Dynamic Chemistry Research Articles

Catalytic resonance theory: the catalytic mechanics of programmable ratchets.

Catalytic reaction networks of multiple elementary steps operating under dynamic conditions via a programmed input oscillation are difficult to interpret and optimize due to reaction system complexity. To understand these dynamic systems, individual elementary catalytic reactions oscillating between catalyst states were evaluated to identify their three fundamental characteristics that define their ability to promote reactions away from equilibrium. First, elementary catalytic reactions exhibit directionality to promote reactions forward or backward from equilibrium as determined by a ratchet directionality metric comprised of the input oscillation duty cycle and the reaction rate constants. Second, catalytic ratchets are defined by the catalyst state of strong or weak binding that permits reactants to proceed through the transition state. Third, elementary catalytic ratchets exhibit a cutoff frequency which defines the transition in applied frequency for which the catalytic ratchet functions to promote chemistry away from equilibrium. All three ratchet characteristics are calculated from chemical reaction parameters including rate constants derived from linear scaling parameters, reaction conditions, and catalyst electronic state. The characteristics of the reaction network's constituent elementary catalytic reactions provided an interpretation of complex reaction networks and a method of predicting the behavior of dynamic surface chemistry on oscillating catalysts.

D-(+)-glucose triggered selective hydrometallogelation in a C3-symmetric gelator

A chiral and conductive hydrometallogel has been synthesized using dynamic boronic acid-cis diol chemistry. A novel tris-boronic acid functionalized C3-symmetric gelator (MB) was obtained from trimesic acid derivative which upon...

Polymer design for solid-state batteries and wearable electronics.

Solid-state batteries are increasingly centre-stage for delivering more energy-dense, safer batteries to follow current lithium-ion rechargeable technologies. At the same time, wearable electronics powered by flexible batteries have experienced rapid technological growth. This perspective discusses the role that polymer design plays in their use as solid polymer electrolytes (SPEs) and as binders, coatings and interlayers to address issues in solid-state batteries with inorganic solid electrolytes (ISEs). We also consider the value of tunable polymer flexibility, added capacity, skin compatibility and end-of-use degradability of polymeric materials in wearable technologies such as smartwatches and health monitoring devices. While many years have been spent on SPE development for batteries, delivering competitive performances to liquid and ISEs requires a deeper understanding of the fundamentals of ion transport in solid polymers. Advanced polymer design, including controlled (de)polymerisation strategies, precision dynamic chemistry and digital learning tools, might help identify these missing fundamental gaps towards faster, more selective ion transport. Regardless of the intended use as an electrolyte, composite electrode binder or bulk component in flexible electrodes, many parallels can be drawn between the various intrinsic polymer properties. These include mechanical performances, namely elasticity and flexibility; electrochemical stability, particularly against higher-voltage electrode materials; durable adhesive/cohesive properties; ionic and/or electronic conductivity; and ultimately, processability and fabrication into the battery. With this, we assess the latest developments, providing our views on the prospects of polymers in batteries and wearables, the challenges they might address, and emerging polymer chemistries that are still relatively under-utilised in this area.

Non-isocyanate Polythiourethane Network from Biowaste: Achieving Circularity via Multidimensional Chemical Recycling with Valuable Small-Molecule Recovery and Reprocessability by Understanding the Dynamic Chemistry

Non-isocyanate Polythiourethane Network from Biowaste: Achieving Circularity via Multidimensional Chemical Recycling with Valuable Small-Molecule Recovery and Reprocessability by Understanding the Dynamic Chemistry

Understanding the Role of Trapezoids in Honeycomb Self-Assembly-Pathways between a Columnar Liquid Quasicrystal and its Liquid-Crystalline Approximants.

Quasiperiodic patterns and crystals-having long range order without translational symmetry-have fascinated researchers since their discovery. In this study, we report on new p-terphenyl-based T-shaped facial polyphiles with two alkyl end chains and a glycerol-based hydrogen-bonded side group that self-assemble into an aperiodic columnar liquid quasicrystal with 12-fold symmetry and its periodic liquid-crystalline approximants with complex superstructures. All represent honeycombs formed by the self-assembly of the p-terphenyls, dividing space into prismatic cells with polygonal cross-sections. In the perspective of tiling patterns, the presence of unique trapezoidal tiles, consisting of three rigid sides formed by the p-terphenyls and one shorter, incommensurate, and adjustable side by the alkyl end chains, plays a crucial role for these phases. A delicate temperature-dependent balance between conformational, entropic and space-filling effects determines the role of the alkyl chains, either as network nodes or trapezoid walls, thus resulting in the order-disorder transitions associated with emergence of quasiperiodicity. In-depth analysis suggests a change from a quasiperiodic tiling involving trapezoids to a modified one with a contribution of trapezoid pair fusion. This work paves the way for understanding quasiperiodicity emergence and develops fundamental concepts for its generation by chemical design of non-spherical molecules, aggregates, and frameworks based on dynamic reticular chemistry.

Understanding the Role of Trapezoids in Honeycomb Self‐Assembly—Pathways between a Columnar Liquid Quasicrystal and its Liquid‐Crystalline Approximants

AbstractQuasiperiodic patterns and crystals—having long range order without translational symmetry—have fascinated researchers since their discovery. In this study, we report on new p‐terphenyl‐based T‐shaped facial polyphiles with two alkyl end chains and a glycerol‐based hydrogen‐bonded side group that self‐assemble into an aperiodic columnar liquid quasicrystal with 12‐fold symmetry and its periodic liquid‐crystalline approximants with complex superstructures. All represent honeycombs formed by the self‐assembly of the p‐terphenyls, dividing space into prismatic cells with polygonal cross‐sections. In the perspective of tiling patterns, the presence of unique trapezoidal tiles, consisting of three rigid sides formed by the p‐terphenyls and one shorter, incommensurate, and adjustable side by the alkyl end chains, plays a crucial role for these phases. A delicate temperature‐dependent balance between conformational, entropic and space‐filling effects determines the role of the alkyl chains, either as network nodes or trapezoid walls, thus resulting in the order‐disorder transitions associated with emergence of quasiperiodicity. In‐depth analysis suggests a change from a quasiperiodic tiling involving trapezoids to a modified one with a contribution of trapezoid pair fusion. This work paves the way for understanding quasiperiodicity emergence and develops fundamental concepts for its generation by chemical design of non‐spherical molecules, aggregates, and frameworks based on dynamic reticular chemistry.

Self‐healing polyurethane based on a substance supplement and dynamic chemistry: Repair mechanisms and applications

AbstractThis review systematically summarizes the repair mechanisms and applications of self‐healing polyurethane (SHPU) materials aiming at energy conservation and safety under different repair methods. As of now, the repair methods that have emerged can be divided into two categories: substance landfill and bond repair. In terms of the repair mechanisms for both, the former involves the release of healing agents from micro‐carriers (microcapsules, hollow fibers, and microvascular) to fill the damaged area upon external impact. In contrast, bond repair combines physical and chemical changes triggered by light, heat, and other factors. To achieve efficient self‐healing in this mode, both the reorganization of broken chemical bonds and the high mobility of chain segments are crucial. Reversible covalent bonds and supramolecular interactions, as two branches of aforementioned reversible chemical bonds, share the responsibility for maintaining efficient self‐healing despite infinite cycling. Additionally, multiple synergistic crosslinked networks, special nanomaterials, and microphase separation are often used to solve the problem of incompatible healing efficiency and mechanical strength in bond repair. When the perspective is focused on the application, this gradually improved SHPU with strong potential and comprehensive performance has provided raw materials for many fields related to human development, such as road, architecture, healthcare, and electronic.

Covalent adaptable networks and thermosets of multi-block ethylene/1-octene copolymers made by free-radical processing: Effects of melt flow index and crystallinity on thermomechanical properties and reprocessability

Chain shuttling polymerization has facilitated the rapid development of olefin block copolymers (OBCs) such as ethylene/1-octene multi-block copolymers. The properties of OBCs stem from various parameters such as average block length, number of blocks per chain, etc., which lead to complexity associated with establishing structure–property relationships between precursor OBCs and properties of cross-linked OBCs. Additionally, permanent cross-linking of OBCs sacrifices their recyclability, and cross-linked OBCs capable of being reprocessed have seldom been reported. Here, permanently cross-linked OBCs (OBCXs) and dynamically cross-linked OBCs, or OBC covalent adaptable networks (CANs), were synthesized by melt-state reactive processing of neat OBCs with various crystallinities and melt flow indices (MFIs). The OBC CANs are capable of dialkylamino disulfide dynamic chemistry via the grafting of bis(2,2,6,6-tetramethyl-4-piperidyl methacrylate) disulfide, or BiTEMPS methacrylate, cross-linkers onto OBC backbone chains. Thermomechanical characterizations indicate that increasing crystallinity and decreasing MFI in precursor OBCs lead to higher cross-link densities in OBCXs and OBC CANs. Dynamically cross-linking OBCs into CANs also significantly improves their elevated-temperature creep resistance. Stress relaxation results of OBC CANs indicate an increased average relaxation time with greater cross-link density. Distinct from other CANs capable of dialkylamino disulfide chemistry, the stress relaxation behaviors of OBC CANs of higher cross-link density show evident dependence on their network viscoelasticities. In OBC CANs of lower cross-link density, the dynamic chemistry more strongly governs their stress relaxation behaviors. Finally, the OBC CANs exhibit full cross-link density and thermomechanical property recovery after reprocessing, whereas the OBCXs cannot be reprocessed due to their irreversible cross-links.

Efficient two-dimensional simulation of primary reference fuel ignition under engine-relevant thermal stratification

Despite vast research on engine knock, there remains a limited understanding of the interaction between reaction front propagation, pressure oscillations, and fuel chemistry. To explore this through computational fluid dynamics, the adoption of advanced numerical methods is necessary. In this context, the current study introduces ARCFoam, a computational framework that combines dynamic mesh balancing, chemistry balancing, and adaptive mesh refinement with an explicit, density-based solver designed for simulating high-speed flows in OpenFOAM. First, the validity and performance of the solver are assessed by simulating directly initiated detonation in a hydrogen/air mixture. Second, the study explores the one/two-dimensional (1D/2D) hotspot ignition for the primary reference fuel and illuminates the impact of transitioning to 2D simulations on the predicted combustion modes. The 2D hotspot simulations reveal a variety of 2D physical phenomena, including the appearance of converging shock/detonation fronts as a result of negative temperature coefficient (NTC) behavior and shock wave reflection-induced detonation. The main results of the paper are as follows: (1) NTC chemistry is capable of drastically changing the anticipated reaction front propagation mode by manipulating the local/global reactivity distribution inside and outside the hotspot, (2) subsonic hotspot ignition can induce detonation (superknock) through the generation of shock waves and subsequent wall reflections, and (3) while the 1D framework predicts the initial combustion mode within the hotspot, significant differences between 1D and 2D results may emerge in scenarios involving ignition-to-detonation transitions and curvature effect on shock/detonation front propagation.

Gas-based dynamic chemistry and assembly

Gas-based dynamic chemistry and assembly

Self‐healing polymers for soft actuators and robots

AbstractAdvances in artificial intelligence technology bring a rising demand on stimuli responsive actuating materials and soft actuators. By the virtue of easy deformation and mechanical resilience, polymers with unique properties like shape‐memory, electro/magneto‐active, and thermal/humidity/chemical‐responsiveness have emerged as promising candidates for soft robotics. Damage tolerance or a degree of self‐healing ability improves soft robots endowed with such materials longevity, and provides safeguards for the function and potentially reduce costs. The combination of stimuli‐responsive actuation and self‐healing function involves elaborate supramolecular chemical and physical structure designs, being a challenging topic within the field of soft robotics and thus intriguing wide research interests. This review aims to discuss some highlights in convenient combination of stimuli‐responsive micro‐nanostructures and dynamic bonds chemistry within last 5 years, that further give the actuators recovery of mechanic and function, and improved comprehensive properties. Through a review of the most remarkable paradigms, the order organization of dynamic bonds with liquid crystal mesogenic units, functional micro‐nanofillers, hierarchical gradient interfaces, etc. are outlined. Finally, the perspectives and main challenges of self‐healable actuators are summarized. It is anticipated that this review will provide scientists with insights and guidance for the future innovative research in this field.

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To imbue traditional plastics with self‐healing attributes akin to living organisms, it is essential to judiciously constitutional dynamic chemistry and adopt precise topological structure designs during the synthesis of repairable plastics. Furthermore, their practical application demands enhancement of their mechanical properties, particularly toughness. Thus, this review encapsulates the existing work and accomplishments in the domain of high‐performance healable plastics by focusing on three main aspects: topological structures, constitutional dynamic chemistry, and strategies for toughening. image

High‐performance healable plastics: Focusing topological structure design based on constitutional dynamic chemistry

AbstractOver the past three decades, significant efforts have been dedicated to developing polymeric materials with exciting healable ability; however, stiff and healable plastics with high glass transition temperatures (Tg) have received relatively less attention compared to their soft counterparts such as gels and elastomers due to the inherent trade‐off between mechanical robustness and dynamics. High‐performance plastics are irreplaceable in the fields of engineering and industry, making it a challenging yet urgent task to confer them with desired healable properties whilst maintaining high mechanical strength. In this review, we first present recent advances in the field of high‐performance healable plastics based on constitutional dynamic chemistry, from the perspective of different topological structures including linear‐, branched‐ and network types. Meanwhile, we also elaborate on various toughening strategies for existing healable plastics, mainly centered around molecular to micrometer scale modifications. Moreover, we also provide a detailed exposition of previous reports on the autonomously room‐temperature self‐healing plastics, which represent a groundbreaking development in the realm of advanced healable plastics. Eventually, we emphasize diverse functionalized healable plastics to illustrate their potential for practical implementation, and propose an outlook on the future development of healable plastics.image

Enhancing hydrolytic stability of dynamic imine bonds and polymers in acidic media with internal protecting groups

Imine bonds are among the most explored building motifs in dynamic chemistry, polymers, and materials, and yet, their acid-resistance remains a longstanding issue. Herein we demonstrate a concept of internal protecting groups for improving the kinetic stability of dynamic imine bonds and polymers. Systematic examination of structure-reactivity relationship of a series of aldehydes/imines bearing a neighboring carboxyl allowed uncovering of required structural features for dynamically masking imine bonds with cyclic structures. Mechanistic studies indicated that noncovalent interactions along with sterics control the ring-chain equilibrium and the stability of imine bonds. The incorporation of internal protecting groups into imine polymers further enabled their controlled stability in acidic media. Moreover, a combination of dynamic covalent network and coordination supramolecular network provided a facile means for the modulation of luminescent and mechanical properties of polymers. The strategies and results reported should be beneficial to molecular assemblies, dynamic polymers, biological delivery, and intelligent materials.

Reprocessable Non-Isocyanate Polyurethane Vitrimers

Non-isocyanate polyurethanes (NIPUs, polyhydroxyurethanes, PHUs), have emerged as sustainable alternatives to conventional isocyanate-polyol polyurethanes. However, the permanent cross-links in traditional linear, crosslinked polyhydroxyurethane polymer networks hinder their recyclability for high-value applications. In this study, we provide a comprehensive overview of polyhydroxyurethane vitrimers – polymers with intrinsic recyclability – containing dynamic covalent adaptable bonds that allow them to be reprocessed or self-healed under external stimuli such as heat or solvents. These materials exhibit a unique combination of the attributes of thermosets, such as improved heat stability, solvent resistance or enhanced mechanical properties, and the reprocessability of thermoplastics. Various strategies have been explored to enable the reprocessability of PHUs. External catalysts, such as 4-(dimethylamino)pyridine (DMAP) have been used to facilitate exchange reactions and promote reprocessing. Additionally, the use of functionalized silica nanoparticles as reinforcing fillers has influenced the material’s behavior during reprocessing. Another method involved the incorporation of dynamic disulfide bonds to expedite reprocessing times for PHU networks, while dissociative dynamic chemistry has enabled self-healing behavior in certain partially cross-linked NIPUs. These advancements demonstrate the potential for tailoring the reprocessability and mechanical attributes of NIPUs, paving the way for sustainable and versatile polymeric materials, and addressing the environmental concerns associated with traditional polyurethanes.

Water‐Insensitive Self‐Healing Materials: From Network Structure Design to Advanced Soft Electronics

AbstractPolymeric materials capable of spontaneously healing physical damages and restoring various functions have been attracting growing interest. Among these, the category of water‐insensitive self‐healing materials emerges as a promising research focus due to their reliable self‐healing and stable mechanical properties in high‐humidity environments and even underwater. In this review, an update on the significant advancements in the design of water‐insensitive self‐healing polymers is presented, which are based on various unique chains. Their advantages and limitations are discussed. Additionally, a series of typical dynamic interactions that are used to enable autonomous self‐healing in underwater environments is highlighted. Moving beyond these fundamental designs, the diverse opportunities to leverage recent synthetic advancements in water‐insensitive self‐healing materials for the progression of soft electronic applications are systematically discussed. Ultimately, the significant challenges and remaining opportunities to present a comprehensive view of the future development of water‐insensitive self‐healing materials are highlighted. This review aims to stimulate further innovation in this burgeoning and emerging field of intrinsic healable materials, interfacing with dynamic chemistry and soft electronics.

Protein fibers with self-recoverable mechanical properties via dynamic imine chemistry

The manipulation of internal interactions at the molecular level within biological fibers is of particular importance but challenging, severely limiting their tunability in macroscopic performances and applications. It thus becomes imperative to explore new approaches to enhance biological fibers’ stability and environmental tolerance and to impart them with diverse functionalities, such as mechanical recoverability and stimulus-triggered responses. Herein, we develop a dynamic imine fiber chemistry (DIFC) approach to engineer molecular interactions to fabricate strong and tough protein fibers with recoverability and actuating behaviors. The resulting DIF fibers exhibit extraordinary mechanical performances, outperforming many recombinant silks and synthetic polymer fibers. Remarkably, impaired DIF fibers caused by fatigue or strong acid treatment are quickly recovered in water directed by the DIFC strategy. Reproducible mechanical performance is thus observed. The DIF fibers also exhibit exotic mechanical stability at extreme temperatures (e.g., −196 °C and 150 °C). When triggered by humidity, the DIFC endows the protein fibers with diverse actuation behaviors, such as self-folding, self-stretching, and self-contracting. Therefore, the established DIFC represents an alternative strategy to strengthen biological fibers and may pave the way for their high-tech applications.

P-Block Element Catecholates: Lewis Superacidic, Constitutionally Dynamic, and Redox Active

AbstractNumerous strategies for enhancing the reactivity and properties of p-block elements have been devised in the past decades. This Account discusses our approaches by distinct ligand control on p-block elements in their normal (group) oxidation states. Catecholato ligands on silicon, germanium, or phosphorus produce a range of rewarding properties. Substantial electron withdrawal paired with structural constraint effects (influence of deformation energy) impart Lewis superacidity to these abundant elements. The ease of synthesis of such species facilitates screening in catalysis, promising a range of applications by powerful bond activation. Low-barrier Si–O/Si–O bond metathesis provides the most abundant bond in our Earth’s crust, with adaptive features under mild conditions, and establishes a new branch of constitutional dynamic chemistry. The redox-active character of catecholates grants access to novel compounds with tunable open-shell features. Overall, p-block catecholates offer unique opportunities due to their versatile features that will enrich the chemistry of the main-group elements.1 Introduction2 Halogenated Catecholates at Silicon Cause Substantial Lewis Acidity3 Constitutional Dynamics Cause a Structural Mystery4 Strong Silicon Lewis Acids Allow the Exploration of Uncharted Structures, Bond Activations, and Catalysis5 The Catechol Approach on Other Elements: Germanium and Phosphorus6 Catechols Are Redox Active: Also at Silicon7 Conclusion

Accurate SCC-DFTB Parametrization of Liquid Water with Improved Atomic Charges and Iterative Boltzmann Inversion.

This work presents improvements of the description of liquid water within the self-consistent-charge density-functional based tight-binding scheme combining the use of Weighted Mulliken (WMull) charges and optimized O-H repulsive potential through the iterative Boltzmann inversion (IBI) process. The quality of the newly developed models is validated considering pair radial distribution functions (RDFs), as well as other structural, energetic, thermodynamic, and dynamic properties. The use of WMull charges certainly improves the agreement with experimental data, however leading to over-structured RDFs at short distance, that can be further improved by considering an optimized O-H repulsive potential obtained by the IBI process. Three different schemes were used to optimize this potential: (i) optimization including short O-H distances. This led to accurate RDFs as well as improved self-diffusion coefficient and heat of vaporization, while the proton transfer energy barrier is severely deteriorated; (ii) optimization starting at long distance. The proton transfer energy barrier is recovered while the heat of vaporization is deteriorated and the O-H RDF is less accurate at short distance; (iii) optimization within the path-integral molecular dynamics scheme which allows us to exclude nuclear quantum effects from the repulsive potential. The latter potential, in conjunction with the WMull improved atomic charges, provides similar results as (i) for structural, dynamic, and thermodynamic properties while recovering a large part of the proton transfer energy barrier. It therefore offers a good compromise to study both dynamic properties and chemistry within liquid water at a quantum chemical level.

A dynamic parameterization of sulfuric acid–dimethylamine nucleation and its application in three-dimensional modeling

Abstract. Sulfuric acid (SA) is a governing gaseous precursor for atmospheric new particle formation (NPF), a major source of global ultrafine particles, in environments studied around the world. In polluted urban atmospheres with high condensation sinks (CSs), the formation of stable SA–amine clusters, such as SA–dimethylamine (DMA) clusters, usually initializes intense NPF events. Coagulation scavenging and cluster evaporation are dominant sink processes of SA–amine clusters in urban atmospheres, yet these loss processes are not quantitatively included in the present parameterizations of SA–amine nucleation. We herein report a parameterization of SA–DMA nucleation, based on cluster dynamic simulations and quantum chemistry calculations, with certain simplifications to greatly reduce the computational costs. Compared with previous SA–DMA nucleation parameterizations, this new parameterization was able to reproduce the dependences of particle formation rates on temperature and CSs. We then incorporated it in a three-dimensional (3-D) chemical transport model to simulate the evolution of the particle number size distributions. Simulation results showed good consistency with the observations in the occurrence of NPF events and particle number size distributions in wintertime Beijing and represented a significant improvement compared to that using a parameterization without coagulation scavenging. Quantitative analysis shows that SA–DMA nucleation contributes significantly to nucleation rates and aerosol population during the 3-D simulations in Beijing (>99 % and >60 %, respectively). These results broaden the understanding of NPF in urban atmospheres and stress the necessity of including the effects of coagulation scavenging and cluster stability in simulating SA–DMA nucleation in 3-D simulations. Representing these processes is thus likely to improve model performance in particle source apportionment and quantification of aerosol effects on air quality, human health, and climate.