Boosting H+ Storage in Aqueous Zinc Ion Batteries via Integrating Redox-Active Sites into Hydrogen-Bonded Organic Frameworks with Strong π-π Stacking.

In the emerging aqueous zinc ion batteries (AZIBs), proton (H+ ) with the smallest molar mass and fast (de)coordination kinetics is considered as the most ideal charge carrier compared with Zn2+ counterpart, however, searching for new hosting materials for H+ storage is still at its infancy. Herein, redox-active hydrogen-bonded organic frameworks (HOFs) assembled from diaminotriazine moiety decorated hexaazatrinnphthalene (HOF-HATN) are for the first time developed as the stable cathode hosting material for boosting H+ storage in AZIBs. The unique integration of hydrogen-bonding networks and strong π-π stacking endow it rapid Grotthuss proton conduction, stable supramolecular structure and inclined H+ storage. As a consequence, HOF-HATN displays a high capacity (320 mAh g-1 at 0.05 A g-1 ) and robust cyclability of (>10000 cycles at 5 A g-1 ) based on three-step cation coordination storage. These findings get insight into the proton transport and storage behavior in HOFs and provide the molecular engineering strategy for constructing well-defined cathode hosting materials for rechargeable aqueous batteries.

Tuning Electron Delocalization of Redox-Active Porous Aromatic Framework for Low-Temperature Aqueous Zn-K Hybrid Batteries with Air Self-Chargeability.

Air self-charging aqueous batteries promise to integrate energy harvesting technology and battery systems, potentially overcoming a heavy reliance on energy and the spatiotemporal environment. However, the exploitation of multifunctional air self-charging battery systems using promising cathode materials and suitable charge carriers remains challenging. Herein, for the first time, we developed low-temperature self-charging aqueous Zn-K hybrid ion batteries (AZKHBs) using a fully conjugated hexaazanonaphthalene (HATN)-based porous aromatic framework as the cathode material, exhibiting redox chemistry using K+ as charge carriers, and regulating Zn-ion solvation chemistry to guide uniform Zn plating/stripping. The unique AZKHBs exhibit the exceptional electrochemical properties in all-climate conditions. Most importantly, the large potential difference causes the AZKHBs discharged cathode to be oxidized using oxygen, thereby initiating a self-charging process in the absence of an external power source. Impressively, the air self-charging AZKHBs can achieve a maximum voltage of 1.15 V, an impressive discharge capacity (466.3 mAh g-1), and exceptional self-charging performance even at -40 °C. Therefore, the development of self-charging AZKHBs offers a solution to the limitations imposed by the absence of a power grid in harsh environments or remote areas.

Conjugation and Topology Engineering of 2D π-d Conjugated Metal-Organic Frameworks for Robust Potassium Organic Batteries.

The evolution of two-dimensional conjugated metal-organic frameworks (2D c-MOFs) provides a significant prospect for researching the next generation of green and advanced energy storage systems (ESSs). Especially, conjugation and topology engineering serve as an irreplaceable character in adjusting the electrochemical properties of ESSs. Herein, we proposed a novel strategy using conjugation and topology engineering to demonstrate the application of 2D c-MOFs in robust potassium-ion batteries (PIBs) for the first time. By comparing 2D c-MOFs with the rhombus/kagome structure as well as three/four-arm core, the rhombus structure (sql-Cu-TBA-MOF) cathode for PIBs can display the impressive electrochemical performance, including a high specific discharge capacity of 178.4 mAh g-1 (at 0.2 A g-1) and a well long-term cycle stability of more than 9,000 (at 10.0 A g-1). Moreover, full PIBs (FPIBs) are constructed by pairing sql-Cu-TBA-MOF cathode with dipotassium terephthalate (KTP) anode, which delivers a high reversible discharge specific capacity of 146.6 mAh g-1 (at 0.1 A g-1) and great practical application prospect. These findings provide reasonable implications for the design of 2D c-MOFs from the perspective of conjugation and topology engineering for advanced energy storage systems.

Immobilizing Quinone-Fused Aza-Phenazine into π-d Conjugated Coordination Polymers with Multiple-Active Sites for Sodium-Ion Batteries.

The development of coordination polymers with π-d conjugation (CCPs) provides ide prospects for exploring the next generation of environmental-friendliness energy storage systems. Herein, the synthesis, experimental characterizations, and Na-ion storage mechanism of π-d CCPs with multiple-active sites are reported, which use quinone-fused aza-phenazine (AP) and aza-phenazin (AP) as the organic ligands coordinated with the metal center (Ni2+ ). Among them, NiQAP as the cathode material exhibits impressive electrochemical properties applied in sodium-ion batteries (SIBs), including the high initial/stable discharge specific capacities (180.0/225.6 mAh g-1 ) at 0.05 A g-1 , a long-term cycle stability up to 10,000 cycles at 1.0 A g-1 with a high reversible capacity of 100.1 mAh g-1 , and good rate capability of 99.6 mAh g-1 even at 5.0 A g-1 . Moreover, the Na-ion storage mechanism of NiQAP is also performed by the density functional theory (DFT) calculation, showing multiple-active sites of C≐O and C≐N (in the quinone and phenazine structure) and NiO4 (in the coordination unit) for Na-ion storage. These results highlight the importance of organic electrode material with the coordination units and provide a foundation for further studying the CCPs with multiple active sites for energy storage systems.

Crystallinity Regulation and Defects Passivation for Efficient and Stable Perovskite Solar Cells Using Fully Conjugated Porous Aromatic Frameworks.

Fully conjugated porous aromatic frameworks (PAFs) have been constructed through Gilch reaction. The obtained PAFs have rigid conjugated backbones, high specific surface area, and excellent stability. The prepared PAF-154 and PAF-155 have been successfully applied in the perovskite solar cells (PSCs) by doping into the perovskite layer. The champion PSC devices afford a power conversion efficiency of 22.8 % and 22.4 %. It is found that the PAFs can be used as an efficient nucleation template, thus regulating the perovskite crystallinity. Meanwhile, PAFs can also passivate defects and promote carriers transporting in the perovskite film. By the comparative study with their linear counterpart, we unravel that the efficacy of PAFs is highly related to their porous structure and rigid fully conjugated networks. The unencapsulated devices with PAFs doping exhibit outstanding long-term stability, retaining 80 % of their initial efficiencies after half-year storage in ambient conditions.

One-Pot Precision Synthesis of AB, ABA and ABC Block Copolymers via Switchable Catalysis.

The switchable catalysis using a commercial salenMn catalyst was firstly developed and applied in the one-pot selective copolymerization from anhydrides, epoxides, CO2 and ϵ-caprolactone (ϵ-CL) mixtures for the precise synthesis of AB, ABA and novel ABC block copolymers. The observed unique double switch process comprising three different polymerization cycles was rationalized by theoretical calculations. Surprisingly, the first block turned out to be an efficient macromolecular initiator for the consecutive introduction of carbonate linkages into copolymers, albeit with dominant cyclization with the catalyst alone. Further, through the selective reaction on different epoxides, the switchable copolymerization of up to five monomers was achieved yielding well-defined multi-block copolymers with structural diversity and functionality.

Continuous Porous Aromatic Framework Membranes with Modifiable Sites for Optimized Gas Separation.

Continuous microporous membranes are widely studied for gas separation, due to their low energy premium and strong molecular specificity. Porous aromatic frameworks (PAFs) with their exceptional stability and structural flexibility are suited to a wide range of separations. Main-stream PAF-based membranes are usually prepared with polymeric matrices, but their discrete entities and boundary defects weaken their selectivity and permeability. The synthesis of continuous PAF membranes is still a major challenge because PAFs are insoluble. Herein, we successfully synthesized a continuous PAF membrane for gas separation. Both pore size and chemistry of the PAF membrane were modified by ion-exchange, resulting in good selectivity and permeance for the gas mixtures H2 /N2 and CO2 /N2 . The membrane with Br- as a counter ion in the framework exhibited a H2 /N2 selectivity of 72.7 with a H2 permeance of 51844 gas permeation units (GPU). When the counter ions were replaced by BF4 - , the membrane showed a CO2 permeance of 23058 GPU, and an optimized CO2 /N2 selectivity of 60.0. Our results show that continuous PAF membranes with modifiable pores are promising for various gas separation situations.

Efficient Suppression of Chain Transfer and Branching via Cs -Type Shielding in a Neutral Nickel(II) Catalyst.

An effective shielding of both apical positions of a neutral NiII active site is achieved by dibenzosuberyl groups, both attached via the same donors' N-aryl group in a Cs -type arrangement. The key aniline building block is accessible in a single step from commercially available dibenzosuberol. This shielding approach suppresses chain transfer and branch formation to such an extent that ultrahigh molecular weight polyethylenes (5×106  g mol-1 ) are accessible, with a strictly linear microstructure (<0.1 branches/1000C). Key features of this highly active (4.3×105  turnovers h-1 ) catalyst are an exceptionally facile preparation, thermal robustness (up to 90 °C polymerization temperature), ability for living polymerization and compatibility with THF as a polar reaction medium.

Understanding conformational and dynamical evolution of semiflexible polymers in shear flow.

A clear description of the conformational and dynamical evolution of polymer chains in shear flow is the fundamental basis of microfluidic separations and macroscopic rheological behaviors. We employ graph theory analysis to analyze the local deformation and dynamics of linear polymer chains with different rigidities in shear flow based on the simulation trajectories that record the instantaneous conformations and dynamics. Our results show that all semiflexible chains experience quasi-periodic tumbling motions when the shear strain overwhelms the U-shape (or S-shape) deformation energy barrier. More interestingly, the contact map provides solid evidence for the asymmetric deformation in the whole tumbling motion. In the stretching process: at small and intermediate shear strength, flexible polymers show a quasi-affine deformation while semiflexible ones are initially unfolded from the center of the chains, then both of them follow the extension with half dumbbell- or dumbbell-like ends; at high shear strength, all polymer chains present only a dumbbell-like extension. In the collapse process, all chains prefer to initiate the folding from chain ends. This finding can facilitate our understanding on how semiflexible polymer chains relax and dissipate the stress in shear flow.

Dissecting the Innate Immune Recognition of Opioid Inactive Isomer (+)-Naltrexone Derived Toll-like Receptor 4 (TLR4) Antagonists.

The opioid inactive isomer (+)-naltrexone is one of the rare Toll-like receptor 4 (TLR4) antagonists with good blood-brain barrier (BBB) permeability, which is a lead with promising potential for treating neuropathic pain and drug addiction. (+)-Naltrexone targets the lipopolysaccharides (LPS) binding pocket of myeloid differentiation protein 2 (MD-2) and blocks innate immune TLR4 signaling. However, the details of the molecular interactions of (+)-naltrexone and its derivatives with MD-2 are not fully understood, which hinders the ligand-based drug discovery. Herein, in silico and in vitro assays were performed to elucidate the innate immune recognition of the opioid inactive (+)-isomers. The results showed that the conserved LPS binding pocket of MD-2 accommodated these opioid inactive (+)-isomers. The calculated binding free energies of (+)-naltrexone and its derivatives in complex with MD-2 correlated well with their experimental binding affinities and TLR4 antagonistic activities. Hydrophobic residues in the MD-2 cavity interacted directly with these (+)-naltrexone based TLR4 antagonists and principally participated in ligand binding. Increasing the hydrophobicity of substituted group at N-17 improved its TLR4 antagonistic activity, while charged groups disfavored the binding with MD-2. Molecular dynamics (MD) simulations showed the binding of (+)-naltrexone or its derivatives to MD-2 stabilized the "collapsed" conformation of MD-2, consequently blocking the binding and signaling of TLR4. Thermodynamics and dynamic analysis showed the topology of substituted group at N-17 of (+)-naltrexone affected the binding with MD-2 and TLR4 antagonistic activity. This study provides a molecular insight into the innate immune recognition of opioid inactive (+)-isomers, which would be of great help for the development of next-generation of (+)-opioid based TLR4 antagonists.

Simultaneous polymer chain growth with the coexistence of bulk and surface initiators: insight from computer simulations.

By Brownian dynamics simulations we study the simultaneous polymer chain growth process with the coexistence of bulk and surface initiators. We find that when the surface initiator density is low enough, the practical experimental way to estimate the dispersity (D) of surface-initiated chains on the basis of the dispersity of bulk-initiated chains remains valid as long as the conformations of grafted chains remain within the mushroom regime (i.e., the grafted chains are sparsely distributed). On the other hand, although the average chain lengths of surface and bulk polymers could be equivalent when certain conditions are met, their mass distributions are still different. We also find that increasing the fraction of surface initiators leads to an enlarged disparity in D and average length between surface and bulk chains, which is inconsistent with previous studies. This study helps in better understanding the cooperative competition and suppressing effect of bulk chains on surface grown chains, as well as the cause of the dispersity of the surface grown chains as compared to their bulk counterparts with the coexistence of bulk and surface initiators.

Polymerization-induced polymer aggregation or polymer aggregation-enhanced polymerization? A computer simulation study.

In this study, using dissipative particle dynamics simulations coupled with the stochastic reaction model, we investigate the polymerization-induced polymer aggregation process and the polymer aggregation-enhanced polymerization process in a binary solution, by simply tuning the solubility of the solvent to one species of copolymerization. Our simulations indicate that it is a complicated interplay of the copolymerization on the formation of aggregates, namely, on one hand the polymerization may induce the aggregation of one species; on the other hand it has an effect of mixing the two species together. We also find that the polymerization process basically follows the first order reaction kinetics. With the increase of insolubility of B species in the solution, it continuously deviates from the first order reaction kinetics. In the symmetric copolymerization system, we find that the dispersity of copolymers monotonically decreases with the increase of reaction probability. This counterintuitive result can be understood via the comparison of diffusion-controlled kinetics and reaction-controlled kinetics. In the asymmetric system, for systems with preferential copolymerization, the mass distribution shapes are Gaussian-like with certain peaks. For comparison, for systems with preferential homopolymerization, the mass distribution shape shows an obviously bimodal form. This study helps to better understand the cooperative competition between the reaction dynamics and the diffusion dynamics during the preparation of copolymer materials, and could act as a guide to better design and improve the copolymerization technologies in laboratories and in industry.

Noncovalent Interactions between Superoxide Dismutase and Flavonoids Studied by Native Mass Spectrometry Combined with Molecular Simulations.

Misfolding and aggregation of Cu, Zn superoxide dismutase (SOD1) is implicated in the etiology of amyotrophic lateral sclerosis (ALS). The use of small molecules may stabilize the spatial structure of SOD1 dimer, thus, preventing its dissociation and aggregation. In this study, "native" mass spectrometry (MS) was used to study the noncovalent interactions between SOD1 and flavonoid compounds. MS experiments were performed on a quadruple time-of-flight (Q-ToF) mass spectrometer with an electrospray ionization (ESI) source and T-wave ion mobility. ESI-MS was used to detect the SOD1-flavonoid complexes and compare their relative binding strengths. The complement of ion mobility separation allowed comparison in the binding affinities between flavonoid isomers and provided information on the conformational changes. Molecular docking together with molecular dynamics simulations and MM/PBSA methods were applied to gain insights into the binding modes and free energies of SOD1-flavonoid complexes at the molecule level. Among all the flavonoids investigated, flavonoid glycosides preferentially bind to SOD1 than their aglycone counterparts. Naringin, one of the compounds that has the strongest binding affinity to SOD1, was subjected to further characterization. Experiment results show that the binding of naringin can stabilize SOD1 dimer and inhibit the aggregation of SOD1. Molecular simulation results suggest that naringin could reduce the dissociation of SOD1 dimers through direct interaction with the dimer interface. This developed analytical strategy could also be applied to study the interactions between SOD1 and other drug-like molecules, which may have the effect to reduce the aggregation.

Quantum mechanical/molecular mechanical/continuum style solvation model: second order Møller-Plesset perturbation theory.

A combined quantum mechanical/molecular mechanical/continuum (QM/MM/C) style second order Møller-Plesset perturbation theory (MP2) method that incorporates induced dipole polarizable force field and induced surface charge continuum solvation model is established. The Z-vector method is modified to include induced dipoles and induced surface charges to determine the MP2 response density matrix, which can be used to evaluate MP2 properties. In particular, analytic nuclear gradient is derived and implemented for this method. Using the Assisted Model Building with Energy Refinement induced dipole polarizable protein force field, the QM/MM/C style MP2 method is used to study the hydrogen bonding distances and strengths of the photoactive yellow protein chromopore in the wild type and the Glu46Gln mutant.

Anchoring π-d Conjugated Metal-Organic Frameworks with Dual-Active Centers on Carbon Nanotubes for Advanced Potassium-Ion Batteries.

Potassium-ion batteries (PIBs) are gradually gaining attention owing to their natural abundance, excellent security, and high energy density. However, developing excellent organic cathode materials for PIBs to overcome the poor cycling stability and slow kinetics caused by the large radii of K+ ions is challenging. This study demonstrates for the first time the application of a hexaazanonaphthalene (HATN)-based 2D π-d conjugated metal-organic framework (2D c-MOF) with dual-active centers (Cu-HATNH) and integrates Cu-HATNH with carbon nanotubes (Cu-HATNH@CNT) as the cathode material for PIBs. Owing to this systematic module integration and more exposed active sites with high utilization, Cu-HATNH@CNT exhibits a high initial capacity (317.5 mA h g-1 at 0.1 A g-1 ), excellent long-term cycling stability (capacity retention of 96.8% at 5 A g-1 after 2200 cycles), and outstanding rate capacity (147.1 mA h g-1 at 10 A g-1 ). The reaction mechanism and performance are determined by combining experimental characterization and density functional theory calculations. This contribution provides new opportunities for designing high-performance 2D c-MOF cathodes with multiple active sites for PIBs.

A Rhombic 2D Conjugated Metal-Organic Framework as Cathode for High-Performance Sodium-Ion Battery.

2D conjugated metal-organic frameworks (2D c-MOFs) have garnered significant attention as promising electroactive materials for energy storage. However, their further applications are hindered by low capacity, limited cycling life, and underutilization of the active sites. Herein, Cu-TBA (TBA = octahydroxyltetrabenzoanthracene) with large conjugation units (narrow energy gap) and a unique rhombus topology is introduced as the cathode material for sodium-ion batteries (SIBs). Notably, Cu-TBA with a rhombus topology exhibits a high specific surface area (613 m2 g-1) and metallic band structure. Additionally, Cu-TBA outperforms its hexagonal counterpart, Cu-HHTP (HHTP = 2,3,6,7,10,11-hexahydroxyltriphenylene), demonstrating superior reversible capacity (153.6 mAh g-1 at 50 mA g-1) and outstanding cyclability with minimal capacity decay even after 3000 cycles at 1 A g-1. This work elucidates a new strategy to enhance the electrochemical performance of 2D c-MOFs cathode materials by narrowing the energy gap of organic linkers, effectively expanding the utilization of 2D c-MOFs for SIBs.

QuanPol: a full spectrum and seamless QM/MM program.

The quantum chemistry polarizable force field program (QuanPol) is implemented to perform combined quantum mechanical and molecular mechanical (QM/MM) calculations with induced dipole polarizable force fields and induced surface charge continuum solvation models. The QM methods include Hartree-Fock method, density functional theory method (DFT), generalized valence bond theory method, multiconfiguration self-consistent field method, Møller-Plesset perturbation theory method, and time-dependent DFT method. The induced dipoles of the MM atoms and the induced surface charges of the continuum solvation model are self-consistently and variationally determined together with the QM wavefunction. The MM force field methods can be user specified, or a standard force field such as MMFF94, Chemistry at Harvard Molecular Mechanics (CHARMM), Assisted Model Building with Energy Refinement (AMBER), and Optimized Potentials for Liquid Simulations-All Atom (OPLS-AA). Analytic gradients for all of these methods are implemented so geometry optimization and molecular dynamics (MD) simulation can be performed. MD free energy perturbation and umbrella sampling methods are also implemented.

Mean field QM/MM method: average position approximation.

The average position mean field combined quantum mechanical (QM) and molecular mechanical (MM) method, denoted as QM/, is described. This method can drastically reduce the QM/ molecular dynamics simulation time to a level similar to pure MM methods, enabling the sampling of millions of configurations. A rigorous analysis shows that there is a general and significant error (up to 7 kcal/mol) in mean field QM/ methods arising from the loss of instantaneous polarization of the QM electronic wavefunction. To reach high level of accuracy and efficiency, polarizable force field should be used to represent the QM region in mean field QM/ methods.

Quantum mechanical/molecular mechanical/continuum style solvation model: time-dependent density functional theory.

A combined quantum mechanical/molecular mechanical/continuum (QM/MMpol/C) style method is developed for time-dependent density functional theory (TDDFT, including long-range corrected TDDFT) method, induced dipole polarizable force field, and induced surface charge continuum model. Induced dipoles and induced charges are included in the TDDFT equations to solve for the transition energies, relaxed density, and transition density. Analytic gradient is derived and implemented for geometry optimization and molecular dynamics simulation. QM/MMpol/C style DFT and TDDFT methods are used to study the hydrogen bonding of the photoactive yellow protein chromopore in ground state and excited state.

Fine-Tuned Ultra-Microporous Metal-Organic Framework in Mixed-Matrix Membrane: Pore-Tailoring Optimization for C2 H2 /C2 H4 Separation.

Effective separation of ethyne from ethyne/ethylene (C2 H2 /C2 H4 ) mixtures is a challenging and crucial industrial process. Herein, an ultra-microporous metal-organic framework (MOF) platform, Cd(dicarboxylate)2 (ditriazole), with triangular channels is proposed for high-efficiency separation of C2 H2 from C2 H4 . The targeted structures are constructed via a mixed-ligand strategy by selecting different-sized ligands, allowing for tunable pore sizes and volumes. The pore properties can be further optimized by additional modification via pore environment tailoring. This concept leads to the successful synthesis of three ultra-microporous Cd-MOFs (JLU-MOF87-89). As intended, C2 H2 uptake and C2 H2 /C2 H4 selectivity gradually increase with progressively optimizing the pore structure by adjusting ligand length and substituents. JLU-MOF89, functionalized with methyl groups, features the most optimal pore chemistry and shows selective recognition of C2 H2 over C2 H4 , owing to the framework-C2 H2 host-guest interactions. Furthermore, JLU-MOFs are fabricated into mixed-matrix membranes for C2 H2 /C2 H4 separation. C2 H2 permeability and C2 H2 /C2 H4 permselectivity are substantially enhanced by ≥400% and ≥200%, respectively, after hybridization of JLU-MOF88 and JLU-MOF89 with a polyimide polymer (6FDA-ODA). These membranes can work efficiently and are stable under different conditions, demonstrating their potential in actual ethyne separation.