Covalent Systems Research Articles

A Strong Supramolecular Mechanophore with Controlled Mechanical Strength.

Supramolecular mechanophores typically exhibit much lower mechanical strengths than covalent counterparts, with strengths usually around 100 pN, which is significantly lower than the nN-scale strength of covalent bonds. Inspired by the slow dissociation kinetics of the cucurbit[7]uril (CB[7])-hexanoate-isoquinoline (HIQ) complex, we discovered that charge-dipole repulsion can be utilized to create strong supramolecular mechanophores. When activated at its -COO- state, the CB[7]-HIQ complex exhibits a high mechanical strength of ~700 pN, comparable to weak covalent bonds such as Au-S bonds or thiol-maleimide adducts. The strength of the CB[7]-HIQ complex can also be tuned with pH in a gradual manner, with a minimum value of ~150 pN at its -COOH state, similar to an ordinary supramolecular conjugate. This research may pave the way for the development of supramolecular architectures that combine the advantages of covalent and supramolecular systems.

Design, optimization, and characterization of covalent organic framework-based nanoparticle drug delivery systems

Drug delivery system has became a research hotspot due to its excellent targeting ability and drug-controlled releases. Herein, a hierarchically flower-like hollow COF (HFH-COF) is synthesized via a simple one-step reaction method at room temperature. The as-prepared HFH-COF has high specific surface area, uniform pore size and pH sensitivity. Based on drug loading experiments using Adriamycin (DOX) as a model molecule, HFH-COF exhibits high drug loading capabilities. The drug release curves under different pH conditions show that HFH-COF is pH sensitive. In vitro cell experiments further confirmed that HFH-COF has good biocompatibility. DOX can be effectively released from HFH-COF to kill tumor cells. The as-prepared HFH-COF drug-loading system has exceptional drug loading ability, excellent biocompatibility, pH sensitivity of the tumor microenvironment, as well as good the potential application prospects in tumor treatment. Overall, a new COF-based drug delivery systems have been developed, and COFs are expanding the field of drug carriers as well.

Intramolecular Triplet Diffusion Facilitates Triplet Dissociation in a Pentacene Hexamer.

Triplet dynamics in singlet fission depend strongly on the strength of the electronic coupling. Covalent systems in solution offer precise control over such couplings. Nonetheless, efficient free triplet generation remains elusive in most systems, as the intermediate triplet pair 1 (T1 T1 ) is prone to triplet-triplet annihilation due to its spatial confinement. In the solid state, entropically driven triplet diffusion assists in the spatial separation of triplets, resulting in higher yields of free triplets. Control over electronic coupling in the solid state is, however, challenging given its sensitivity to molecular packing. We have thus developed a hexameric system (HexPnc) to enable solid-state-like triplet diffusion at the molecular scale. This system is realized by covalently tethering three pentacene dimers to a central subphthalocyanine scaffold. Transient absorption spectroscopy, complemented by theoretical structural optimizations and steady-state spectroscopy, reveals that triplet diffusion is indeed facilitated due to intramolecular cluster formation. The yield of free triplets in HexPnc is increased by a factor of up to 14 compared to the corresponding dimeric reference (DiPnc). Thus, HexPnc establishes crucial design aspects for achieving efficient triplet dissociation in strongly coupled systems by providing avenues for diffusive separation of 1 (T1 T1 ), while, concomitantly, retaining strong interchromophore coupling which preserves rapid formation of 1 (T1 T1 ).

Intramolekulare Triplett‐Diffusion erleichtert die Triplett‐Dissoziation in einem Pentacen‐Hexamer

AbstractDie Triplett‐Dynamik bei der Singulettspaltung hängt stark von der Stärke der elektronischen Kopplung ab. Kovalente Systeme in Lösung bieten eine präzise Kontrolle über solche Kopplungen. Dennoch bleibt die effiziente Erzeugung freier Triplett‐Zustände in den meisten Systemen schwer fassbar, da das intermediäre Triplett‐Paar 1(T1T1) aufgrund seiner räumlichen Begrenzung anfällig für Triplett‐Triplett‐Annihilation ist. Im Festkörper unterstützt die durch Entropie angetriebene Triplett‐Diffusion die räumliche Trennung der Triplett‐Zustände, was zu vermehrten Bildung freier Triplett‐Zustände führt. Einfluss auf die elektronische Kopplung im Festkörper zu nehmen ist jedoch herausfordernd, da sie sich mit der Anordnung der Moleküle im Festkörper ändert.. Daher haben wir ein hexameres System (HexPnc) entwickelt, um eine festkörperähnliche Triplett‐Diffusion auf molekularer Ebene zu ermöglichen. Dieses System besteht aus drei Pentacen‐Dimeren, die kovalent an ein zentrales Subphthalocyanin gebunden sind. Transiente Absorptionsspektroskopie, ergänzt durch theoretische Strukturoptimierungen und stationäre Spektroskopie, zeigt, dass die Triplett‐Diffusion tatsächlich durch intramolekulare Clusterbildung erleichtert wird. Die Ausbildung freier Triplett‐Zustände in HexPnc ist im Vergleich zum entsprechenden dimeren Referenzsystem (DiPnc) bis zu 14‐mal höher. Somit etabliert HexPnc entscheidende Designaspekte für die effiziente Triplett‐Dissoziation in stark gekoppelten Systemen, indem es Wege für die diffusive Trennung von 1(T1T1) aufzeigt. Gleichzeitig wird jedoch eine starke interchromophore Kopplung beibehalten, die die schnelle Bildung von 1(T1T1) nicht einschränkt.

Enantiomer Recognition Based on Chirality Transfer from Chiral Amines to Ternary Dynamic Covalent Systems.

Enantiomer recognition is usually required in organic synthesis and materials and life sciences. This paper describes an enantiomer recognition method based on ternary dynamic covalent systems constructed via the complexation of chiral amines with a chiral boronate derived from 1,4-phenylenediboric acid and an L-DOPA-modified naphthalenediimide. The ternary systems aggregate into chiral assemblies driven by π-π interactions, and the chirality is transferred from the chiral amines to assemblies with high stereospecificity. Consequently, the enantiomer composition of chiral amines and the absolute configuration of the major enantiomer can be determined according to the sign of the Cotton effect of the ternary system by using circular dichroism (CD) spectroscopy. This method offers the advantage of using the long wavelength CD signals of the boronate at around 520 nm, thereby avoiding interference with those of the carbon skeleton. This ternary system provides a novel approach to the design of enantiomer recognition systems.

Dynamic covalent synthesis.

Dynamic covalent synthesis aims to precisely control the assembly of simple building blocks linked by reversible covalent bonds to generate a single, structurally complex, product. In recent years, considerable progress in the programmability of dynamic covalent systems has enabled easy access to a broad range of assemblies, including macrocycles, shape-persistent cages, unconventional foldamers and mechanically-interlocked species (catenanes, knots, etc.). The reversibility of the covalent linkages can be either switched off to yield stable, isolable products or activated by specific physico-chemical stimuli, allowing the assemblies to adapt and respond to environmental changes in a controlled manner. This activatable dynamic property makes dynamic covalent assemblies particularly attractive for the design of complex matter, smart chemical systems, out-of-equilibrium systems, and molecular devices.

Recent Progress in the Field of Intrinsic Self-Healing Elastomers

Self-healing elastomers refer to a class of synthetic polymers that possess the unique ability to autonomously repair from internal and external damages. In recent years, significant progress has been made in the field of self-healing elastomers. In particular, intrinsic self-healing elastomers have garnered a great deal of attention. This mini-review outlines recent advancements in the mechanisms, preparation methods, and properties of various intrinsic self-healing elastomers based on non-covalent bond systems, reversible covalent bond systems, and multiple dynamic bond composite systems. We hope that this review will prove valuable to researchers in order to facilitate the development of novel strategies and technologies for preparing high-performance self-healing elastomers for advanced applications.

Alterferroicity with seesaw-type magnetoelectricity.

Primary ferroicities like ferroelectricity and ferromagnetism are essential physical properties of matter. Multiferroics, with coexisting multiple ferroic orders in a single phase, provide a convenient route to magnetoelectricity. Even so, the general trade-off between magnetism and polarity remains inevitable, which prevents practicable magnetoelectric cross-control in the multiferroic framework. Here, an alternative strategy, i.e., the so-called alterferroicity, is proposed to circumvent the magnetoelectric exclusiveness, which exhibits multiple but noncoexisting ferroic orders. The natural exclusion between magnetism and polarity, as an insurmountable weakness of multiferroicity, becomes a distinct advantage in alterferroicity, making it an inborn rich ore for intrinsic strong magnetoelectricity. The general design rules for alterferroic materials rely on the competition between the instabilities of phononic and electronic structures in covalent systems. Based on primary density functional theory calculations, Ti-based trichalcogenides are predicted to be alterferroic candidates, which exhibit unique seesaw-type magnetoelectricity. This alterferroicity, as an emerging branch of the ferroic family, reshapes the framework of magnetoelectricity, going beyond the established scenario based on multiferroicity.

A Continuous Action Space Tree search for INverse desiGn (CASTING) framework for materials discovery

Material properties share an intrinsic relationship with their structural attributes, making inverse design approaches crucial for discovering new materials with desired functionalities. Reinforcement Learning (RL) approaches are emerging as powerful inverse design tools, often functioning in discrete action spaces. This constrains their application in materials design problems, which involve continuous search spaces. Here, we introduce an RL-based framework CASTING (Continuous Action Space Tree Search for inverse design), that employs a decision tree-based Monte Carlo Tree Search (MCTS) algorithm with continuous space adaptation through modified policies and sampling. Using representative examples like Silver (Ag) for metals, Carbon (C) for covalent systems, and multicomponent systems such as graphane, boron nitride, and complex correlated oxides, we showcase its accuracy, convergence speed, and scalability in materials discovery and design. Furthermore, with the inverse design of super-hard Carbon phases, we demonstrate CASTING’s utility in discovering metastable phases tailored to user-defined target properties and preferences.

Interplay of Mechanochemistry and Material Processes in the Graphite to Diamond Phase Transformation.

The manifestation of intramolecular strains in covalent systems is widely known to accelerate chemical reactions and open alternative reaction paths. This process is moderately well understood for isolated molecules and unimolecular processes. However, in condensed matter processes such as phase transformations, material properties and structure may influence typical mechanochemical effects. Therefore, we utilize steered molecular dynamics to induce out of plane strains in graphite and compress the system under a constant strain rate to induce phase transformation. We show that the out of plane strain allows phase transformations to initiate at small amounts of compressive strain. However, in contrast to typical mechanochemical results, the sum of compressive and out of plane work needed to form a diamond has a local minimum due to altered defect formation processes during phase transformation. Additionally, these altered processes slow the kinetics of the phase transformation, taking longer from initiation to total material transformation.

Universal approach for developing reprocessable and reprintable plant oil-based resins for digital light processing 3D printing

Recently, researchers have shown great interest in the development of biobased and reprintable 3D printing materials for sustainable 3D printing. Herein, a method for developing plant oil (PO)-based digital light processing (DLP) printing resins that are both reprocessable and reprintable is proposed. Biobased UV-curable monomers (POPITs) containing dynamic hindered urea bonds (HUBs) from POs were synthesized via the thiol-ene click reaction. A range of DLP printing resins (POPIT-I) with high biobased content (52.6%–58.1%) were prepared by blending POPITs with the biobased dilute monomer isobornyl acrylate. These resins demonstrated good mechanical and thermal properties (e.g., tensile strength: 45.1–49.5 MPa and Tg: 74–92 °C), as well as high DLP printing quality. Reprocessable DLP printing was employed to fabricate large-volume parts through the dissociation and reorganization of HUBs, thereby reducing printing difficulty and printing time. Additionally, a powder blending and modification method was used to recycle and reprint printed materials. The printing materials, including printed green parts and discarded supporting materials, were milled into micron-sized powders and then blended with POPIT-I to prepare the powder blending resins. The milled powders in the powder blending resins were further modified by 2-(tert-butylamino) ethyl methacrylate to prepare reprinting resins. This process resulted in the grafting of C = C onto the powder surface, which eliminated heterogeneity between the powders and POPIT-I. The mechanical and thermal properties of the reprinting resins were comparable with those of POPIT-I even after three rounds of recycling. Furthermore, the reprinting method reported here is applicable to other dynamic covalent bond-based 3D printing systems.

Counterion-induced antibiotic-based small-molecular micelles for methicillin-resistant Staphylococcus aureus infections.

A new counterion-induced small-molecule micelle (SM) with surface charge-switchable activities for methicillin-resistant Staphylococcus aureus (MRSA) infections is proposed. The amphiphilic molecule formed by zwitterionic compound and the antibiotic ciprofloxacin (CIP), via a "mild salifying reaction" of the amino and benzoic acid groups, can spontaneously assemble into counterion-induced SMs in water. Through vinyl groups designed on zwitterionic compound, the counterion-induced SMs could be readily cross-linked using mercapto-3, 6-dioxoheptane by click reaction, to create pH-sensitive cross-linked micelles (CSMs). Mercaptosuccinic acid was also decorated on the CSMs (DCSMs) by the same click reaction to afford charge-switchable activities, resulting in CSMs that were biocompatible with red blood cells and mammalian cells in normal tissues (pH 7.4), while having strong retention to negatively charged bacterial surfaces at infection sites, based on electrostatic interaction (pH 5.5). As a result, the DCSMs could penetrate deep into bacterial biofilms and then release drugs in response to the bacterial microenvironment, effectively killing the bacteria in the deeper biofilm. The new DCSMs have several advantages such as robust stability, a high drug loading content (∼ 30%), easy fabrication, and good structural control. Overall, the concept holds promise for the development of new products for clinical application. STATEMENT OF SIGNIFICANCE: We fabricated a new counterion-induced small-molecule micelle with surface charge-switchable activities (DCSMs) for methicillin-resistant Staphylococcus aureus (MRSA) infections. Compared with reported covalent systems, the DCSMs not only have improved stability, high drug loading content (∼ 30%), and good biosafety, but also have the environmental stimuli response, and antibacterial activity of the original drugs. As a result, the DCSMs exhibited enhanced antibacterial activities against MRSA both in vitro and in vivo. Overall, the concept holds promise for the development of new products for clinical application.

Thin-Film Organic Heteroepitaxy.

Incorporating crystalline organic semiconductors into electronic devices requires understanding of heteroepitaxy given the ubiquity of heterojunctions in these devices. However, while rules for commensurate epitaxy of covalent or ionic inorganic material systems are known to be dictated by lattice matching constraints, rules for heteroepitaxy of molecular systems are still being written. Here, it is found that lattice matching alone is insufficient to achieve heteroepitaxy in molecular systems, owing to weak intermolecular forces that describe molecular crystals. It is found that, in addition, the lattice matched plane also must be the lowest energy surface of the adcrystal to achieve one-to-one commensurate molecular heteroepitaxy over a large area. Ultraviolet photoelectron spectroscopy demonstrates the lattice matched interface to be of higher electronic quality than a disordered interface of the same materials.

Epoxy Adhesives with Reversible Hardeners: Controllable Thermal Debonding in Bulk and at Interfaces.

On-demand adhesive dismantling has the potential to improve multi-material product recycling, but its implementation has been hampered by a critical trade-off between strong bonding and easy debonding. As a result, the temperature range in which these temporary adhesives can be used is relatively limited. Here, wereport a new class of dynamic epoxy resins that significantly extends this upper temperature limit and still achieves fast debonding. Specifically, two types of dynamic polyamidoamine curing agents for epoxy hardening weredeveloped, being polysuccinamides (PSA) and polyglutaramides (PGA). As the dynamic debonding/rebonding process of PSA and especially PGA linkages is more thermally demanding and at the same time more thermally robust than previously reported dynamic covalent systems, the resulting materials can be triggered at high temperatures, and at the same time remain bonded over a wide temperature range. The versatility of the PSA and PGA dynamic adhesive curing system wasdemonstrated in classical bulk adhesive formulations, as well as in dynamic covalent linking to a PSA- or PGA-functionalised surface. As a result, an attractive drop-in strategy wasachieved for producing debondable and rebondable epoxy adhesives, with high complementarity to existing adhesive resin technologies and applicable in an industrially relevant temperature window. This article is protected by copyright. All rights reserved.

Dynamic Covalent Self‐sorting in Molecular and Polymeric Architectures Enabled by Spiroborate Bond Exchange

AbstractSelf‐sorting is commonly observed in complex reaction systems, which has been utilized to guide the formation of single major by‐design molecules. However, most studies have been focused on non‐covalent systems, and using self‐sorting to achieve covalently bonded architectures is still relatively less explored. Herein, we first demonstrated the dynamic nature of spiroborate linkage and systematically studied the self‐sorting behavior observed in the transformation between spiroborate‐linked well‐defined polymeric and molecular architectures, which is enabled by spiroborate bond exchange. The scrambling between a macrocycle and a 1D helical covalent polymer led to the formation of a molecular cage, whose structures are all unambiguously elucidated by single‐crystal X‐ray diffraction. The results indicate that the molecular cage is the thermodynamically favored product in this multi‐component reaction system. This work represents the first example of a 1D polymeric architecture transforming into a shape‐persistent molecular cage, driven by dynamic covalent self‐sorting. This study will further guide the design of spiroborate‐based materials and open the possibilities for the development of novel complex yet responsive dynamic covalent molecular or polymeric systems.

Dynamic Covalent Self-sorting in Molecular and Polymeric Architectures Enabled by Spiroborate Bond Exchange.

Self-sorting is commonly observed in complex reaction systems, which has been utilized to guide the formation of single major by-design molecules. However, most studies have been focused on non-covalent systems, and using self-sorting to achieve covalently bonded architectures is still relatively less explored. Herein, we first demonstrated the dynamic nature of spiroborate linkage and systematically studied the self-sorting behavior observed in the transformation between spiroborate-linked well-defined polymeric and molecular architectures, which is enabled by spiroborate bond exchange. The scrambling between a macrocycle and a 1D helical covalent polymer led to the formation of a molecular cage, whose structures are all unambiguously elucidated by single-crystal X-ray diffraction. The results indicate that the molecular cage is the thermodynamically favored product in this multi-component reaction system. This work represents the first example of a 1D polymeric architecture transforming into a shape-persistent molecular cage, driven by dynamic covalent self-sorting. This study will further guide the design of spiroborate-based materials and open the possibilities for the development of novel complex yet responsive dynamic covalent molecular or polymeric systems.

Strengths and limitations of the adiabatic exact-exchange kernel for total energy calculations.

We investigate the adiabatic approximation to the exact-exchange kernel for calculating correlation energies within the adiabatic-connection fluctuation-dissipation framework of time-dependent density functional theory. A numerical study is performed on a set of systems having bonds of different character (H2 and N2 molecules, H-chain, H2-dimer, solid-Ar, and the H2O-dimer). We find that the adiabatic kernel can be sufficient in strongly bound covalent systems, yielding similar bond lengths and binding energies. However, for non-covalent systems, the adiabatic kernel introduces significant errors around equilibrium geometry, systematically overestimating the interaction energy. The origin of this behavior is investigated by studying a model dimer composed of one-dimensional, closed-shell atoms, interacting via soft-Coulomb potentials. The kernel is shown to exhibit a strong frequency dependence at small to intermediate atomic separation that affects both the low-energy spectrum and the exchange-correlation hole obtained from the corresponding diagonal of the two-particle density matrix.

Display of multiple proteins on engineered canine parvovirus-like particles expressed in cultured silkworm cells and silkworm larvae.

Recent progress has been made dramatically in decorating virus-like particles (VLPs) on the surface or inside with functional molecules, such as antigens or nucleic acids. However, it is still challenging to display multiple antigens on the surface of VLP to meet the requirement as a practical vaccine candidate. Herein this study, we focus on the expression and engineering of the capsid protein VP2 of canine parvovirus for VLP display in the silkworm-expression system. The chemistry of the SpyTag/SpyCatcher (SpT/SpC) and SnoopTag/SnoopCatcher (SnT/SnC) are efficient protein covalent ligation systems to modify VP2 genetically, where SpyTag/SnoopTag are inserted into the N-terminus or two distinct loop regions (Lx and L2) of VP2. The SpC-EGFP and SnC-mCherry are employed as model proteins to evaluate their binding and display on six SnT/SnC-modified VP2 variants. From a series of protein binding assays between indicated protein partners, we showed that the VP2 variant with SpT inserted at the L2 region significantly enhanced VLP display to 80% compared to 5.4% from N-terminal SpT-fused VP2-derived VLPs. In contrast, the VP2 variant with SpT at the Lx region failed to form VLPs. Moreover, the SpT (Lx)/SnT (L2) double-engineered chimeric VP2 variants showed covalent conjugation capacity to both SpC/SnC protein partners. The orthogonal ligations between those binding partners were confirmed by both mixing purified proteins and co-infecting cultured silkworm cells or larvae with desired recombinant viruses. Our results indicate that a convenient VLP display platform was successfully developed for multiple antigen displays on demand. Further verifications can be performed to assess its capacity for displaying desirable antigens and inducing a robust immune response to targeted pathogens.

Aspherical atom refinements on X-ray data of diverse structures including disordered and covalent organic framework systems: a time-accuracy trade-off.

Aspherical atom refinement is the key to achieving accurate structure models, displacement parameters, hydrogen-bond lengths and analysis of weak interactions, amongst other examples. There are various quantum crystallographic methods to perform aspherical atom refinement, including Hirshfeld atom refinement (HAR) and transferable aspherical atom model (TAAM) refinement. Both HAR and TAAM have their limitations and advantages, the former being more accurate and the latter being faster. With the advent of non-spherical atoms in Olex2 (NoSpherA2), it is now possible to overcome some limitations, like treating disorder, twinning and network structures, in aspherical refinements using HAR, TAAM or both together. TAAM refinement in NoSpherA2 showed significant improvement in refinement statistics compared with independent atom model (IAM) refinements on a diverse set of X-ray diffraction data. The sensitivity of TAAM towards poor data quality and disorder was observed in terms of higher refinement statistics for such structures. A comparison of IAM with TAAM and HAR in NoSpherA2 indicated that the time taken by TAAM refinements was of the same order of magnitude as that taken by IAM, while in HAR the time taken using a minimal basis set was 50 times higher than for IAM and rapidly increased with increasing size of the basis sets used. The displacement parameters for hydrogen and non-hydrogen atoms were very similar in both HAR and TAAM refinements. The hydrogen-bond lengths were slightly closer to neutron reference values in the case of HAR with higher basis sets than in TAAM. To benefit from the advantages of each method, a new hybrid refinement approach has been introduced, allowing a combination of IAM, HAR and TAAM in one structure refinement. Refinement of coordination complexes involving metal-organic compounds and network structures such as covalent organic frameworks and metal-organic frameworks is now possible in a hybrid mode such as IAM-TAAM or HAR-TAAM, where the metal atoms are treated via either the IAM or HAR method and the organic part via TAAM, thus reducing the computational costs without compromising the accuracy. Formal charges on the metal and ligand can also be introduced in hybrid-mode refinement.

Highly tunable β-relaxation enables the tailoring of crystallization in phase-change materials

In glasses, secondary (β-) relaxations are the predominant source of atomic dynamics. Recently, they have been discovered in covalently bonded glasses, i.e., amorphous phase-change materials (PCMs). However, it is unclear what the mechanism of β-relaxations is in covalent systems and how they are related to crystallization behaviors of PCMs that are crucial properties for non-volatile memories and neuromorphic applications. Here we show direct evidence that crystallization is strongly linked to β-relaxations. We find that the β-relaxation in Ge15Sb85 possesses a high tunability, which enables a manipulation of crystallization kinetics by an order of magnitude. In-situ synchrotron X-ray scattering, dielectric functions, and ab-initio calculations indicate that the weakened β-relaxation intensity stems from a local reinforcement of Peierls-like distortions, which increases the rigidity of the bonding network and decreases the dynamic heterogeneity. Our findings offer a conceptually new approach to tuning the crystallization of PCMs based on manipulating the β-relaxations.