properties and shape memory functions, while hydrogen-bonded LC networks only show self-healing properties. The combination of hydrogen bonds and metal-ligand interactions allows the tuning of intermolecular interactions and self-assembled structures, leading to the formation of the dynamic supramolecular LC materials. The new material design presented here has potential for the development of smart LC materials and functional LC membranes with tunable responsiveness.Intermolecular interactions play a critical role in the binding strength of molecular assemblies on surfaces. The ability to harness them enables molecularly-tunable interfacial structures and properties. Herein we report the tuning of the intermolecular interactions in monolayer assemblies derived from organothiols of different structures for the creation of nanoelectrode arrays or ensembles with effective mass transport by a molecular-level perforation strategy. The homo- and hetero-intermolecular interactions can be fully controlled, which is demonstrated not only by thermodynamic analysis of the fractional coverage but also by surface infrared reflection absorption and X-ray photoelectron spectroscopic characterizations. This understanding enables controllable electrochemical perforation for the creation of ensembles or arrays of channels across the monolayer thickness with molecular and nanoscale dimensions. learn more Redox reactions on the nanoelectrode array display molecular tunability with a radial diffusion characteristic in good agreement with theoretical simulation results. These findings have implications for designing membrane-type ion-gating, electrochemical sensing, and electrochemical energy storage devices with molecular level tunability.Recent breakthrough in synthesizing arbitrary vertical heterostructures of Ruddlesden-Popper (RP) perovskites opens doors to myriad quantum optoelectronic applications. However, it is not clear whether moiré excitons and flat bands can be formed in such heterostructures. Here, we predict from first principles that twisted homobilayers of RP perovskite, MA2PbI4, can host moiré excitons and yield flat energy bands. The moiré excitons exhibit unique and hybridized characteristics with electrons confined in a single layer of a striped distribution while holes localized in both layers. Nearly flat valence bands can be formed in the bilayers with relatively large twist angles, thanks to the presence of hydrogen bonds that strengthen the interlayer coupling. External pressures can further increase the interlayer coupling, yielding more localized moiré excitons and flatter valence bands. Finally, electrostatic gating is predicted to tune the degree of hybridization, energy, position and localization of moiré excitons in twisted MA2PbI4 bilayers.