Strengthening-Durable Trade-Off and Self-Healing, Recyclable Shape Memory Polyurethanes Enabled by Dynamic Boron-Urethane Bonds.

Addressing the demand for integrating strength and durability reinforcement in shape memory polyurethane (SMPU) for diverse applications remains a significant challenge. Here a series of SMPUs with ultra-high strength, self-healing and recyclability, and excellent shape memory properties through introducing dynamic boron-urethane bonds are synthesized. The introducing of boric acid (BA) to polyurethane leading to the formation of dynamic covalent bonds (DCB) boron-urethane, that confer a robust cross-linking structure on the SMPUs led to the formation of ordered stable hydrogen-bonding network within the SMPUs. The flexible crosslinking with DCB represents a novel strategy for balancing the trade-off between strength and durability, with their strengths reaching up to 82.2 MPa while also addressing the issue of durability in prolonged usage through the provision of self-healing and recyclability. The self-healing and recyclability of SMPU are demonstrated through rapid dynamic exchange reaction of boron-urethane bonds, systematically investigated by dynamic mechanical analysis (DMA). This study sheds light on the essential role of such PU with self-healing and recyclability, contributing to the extension of the PU's service life. The findings of this work provide a general strategy for overcoming traditional trade-offs in preparing SMPUs with both high strength and good durability.

14C-Isotope Use to Quantify Covalent Reactions between Flavor Compounds and ß-Lactoglobulin.

A 14C-based method was developed to study the rate and extent of covalent bond formation between ß-lactoglobulin and three model flavor compounds: a ketone (2-undecanone UDO), an aldehyde (decanal DAL), an isothiocyanate (2-phenylethyl isothiocyanate PEITC), and an unreactive "methods blank" (decane DEC). Aqueous protein solutions with one of the 14C-labeled model flavor compounds were placed in water baths at 25, 45, and 65 °C for 4 weeks measuring the amount of flavor: protein reaction at 1, 3, 7, 14, 21, and 28 days. UDO showed lowest reactivity (max of 0.9% of added compound reacted), DAL (max of 16.4% reacted), and PEITC (max of 71.8% reacted). All compounds showed a rapid initial reaction rate which slowed after ca. 7 days. It appears that only PEITC (at 65 °C) saturated all potential protein-reactive sites over the storage period.

Rigid covalent bond ofα-sulfur investigated via temperature-dependent EXAFS.

This study performs extended x-ray absorption fine structure (EXAFS) measurements for the S-K edge in the temperature range of 10 and 300 K in the transmission mode using a photodiode to detect the transmitted x-rays. It provides the first report of temperature variations in the structural parameters ofα-S. As the temperature increases from 10 to 300 K in the Fourier transform ofkχ(k)the first peak corresponding to the covalent bond of the eight-membered ring becomes slightly low anomalously despite thermal disturbances. However, as in normal materials, the second peak at 300 K decreases to approximately half of that at 10 K, which contains several intra- and inter-ring correlations. All structural parameters of the covalent bond obtained by nonlinear least squares fitting exhibit missing temperature variations. A value of zero for the asymmetric parameter in the EXAFS (C3) implies that the potential of the covalent bond is symmetric, and the constant value of the mean square relative displacement (MSRD) with temperature implies that the potential is extremely high. The Einstein model fitting for the temperature variation in the MSRD yields an Einstein temperature of 942 K and force constant (K) of 405 N m-1. The value ofKis the largest among those of chalcogen elements.

Dynamically bonded cellulose nanocrystal hydrogels: Structure, rheology and fire prevention performance.

Flame retardant composite hydrogels offer many advantages over conventional flame retardants, such as high water-retention capacity, enhanced fire resistance, and mechanical tunability. Herein, we developed flame-retardant dynamic covalent hydrogels using wood-derived cellulose nanocrystals (CNCs) crosslinked with boronate ester bonds, addressing environmental and health issues associated with the presence of non-biodegradable synthetic polymer and/or inorganic nanoparticle components in the existing systems. Our rheological investigation shows a liquid-to-soft-solid transition of CNC dispersions with tunable network elasticity ranging between ≈ 0.2 kPa to 3.5 kPa and an immediate self-healing ability. Coating pine wood with these hydrogels delayed ignition by about 30 s compared to native wood, and achieved a remarkable limiting oxygen index of 64.5 %. Also, the increased borax content of the gels was found to decrease and delay the first peak of the heat release rate up to 40 s, causing an increase in the fire retardancy index by 277 %. We correlate the microstructure and rheological behavior with the fire prevention mechanisms for the rational design of sustainable fire-retardant materials, and the results showcased a circular use of plant-based dynamic gels to prevent wood fires, even after drying- a feature lacking in conventional hydrogels.

Polypropylene-Rendered Antiviral by Three-Dimensionally Surface-Grafted Poly(N-benzyl-4-vinylpyridinium bromide).

To inhibit viral infection, it is necessary for the surface of polypropylene (PP), a polymer of significant industrial relevance, to possess biocidal properties. However, due to its low surface energy, PP weakly interacts with other organic molecules. The biocidal effects of quaternary ammonium compounds (QACs) have inspired the development of nonwoven PP fibers with surface-bound quaternary ammonium (QA). Despite this advancement, there is limited knowledge regarding the durability of these coatings against scratching and abrasion. It is hypothesized that the durability could be improved if the thickness of the coating layer were controlled and increased. We herein functionalized PP with three-dimensionally surface-grafted poly(N-benzyl-4-vinylpyridinium bromide) (PBVP) by a simple and rapid method involving graft polymerization and benzylation and examined the influence of different factors on the antiviral effect of the resulting plastic by using a plaque assay. The thickness of the PBVP coating, surface roughness, and amount of QACs, which jointly determine biocidal activity, could be controlled by adjusting the duration and intensity of the ultraviolet irradiation used for grafting. The best-performing sample reduced the viral infection titer of an enveloped model virus (bacteriophage ϕ6) by approximately 5 orders of magnitude after 60 min of contact and retained its antiviral activity after surface polishing-simulated scratching and abrasion, which indicated the localization of QACs across the coating interior. Our method may expand the scope of application to resin plates as well as fibers of PP. Given that the developed approach is not limited to PP and may be applied to other low-surface-energy olefinic polymers such as polyethylene and polybutene, our work paves the way for the fabrication of a wide range of biocidal surfaces for use in diverse environments, helping to prevent viral infection.

Biomass- and Carbon Dioxide-Derived Polyurethane Networks for Thermal Interface Material Applications.

Recent environmental concerns have increased demand for renewable polymers and sustainable green resource usage, such as biomass-derived components and carbon dioxide (CO2). Herein, we present crosslinked polyurethanes (CPUs) fabricated from CO2- and biomass-derived monomers via a facile solvent-free ball milling process. Furan-containing bis(cyclic carbonate)s were synthesized through CO2 fixation and further transformed to tetraols, denoted FCTs, by aminolysis and utilized in CPU synthesis. Highly dispersed polyurethane-based hybrid composites (CPU-Ag) were also manufactured using a similar ball milling process. Due to the malleability of the CPU matrix, enabled by transcarbamoylation (dynamic covalent chemistry), CPU-based composites are expected to present very low interfacial thermal resistance between the heat sink and heat source. The characteristics of the dynamic covalent bond (i.e., urethane exchange reaction) were confirmed by the results of dynamic mechanical thermal analysis and stress relaxation analysis. Importantly, the high thermal conductivity of the CPU-based hybrid material was confirmed using laser flash analysis (up to 51.1 W/m·K). Our mechanochemical approach enables the facile preparation of sustainable polymers and hybrid composites for functional application.

Relief of Residual Stress in Bulk Thermosets in the Glassy State by Local Bond Exchange.

The covalently cross-linked network gives thermosets superior thermal, mechanical, and electrical properties, which, however, squarely makes the large residual stress that is inevitably induced during preparation hardly relieved in the glassy state. In this work, an incredible reduction in residual stress is successfully achieved in bulk thermosets in the glassy state through introducing highly dynamic thiocarbamate bonds by "click" reactions of thiols and isocyanates. Due to the excellent dynamic behaviors of thiocarbamate bonds, local network rearrangement is achieved through thermal stimulation, while the strong 3D cross-linked network is well maintained. Ultimately, a decrease by 44% in residual stress is detected by simply annealing samples at 30 °C below glass transition temperature (Tg), during which they could well maintain more than 98.4% of the storage modulus. After the annealing, more uniform residual stress distribution is also observed, showing a 32% decline in sample standard deviation. However, the residual stress of epoxy resin, a typical thermoset as a reference, changes little even after annealing at Tg. The results prove it a feasible strategy to reduce residual stress in bulk thermosets in the glassy state by introducing proper dynamic covalent bonds.

A pseudo-Double-Network Hydrogel Built upon Layered Double Hydroxides with Self-Strengthening Properties.

While great achievements have been made in the development of mechanically robust nanocomposite hydrogels, incorporating multiple interactions on the bases of two demensional inorganic cross-linkers to construct self-strengthening hydrogels has rarely been investigated. To this end, we propose here a new method for the coupling the dynamic covalent bonds and non-covalent interactions within a pseudo double-network system. The pseudo first network, formed through the Schiff Base reation between Tris-modified layered double hydroxides (Tris-LDHs) and oxidized dextran (ODex), is linked to the second network built upon non-covalent interactions between Tris-LDHs and poly(acrylamide-co-2-acrylamido-2-methyl-propanesulfonate) (p-(AM-co-AMPS). The swelling and mechanical properties of the resulting hydrogels have been investigated as a function of the ODex and AMPS contents. The as-prepared hydrogel can swell to 420 times of its original size and retain more than 99.9 wt.% of water. Mechanical tests show that the hydrogel can bear 90 % of compression and is able to be stretched to near 30 times of its original length. Cyclic tensile tests reveal that the hydrogels are capable of self-strengthening after mechanical training. The unique energy dissipation mechanism based on the dynamic covalent and non-covalent interactions is considered to be responsible for the outstanding swelling and mechanical performances.

Tailoring Three-Dimensional Cross-Linked Networks Based on Water-Soluble Polymeric Materials for Stable Silicon Anode.

For stable battery operation of silicon (Si)-based anodes, utilizing cross-linked three-dimensional (3D) network binders has emerged as an effective strategy to mitigate significant volume fluctuations of Si particles. In the design of cross-linked network binders, careful selection of appropriate cross-linking agents is crucial to maintaining a balance between the robustness and functionality of the network. Herein, we strategically design and optimize a 3D cross-linked network binder through a comprehensive analysis of cross-linking agents. The proposed network is composed of poly(vinyl alcohol) grafted poly(acrylic acid) (PVA-g-PAA, PVgA) and aromatic diamines. PVgA is chosen as the polymer backbone owing to its high flexibility and facile synthesis using an ecofriendly water solvent. Subsequently, an aromatic diamine is employed as a cross-linker to construct a robust amide network that features a resonance-stabilized high modulus and enhanced adhesion. Comparative investigations of three cross-linkers, 2,2'-bis(trifluoromethyl)benzidine, 3,3'-oxidianiline, and 4,4'-oxybis[3-(trifluoromethyl)aniline] (TFODA), highlight the roles of the trifluoromethyl group (-CF3) and the ether linkage. Consequently, PVgA cross-linked with TFODA (PVgA-TFODA), featuring both -CF3 and -O-, establishes a well-balanced 3D network characterized by heightened elasticity and improved binding forces. The optimized Si and SiOx/graphite composite electrodes with the PVgA-TFODA binder demonstrate impressive structural stability and stable cycling. This study offers a novel perspective on designing cross-linked network binders, showcasing the benefits of a multidimensional approach considering chemical and physical interactions.

Dynamic Covalent Bonds in the Ebselen Class of Antioxidants Probed by X-ray Quantum Crystallography.

Dynamic bonds are essential structural ingredients of dynamic covalent chemistry that involve reversible cleavage and formation of bonds. Herein, we explore the electronic characteristics of Se-N bonds in the organo-selenium antioxidant ebselen and its derivatives for their propensity to function as dynamic covalent bonds by employing high-resolution X-ray quantum crystallography and complementary computational studies. An analysis of the experimentally reconstructed X-ray wavefunctions reveals the salient electronic features of the Se-N bonds with very low electron density localized at the bonding region and a positive Laplacian value at the bond critical point. Bond orders and percentage covalency and ionicity estimated from the X-ray wavefunctions, along with localized orbital locator (LOL) and electron localization function (ELF) analyses show that the Se-N bond is unique in its closed shell-like features, despite being a covalent bond. Time-dependent DFT calculations simulate the cleavage of Se-N bonds in ebselen in the excited state, further substantiating their nature as dynamic bonds.

Self-Supporting Triphase Photocatalytic CO2 Reduction to CH3OH on Controllable Core-Shell Structure with Tunable Interfacial Wettability.

Enhancing the CO2 mass transfer and proton supply in the photocatalytic reduction of CO2 with H2O into CH3OH (PRC-M), while avoiding the hydrogen evolution reaction (HER), remains a challenge. Herein, we propose an approach to control the surface coverage of CO2 and H2O by modifying interfacial wettability, which is achieved by modulating the core-shell structure to expose either hydrophobic melamine-resorcinol-formaldehyde (MRF) or hydrophilic NiAl-layered double hydroxides (NAL). Characterizations reveal that an insufficient proton supply leads to the production of competing CO, while excessive coverage of H2O results in undesired HER. The NAL-MRF integrates hydrophobic and hydrophilic interfaces, contributing to the CO2 mass transfer and H2O adsorption, respectively. This combination forms a microreactor that facilitates the triphase photocatalysis of CO2, H2O, and catalyst, allowing for high local concentrations of both *CO and *H without competing binding sites. Importantly, the formation of covalent bonds and a Z-type heterojunction between hydrophilic NAL and hydrophobic MRF layers accelerates the charge separation. Furthermore, the density functional theory results indicate that the NAL linking promotes the continuous hydrogenation of *CO. As a result, an enhanced CH3OH yield of 31.41 µmol g-1 h-1, with selectivity of 93.62%, is achieved without hole scavengers or precious metals.

Amide Covalent Bonding Engineering in Heterojunction for Efficient Solar-Driven CO2 Reduction.

Inefficient charge separation and slow interfacial reaction dynamics significantly hamper the efficiency of photocatalytic CO2 reduction. Herein, a facile EDC/NHS-assisted linking strategy was developed to enhance charge separation in heterojunction photocatalysts. Using this approach, we successfully synthesized amide-bonded carbon quantum dot-g-C3N4 (CQD-CN) heterojunction photocatalysts. The formation of amide covalent bonds between CN and CQDs in the CN-CQD facilitates efficient carrier migration, CO2 adsorption, and activation. Exploiting these advantages, the CN-CQD photocatalysts exhibit high selectivity with CO and CH4 evolution rates of 79.2 and 2.7 µmol g-1 h-1, respectively. These rates are about 1.7 and 3.6 times higher than those of CN@CQD and bulk CN, respectively. Importantly, the CN-CQD photocatalysts demonstrate exceptional stability, even after 12 h of continuous testing. The presence of the COOH* signal is identified as a crucial intermediate species in the conversion of CO2 to CO. This study presents a covalent bonding engineering strategy for developing high-performance heterojunction photocatalysts for efficient solar-driven reduction of CO2.

Development of the Colorimetric and/or Fluorescent Probes for Detecting Fluoride ions in Aqueous Solution.

Fluoride ion is a strong Lewis base and one of the essential trace elements in human body. It plays a very important role in human health and ecological balance. The deficiency or excessive intake of fluoride ions will cause serious health problems, so the development of a sensitive and accurate detection method for fluoride ions is very important. The colorimetric and/or fluorescence sensing method has been a long standing attractive technique with high sensitivity and fast response. To date, most reported probes for fluoride ion are applicable only in organic solvents or organic-containing aqueous solutions. However, the probes for fluoride ion used in aqueous solution are more practically needed in view of environment protection and human health. In this paper, the materials and designing ideas of the colorimetric and/or fluorescent probes for fluoride ion based on different detection mechanisms in recent years were reviewed. Two main categories including formation of hydrogen bonds and formation of coordination covalent bonds were discussed. The latter one is further subdivided into three types, formation of B-F bond, formation of Si-F bond and formation of Mn+-F bond.

Post-translational modifications and their implications in cancer.

Post-translational modifications (PTMs) are crucial regulatory mechanisms that alter the properties of a protein by covalently attaching a modified chemical group to some of its amino acid residues. PTMs modulate essential physiological processes such as signal transduction, metabolism, protein localization, and turnover and have clinical relevance in cancer and age-related pathologies. Majority of proteins undergo post-translational modifications, irrespective of their occurrence in or after protein biosynthesis. Post-translational modifications link to amino acid termini or side chains, causing the protein backbone to get cleaved, spliced, or cyclized, to name a few. These chemical modifications expand the diversity of the proteome and regulate protein activity, structure, locations, functions, and protein-protein interactions (PPIs). This ability to modify the physical and chemical properties and functions of proteins render PTMs vital. To date, over 200 different protein modifications have been reported, owing to advanced detection technologies. Some of these modifications include phosphorylation, glycosylation, methylation, acetylation, and ubiquitination. Here, we discuss about the existing as well as some novel post-translational protein modifications, with their implications in aberrant states, which will help us better understand the modified sites in different proteins and the effect of PTMs on protein functions in core biological processes and progression in cancer.

The Origin of Anomalous Density Behavior of Silica Glass.

The anomalous density-temperature relationship of vitreous silica with low hydroxyl content is explained by the formation of medium-range ordering structure in the glass transition process. The ordered medium-range structure has the shape of a "nanoflake" and consists of two layers of SiO4 tetrahedra, bonded by O atoms located in the middle of the structure. The nanoflakes interact with their surrounding structures through both covalent chemical bonds and van der Waals bonds. In the formation of the van der Waals bonds, the orientation of SiO4 tetrahedra can change, which results in an increase in distance between the nanoflakes and their surrounding structures. Thus, there is a slight volume enlargement associated with the formation of nanoflakes. Since the nanoflakes' formation starts at a temperature near 1480 °C, and the population of the nanoflakes grows continuously as temperature decreases until about 950 °C, the bulk volume of silica glass increases in the temperature range from about 1480 °C to 950 °C. Therefore, the density anomaly of silica glass can be explained as a byproduct of forming of medium-range ordering structure in the silica glass transition.

Re-Assemblable, Recyclable, and Self-Healing Epoxy Resin Adhesive Based on Dynamic Boronic Esters.

Thermosetting adhesives are commonly utilized in various applications. However, covalent cross-linked networks prevent thermosetting adhesives from being re-assembled, which necessitates higher machining precision. Additionally, the primary raw materials used in adhesive preparation are derived from non-renewable petroleum resources, which further constrain adhesive development. In this study, a recyclable adhesive was developed by incorporating dynamic boronic esters into epoxy resin derived from soybean oil. The successful synthesis of epoxidized soybean oil and boronic esters was confirmed through the analysis of proton nuclear magnetic resonance spectra and differential scanning calorimetry results. Swelling tests and tensile curves demonstrated the presence of covalently cross-linked networks. Self-healing and reprocessing experiments indicated that the cross-linked network topology could be re-assembled under mild conditions.

Open shell versus closed shell bonding interaction in cyclopropane derivatives: EDA-NOCV analyses.

Cyclopropane ring is a very common motif in organic/bio-organic compounds. The chemical bonding of this strained ring is taught to all chemistry students. This three-membered cyclic, C3 ring is quite reactive which has attracted both, synthetic and theoretical chemists to rationalize/correlate its stability and bonding with its reactivity and physical properties over a century. There are a few bonding models (mainly the Bent-Bond model and Walsh model) of this C3 ring that are debated to date. Herein, we have carried out energy decomposition analysis coupled with natural orbital for chemical valence (EDA-NOCV) to study the two most reactive bonds of cyclopropane rings of 49 different organic compounds containing different functional groups to obtain a much deeper bonding insight toward a more general bonding model of this class of compounds. The EDA-NOCV analyses of fragment orbitals and susequent bond formation revealed that the nature of the CC bond of the cyclopropane (splitting two bonds at a time out of three CC bonds) ring is preferred to form two dative covalent CC bonds (between a singlet olefin-fragment and an excited singlet carbene-fragment with a vacant sp2 orbital and a filled p-orbital) for the majority (37/49) of compounds over two covalent electron sharing bonds in some (7/49) compounds (between an excited triplet olefin and triplet carbene), while a few (5/49) compounds show flexibility to adopt either the electron sharing or dative covalent bond as both are equally possible. The effects of functional groups on the nature of chemical bond in cyclopropane rings have been studied in detail. Our bonding analyses are in line with the QTAIM analyses which produce small negative values of the Laplacian, significantly positive values of bond ellipticity, and accumulation of electron densities around the ring critical point of C3 -rings. These corresponding QTAIM parameters of C3 -rings are quite different for CC single bonds of normal hydrocarbons as expected. The chemical bonding in the majority of cyclopropane rings can be very similar to those of metal-olefin systems.

Self-healing, flame-retardant, and antimicrobial chitosan-based dynamic covalent hydrogels.

This study reports the fabrication of chitosan-based hydrogels with potential to be applied as a flame-retardant coating on skin or other surfaces. These hydrogels possess remarkable antimicrobial properties that are highly desirable for the protection of epidermises. Hydrogels in this study were prepared via the cross-linking reaction of chitosan with a vanillin-based cross linker containing flame-retarding moieties through Schiff's base reaction. The synthesized hydrogels possess imine linkages enabling them to self-heal at room temperature. Self-healing abilities offered these hydrogels the ability to protect the skin for a longer time. One flame retarding mechanism of these hydrogels was by retaining the water in their polymeric network; thus, the role of bound and unbound water molecules was studied using DSC and Raman spectroscopy. The hydrogels synthesized in this study retained their flame-retarding properties even after drying due to the charring process that inhibited the pyrolysis process. Therefore, these chitosan-based hydrogels are able to prolong the protection time against fire.

B-N/B-O Contained Heterocycles as Fusion Locker in Multi-Resonance Frameworks towards Highly-efficient and Stable Ultra-Narrowband Emission.

Fusing condensed aromatics into multi-resonance (MR) frameworks has been an exquisite strategy to modulate the optoelectronic properties, which, however, always sacrifices the small full width at half maxima (FWHM). Herein, we strategically embed B-N/B-O contained heterocycles as fusion locker into classical MR prototypes, which could enlarge the π-extension and alleviate the steric repulsion for an enhanced planar skeleton to suppress the high-frequency stretching/ scissoring vibrations for ultra-narrowband emissions. Sky-blue emitters with extremely small FWHMs of 17-18 nm are thereafter obtained for the targeted emitters, decreased by (1.4-1.9)-fold compared with the prototypes. Benefiting from their high photoluminescence quantum yields of >90 % and fast radiative decay rates of >108  s-1 , one of those emitters shows a high maximum external quantum efficiency of 31.9 % in sensitized devices, which remains 25.8 % at a practical luminance of 1,000 cd m-2 with a small FWHM of merely 19 nm. Notably a long operation half-lifetime of 1,278 h is also recorded for the same device, representing one of the longest lifetimes among sky-blue devices based on MR emitters.

Using a Dynamic Hydrophilization Strategy to Achieve Nanodispersion, Full Wetting, and Precise Delivery of Hydrophobic Pesticide.

Various strategies have been developed to improve the applicability of hydrophobic pesticides for better effectiveness in agriculture. However, existing formulations of hydrophobic pesticides still suffer from complicated processing, abused organic solvents, indispensable surfactants, or inescapable ecotoxicity, which strictly limit their applications. Herein, a dynamic covalent bond tailored pesticide (fipronil) amphiphile is constructed to address the above issues, which accomplishes the nanodispersion, full wetting, and precise delivery without organic solvents, surfactants, and materials simultaneously. By introducing a hydrophilic ligand on the hydrophobic fipronil through an imine bond, the cleavable fipronil amphiphile (FPP) exhibits superior water solubility and can even self-assemble into micelles at higher concentrations, which can be directly applied in powder form without organic solvents. Attributed to the suitable hydrophilic/hydrophobic ratio, FPP achieves full wetting and effective deposition on superhydrophobic rice leaves without surfactants. Moreover, benefiting from the unique dynamic nature of the imine bond, FPP maintains good storage stability while sensitively releasing back to fipronil under the humidity and pH trigger, consequently implementing the precise delivery for nontarget Apis cerana and target Chilo suppressalis without materials. To our knowledge, this dynamic covalent bond tailored amphiphile strategy is the first idea that simultaneously takes the dispersibility, wettability, and responsiveness of hydrophobic pesticides into account, providing a possibility to control the entire journey of field application and even promising to be incorporated into the synthesis process, thus paving the way for modern sustainable agriculture.