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Ti doping can improve the interfacial wettability and bonding condition between ZTA ceramic and high chromium cast iron (HCCI), but the underlying mechanism is still unclear. Therefore, the effects of Ti doping on the interfacial characters between ZTA and HCCI were investigated by experiment and first-principles calculations. Results of XRD, SEM, and high-temperature drop test indicate the presence of Ti at the interface and its effect on the formation of interfacial diffusion layer to improve the interface wettability and bonding obviously. The heat of segregation and work of adhesion obtained by first-principle calculations shows that the improvement in interface wettability and bonding is due to the promotion of dopped Ti atoms on the diffusion of Fe, Al, and Zr elements, but not the diffusion of Ti itself. Further investigation from the electronic level reveals that the doped Ti changes the charge distribution and orbital hybridization, and thus makes the formation or enhancement of strong ionic bonds and covalent bonds at the interface, improving the bonding strength and wettability of interfaces in ZTA/HCCI. The findings of this research can offer new insights into the modification of ceramics and enlarge the application of advanced ceramic materials. [ABSTRACT FROM AUTHOR]

Biocatalytic membranes have great potential in various industrial sectors, with the immobilization of enzymes being a crucial stage. Immobilizing enzymes through covalent bonds is a complex and time-consuming process for large-scale applications. Polydopamine (PDA) offers a more sustainable and eco-friendly alternative for enzyme immobilization. Therefore, surface modification with polydopamine as mussel-inspired antifouling coatings has increased resistance to fouling. In this study, α-amylase enzyme was covalently bound to a bioactive PDA-coated polyethersulfone (PES) membrane surface using cyanuric chloride as a linker. The optimal activity of α-amylase enzyme immobilized on PES/PDA membrane was obtained at temperature and pH of 55°C and 6.5, respectively. The immobilized enzyme can be reused up to five reaction cycles with 55 % retention of initial activity. Besides, it maintained 60 % of its activity after being stored for five weeks at 4°C. Additionally, the immobilized enzyme demonstrated increased Michaelis constant and maximum velocity values during starch hydrolysis. The results of the biofouling experiment of various membranes in a dead-end cell demonstrated that the PES membrane's water flux increased from 6722.7 Lmh to 7560.2 Lmh after PDA modification. Although α-amylase immobilization reduced the flux to 7458.5 Lmh due to enhanced hydrophilicity, compared to unmodified membrane. The findings of this study demonstrated that the membrane produced through co-deposition exhibited superior hydrophilicity, enhanced coating stability, and strong antifouling properties, positioning it as a promising candidate for industrial applications. [Display omitted] • α-Amylase was covalently immobilized onto polydopamine-functionalized polyethersulfone membrane. • Surface modification with polydopamine generated a mussel-inspired coating to inhibit fouling. • The immobilization technique effectively preserved the activity of α-amylase enzyme. • The biocatalyst membrane exhibited superior stability and strong antifouling properties. [ABSTRACT FROM AUTHOR]

When asphalt pavement is in practical use, it is prone to cracking and other diseases due to the long-term effects of load and climate and the restricted self-healing properties of the asphalt material. In order to improve the properties and durability of asphalt pavement, we introduced disulfide bonds into polyurethane (PU) in this study. We prepared polyurethane-modified asphalt (PUA) containing dynamic disulfide covalent bonds using polytetrahydrofuran (PTMG), polyethylene adipate (PEA), and hydroxyl-terminated polybutadiene (HTPB) as soft segments. Subsequently, the rheological properties, healing performance, and microstructure of the PUA were studied. The results indicated that the PU with disulfide bonds was integrated into the asphalt and had good dispersity. A cross-linked network structure formed between them. PUA with HTPB as the soft segment had excellent high-temperature deformation and low-temperature cracking resistance and a prominent advantage in durability. In comparison, PUA synthesized with PEA had better high-temperature performance and fatigue resistance, and PUA synthesized with PTMG had considerable low-temperature properties and stability. The disulfide bonds had a positive impact on the high-temperature performance, aging resistance, and healing properties of PUA through constant dynamic exchange and topological rearrangement effects. This study provides a reference for the preparation of PUA with ideal self-healing ability and has instructive significance for the selection of soft segment materials for synthesizing PUA. [ABSTRACT FROM AUTHOR]

Inspired by the Mimosa plant, this study herein develops a unique dynamic shape memory polymer (SMP) network capable of transitioning from hard to pliable with heat, featuring reversible actuation, self‐healing, recyclability, and degradability. This material is adept at simulating the functionalities of artificial muscles for a variety of tasks, with a remarkable specific energy density of 1.8 J g−1—≈46 times higher than that of human skeletal muscle. As an intelligent manipulator, it demonstrates remarkable proficiency in identifying and handling items at high temperatures. Its suitable rate of shape recovery around human body temperature indicates its promising utility as an implant material for addressing acute obstructions. The dynamic covalent bonding within the network structure not only provides excellent resistance to solvents but also bestows remarkable abilities for self‐healing, reprocessing, and degradation. These attributes significantly boost its practicality and environmental sustainability. Anticipated to promote advancements in the sectors of biomedical devices, soft robotics, and smart actuators, this SMP network represents a forward leap in simulating artificial muscles, marking a stride toward the future of adaptive and sustainable technology. [ABSTRACT FROM AUTHOR]

During the production of bispecific antibodies (bsAbs), nonspecific pairing results in low yields of target bsAb molecules, an issue known as the "mispairing problem." Several antibody engineering techniques have been developed to overcome mispairing issues. Here, we introduce "bsAb by external pairing and excision" (BAPE), a novel chain pairing method that induces specific chain pairing by fusing external SpyCatcher/Tag and SnoopCatcher/Tag units. These tags are then removed via protease cleavage. In this study, we applied this method to force the correct pairings of heavy and light chains while the heavy-chain pairing was achieved by the Knobs-into-Holes mutation. We then confirmed the formation of interchain bridges with covalent isopeptide bonds. Both anti-CD3/anti-Her2 and anti-CD3/anti-EGFR bsAbs displayed satisfactory target binding activities and in vitro cell-killing activity with activated T-cells. [ABSTRACT FROM AUTHOR]

We introduce N-P pair into the carbon matrix to construct N,P-C electrocatalyst by a facile pyrolysis strategy. Benefiting from the moderate adsorption energy of *OH on the active sites (C adjacent to P atom in N-P), the achieved N,P-C-1000 displays outstanding alkaline ORR performance and high power density primary liquid and solid ZABs. [Display omitted] • N-P pair was introduced into the carbon matrix to construct N,P-C electrocatalyst by a facile pyrolysis strategy. • The catalyst exhibits superior ORR activity with a E 1/2 of 0.83 V, comparable to that of commercial 20 wt% Pt/C. • Its C-2p orbit has higher interaction strength with the intermediates, thus reducing the overall reaction energy barrier. • High power density primary liquid and solid ZABs are achieved using N,P-C-1000 as cathodic catalysts. Developing sustainable metal-free carbon-based electrocatalysts is essential for the deployment of metal-air batteries such as zinc-air batteries (ZABs), among which doping of heteroatoms has attracted tremendous interest over the past decade. However, the effect of the heteroatom covalent bonds in carbon matrix on catalysis was neglected in most studies. Here, an efficient metal-free oxygen reduction reaction (ORR) catalyst is demonstrated by the N-P bonds anchored carbon (termed N,P-C-1000). The N,P-C-1000 catalyst exhibits superior specific surface area of 1362 m2 g−1 and ORR activity with a half-wave potential of 0.83 V, close to that of 20 wt% Pt/C. Theoretical computations reveal that the p-band center for C-2p orbit in N,P-C-1000 has higher interaction strength with the intermediates, thus reducing the overall reaction energy barrier. The N,P-C-1000 assembled primary ZAB can attain a large peak power density of 121.9 mW cm−2 and a steady discharge platform of ∼1.20 V throughout 120 h. Besides, when served as the cathodic catalyst in a solid-state ZAB, the battery shows flexibility, conspicuous open circuit potential (1.423 V), and high peak power density (85.8 mW cm−2). Our findings offer a strategy to tune the intrinsic structure of carbon-based catalysts for improved electrocatalytic performance and shed light on future catalysts design for energy storage technologies beyond batteries. [ABSTRACT FROM AUTHOR]

The interplay of spin-orbit coupling with other relevant parameters gives rise to the rich phase competition in complex ruthenates featuring octahedrally coordinated Ru4+. While locally, spin-orbit coupling stabilizes a nonmagnetic Jeff = 0 state, intersite interactions resolve one of two distinct phases at low temperatures: an excitonic magnet stabilized by the magnetic exchange of upper-lying Jeff = 1 states or Ru2 molecular orbital dimers driven by direct orbital overlap. Pyrochlore ruthenates A2Ru2O7 (A = rare earth, Y) are candidate excitonic magnets with geometrical frustration. We synthesized In2Ru2O7 with covalent In-O bonds. This pyrochlore ruthenate hosts a local Jeff = 0 state at high temperatures; however, at low temperatures, it forms a unique nonmagnetic ground state with nearly linear Ru-O-Ru molecules, in stark contrast to other A2Ru2O7 compounds. The disproportionation of covalent In-O bonds drives Ru2O molecule formation, quenching not only the local spin-orbit singlet but also geometrical frustration. [ABSTRACT FROM AUTHOR]

Traditionally, the surface charge number (SCN) of permanently charged soils/clay minerals is believed to be unaffected by environmental pH. However, recent studies have revealed the occurrence of polarization-induced covalent bonding between H+ and the surface O atoms of permanently charged clay minerals. This discovery challenges the traditional notions of "permanently charged soil" and "permanently charged clay mineral". The purpose of this study is to confirm that there are no true "permanently charged clay" or "permanently charged soil". In this study, the SCNs of two permanently charged clay minerals, two variably charged clay minerals, five permanently charged soils (temperate soils), and four variably charged soils (tropical or subtropical soils) were measured at different pH values using the universal determination method of SCN. The results showed that: (1) The SCNs of the permanently/variably charged soils and clay minerals decreased significantly with decreasing pH; (2) the SCN of montmorillonite decreased less with decreasing pH than the SCNs of variably charged minerals, whereas the SCN of illite decreased to nearly the same extent, indicating strong polarization-induced covalent bonding between H+ and the surface O atoms of illite; (3) the SCNs of permanently charged soils decreased to a similar extent as those of variably charged soils with decreasing pH. This study demonstrated that the concepts, "permanently charged clay mineral" or "permanently charged soil", are questionable because of the polarization-induced covalent bonding between H+ and the surface O atoms of clay minerals. [ABSTRACT FROM AUTHOR]

Petroleum‐derived plastics are harmful to ecosystems because they are not decomposed in the natural environment. Therefore, the replacement of petroleum‐derived plastics with biodegradable plastics has attracted considerable attention. UV‐barrier films in the agricultural and packaging fields are mainly composed of petroleum‐derived plastics, which have a negative impact on the ecosystem when they leak into the environment. Thermoplastic starch (TPS) is an inexpensive and sustainable biodegradable plastic that has recently attracted considerable attention. In this study, the addition of UV barrier properties and remolding ability to TPS for replacing petroleum‐derived UV barrier films are investigated. Also, a biodegradable polyester coating is studied to improve the water resistance of the prepared UV‐barrier TPS (U‐TPS). To prepare U‐TPS, a conjugated enamine structure is formed by reacting starch acetoacetate with diamine monomers during melt kneading. U‐TPS exhibits high UV barrier properties across the UV regions (200–400 nm) owing to the presence of acetoacetyl groups and enamines. These results indicate the possibility of increasing the utilization of TPS in agriculture and as a packaging material. [ABSTRACT FROM AUTHOR]

Supercapacitors (SCs) are studied and used in various fields due to their high power density, fast charging/discharging rate, as well as long cycle life. Compared to other traditional electrode and electrolyte materials, supramolecular hydrogels have great advantages in the application of SCs due to their excellent properties. Unlike covalent bonds, supramolecular systems are assembled through dynamic reversible bonds, including host–guest interactions, ion interactions, electrostatic interactions, hydrogen bonding, coordination interactions, etc. The resulting supramolecular hydrogels show some special functions, such as stretching, compression, adhesion, self‐healing, stimulus responsiveness, etc., making them strong candidates for the next generation of energy storage devices. This paper reviews the representative progress of electrodes, electrolytes, and SCs based on supramolecular hydrogels. Besides, the properties of supramolecular hydrogels, such as conductivity, extensibility, compressibility and elasticity, self‐healing, frost resistance, adhesion, and flexibility, are also reviewed to highlight the key role of excellent properties of hydrogel materials in SCs. In addition, this article also discusses the challenges faced by current technologies, hoping to continue promoting future research in this field. [ABSTRACT FROM AUTHOR]

Poor vacuum stability limits the application of many matrices in matrix‐assisted laser desorption/ionization mass spectrometry imaging (MALDI MSI) that requires long‐term measurement duration in high vacuum. In this study, a new approach using conjugate polymer anchor to protect unstable matrix from volatilizing in MALDI source based on ion bond is provided. Unlike strong covalent bonds which often introduce unnecessary groups, the weaker ion bonds are more conducive to breaking under laser radiation while effectively preventing matrix volatilization in a vacuum environment. The results confirm that conjugate polymer anchor will neither introduce additional ion peaks nor affect signal intensity, yet maintains comparable quantification properties. Vacuum stability of three kinds of typical matrices is enhanced using polymer anchors, and the in situ MALDI MS imaging of mouse brain and liver cancer is improved significantly. [ABSTRACT FROM AUTHOR]

Previous research highlights the potential of polyaniline-based biocomposites as unique adsorbents for humidity sensors. This study examines several preparative routes for creating polyaniline (PANI) and chitosan (CHT) composites: Type 1—in situ polymerization of aniline with CHT; Type 2—molecular association in acidic aqueous media; and a control, Type 3—physical mixing of PANI and CHT powders (without solvent). The study aims to differentiate the bonding nature (covalent vs. noncovalent) within these composites, which posits that noncovalent composites should exhibit similar physicochemical properties regardless of the preparative route. The results indicate that Type 1 composites display features consistent with covalent and hydrogen bonding, which result in reduced water swelling versus Type 2 and 3 composites. These findings align with spectral and thermogravimetric data, suggesting more compact structure for Type 1 materials. Dye adsorption studies corroborate the unique properties for Type 1 composites, and 1H NMR results confirm the role of covalent bonding for the in situ polymerized samples. The structural stability adopts the following trend: Type 1 (covalent and noncovalent) > Type 2 (possible trace covalent and mainly noncovalent) > Type 3 (noncovalent). Types 2 and 3 are anticipated to differ based on solvent-driven complex formation. This study provides greater understanding of structure-function relationships in PANI-biopolymer composites and highlights the role of CHT as a template that involves variable (non)covalent contributions with PANI, according to the mode of preparation. The formation of composites with tailored bonding modalities will contribute to the design of improved adsorbent materials for environmental remediation to versatile humidity sensor systems. [ABSTRACT FROM AUTHOR]

Developing effective inhibitors of the DNA repair enzyme tyrosyl-DNA phosphodiesterase 1 (TDP1) has been challenging because of the enzyme shallow catalytic pocket and non-specific substrate binding interactions. Recently, we discovered a quinolone-binding hot spot in TDP1's active site proximal to the evolutionary conserved Y204 and F259 residues that position DNA. Sulfur (VI) fluoride exchange (SuFEx) is a biocompatible click chemistry reaction that enables acylation of protein residues, including tyrosine. Selective protein modifications can provide insights into the biological roles of proteins and inform ligand design. As we report herein, we used SuFEx chemistries to prepare covalent TDP1-bound binders showing site-specific covalent bonds with Y204. Our work presents the first application of SuFEx chemistries to TDP1 ligands. It validates the ability to covalently modify specific TDP1 residues by designed targeting and adds to the chemical biology resource toolbox for studying TDP1. Developing effective inhibitors of the DNA repair enzyme tyrosyl-DNA phosphodiesterase 1 (TDP1) is challenging because of the enzyme's shallow catalytic pocket and non-specific substrate binding interactions. Here, the authors use Sulfur (VI) fluoride exchange chemistries to prepare covalent TDP1-bound binders showing site-specific covalent bonds with the Y204 residue that position DNA. [ABSTRACT FROM AUTHOR]

Herein, inspired by the macrophage's defensive behavior of releasing free radicals to kill bacteria and viruses, a marine antifouling coating with dynamic surfaces is prepared by precise regulation of dynamic covalent bonds. Alkyl radical (R·) derived from oxime-urethane structure attracts and disrupts microbe cell membrane and pili between intimate cells, resulting in excellent anti-biofouling effect. Moreover, the newly exposed coating then continues to break, which ultimately results in the peeling of the layers, thus making barnacles, mussels and other fouling organisms less likely to adhere. [Display omitted] • Macrophage-inspired marine antifouling coating with dynamic surfaces is prepared. • Alkyl radical (R·) derived from oxime-urethane structure offers excellent anti-fouling performance. • The newly exposed coating continues to break making it less likely that fouling organisms will adhere to it. • This study presents a novel methodology for fulfilling the technological gap of marine coatings with dynamic surface. Macrophages can kill bacteria and viruses by releasing free radicals, which provides a possible approach to construct antifouling coatings with dynamic surfaces that release free radicals if the breaking of dynamic covalent bonds is precisely regulated. Herein, inspired by the defensive behavior of macrophages of releasing free radicals to kill bacteria and viruses, a marine antifouling coating composed of polyurethane incorporating dimethylglyoxime (PU x -DMG) is prepared by precise regulation of dynamic oxime-urethane covalent bonds. The obtained alkyl radical (R·) derived from the cleavage of the oxime-urethane bonds manages to effectively suppress the attachment of marine biofouling. Moreover, the intrinsic dynamic surface makes it difficult for biofouling to adhere and ultimately achieves sustainable antifouling property. Notably, the PU 50 -DMG coating not only presents efficient antibacterial and antialgae properties, but also prevents macroorganisms from settling in the sea for up to 4 months. This provides a pioneer broad-spectrum strategy to explore the marine antifouling coatings. [ABSTRACT FROM AUTHOR]

Poly(acrylic acid) (PAAc) hydrogels are essential functional materials. However, their mechanical properties do not meet the required standards. In this study, a one‐pot method is employed to prepare cellulose‐reinforced PAAc hydrogels by dissolving allyl cellulose (AC) in acrylic acid (AAc) solutions. Fourier transform infrared (FTIR), solid‐state 13C nuclear magnetic resonance (NMR), and thermogravimetric (TG) analysis are used to demonstrate that the incorporation of AC results in the formation of covalent and hydrogen bonds, which contribute to the crosslink network of the PAAc hydrogels. Significantly, by modifying the ratio of AC to AAc in the pre‐polymerization solution, the prepared AC–PAAc hydrogels exhibit a transition from transparent to opaque. This suggests that phase separation is induced by hydrogen bonding. The occurrence of phase separation is verified by observing the hydrogel microstructures using scanning electron microscopy. Phase separation leads to enhanced polymer–polymer interactions in the hydrogels, resulting in a maximum fracture stress of 2.34 MPa. The AC–PAAc hydrogels display distinct swelling behavior under various pH conditions. Moreover, they demonstrate differences in transparency and mechanical properties when exposed to dimethyl sulfoxide (DMSO) and water, indicating their responsiveness to solvents. This work demonstrates the great potential of enhancing the mechanical performance and responsiveness of PAAc hydrogels. [ABSTRACT FROM AUTHOR]

The scientific strategies reported in the literature for developing biobased epoxy vitrimers are summarized. Biomass resources such as lignin, cellulose, or different vegetable oils can be exploited as biobased building blocks for epoxy thermosets as an alternative to the bisphenol‐A‐based ones. Biorenewable resources have been synthesized introducing dynamic covalent bonds in the cross‐linked networks. This combination allows to achieve cross‐linked biobased epoxy networks with thermoset‐like properties at a temperature of use, but showing (re)processability, recyclability, and self‐healing properties above a well‐defined temperature named topology freezing transition temperature (Tv). [ABSTRACT FROM AUTHOR]

The surface properties of bastnaesite and parisite are similar to their associated gangue mineral, fluorite, which makes the flotation separation of these two rare earth minerals from fluorite one of the industry's most significant challenges. This study systematically investigates the inhibitory effects and mechanisms of sodium silicate (SS) on bastnaesite, parisite, and fluorite in an octyl hydroxamic acid (OHA) collector system through flotation experiments, various modern analytical methods, and DFT simulations. The flotation test results indicate that the inhibition effects of SS on the three minerals are in the order: fluorite > parisite > bastnaesite. Detection and analysis results indicate that SS forms hydrophilic complexes with Ca atoms on the surfaces of fluorite and parisite, enhancing surface hydrophilicity and inhibiting OHA adsorption, but its impact on bastnaesite is relatively minor. DFT simulation results show that OHA forms covalent bonds with metal ions on mineral surfaces, favoring five-membered hydroxamic-(O-O)-Ce/Ca complexes, and reacts more strongly with Ce atoms than Ca atoms. SS primarily forms covalent bonds with metal atoms on mineral surfaces via the SiO(OH)3− component, and OHA and SS compete for adsorption on the mineral surfaces. OHA has a stronger affinity for bastnaesite, whereas SS shows the highest affinity for fluorite, followed by parisite, and the weakest affinity for bastnaesite. [ABSTRACT FROM AUTHOR]

We report the reticular synthesis and structural investigations through the spectroscopic analysis of a novel polyhedral oligomeric silsesquioxane (POSS)-modified framework, hereby ascribed as a catalyst for the selective reduction of aryl nitriles to amines. The integration of the unique features of the polyhedral oligomeric silsesquioxane with 2,2′-Bipyridine-4,4′-dicarboxaldehyde and subsequently coordination to cobalt acetate manifests a distinctive feature, which is a stable covalent bond between Co and the functionalized POSS, effectively preventing catalyst leaching. The cobalt acetate-modified POSS–COF, synthesized with this approach, underwent a comprehensive characterization employing various analytical techniques including FTIR, XRD, SEM, XPS, TGA, and 29Si NMR. This thorough characterization provides a detailed insight into the structural and chemical attributes of the catalyst. Our catalyst, with its exceptional catalytic efficiency in catalyzing reduction reactions compared to its homogeneous counterparts, and its distinctive three-dimensional metalated POSS system, shows outstanding catalytic performance attributed to its diverse coordination interactions with ligands. Moreover, this catalyst presents additional merits, such as facile recovery and recyclability, making it a promising candidate for sustainable and efficient catalytic processes and thus instilling hope for a greener future. [ABSTRACT FROM AUTHOR]

Antibacterial resistance is one of the most important global threats to human health. Several studies have been performed to overcome this problem and infection-preventive approaches appear as promising solutions. Novel antimicrobial preventive molecules are needed and microbial biosurfactants have been explored in that scope. Considering their structure, these biomolecules can be divided into different classes, glycolipids and lipopeptides being the most studied. Besides their antimicrobial activity, biosurfactants have the advantage of being biocompatible, biodegradable, and non-toxic, which favor their application in several areas, including the health sector. Often, the most difficult infections to fight are associated with biofilm formation, particularly in medical devices. Strategies to overcome micro-organism attachment are thus emergent, and it is possible to take advantage of the antimicrobial/antibiofilm properties of biosurfactants to produce surfaces that are more resistant to the deposition/attachment of bacteria. Approaches such as the covalent bond of biosurfactants to the medical device surface leading to repulsive physical–chemical interactions or contact killing can be selected. Simpler strategies such as the absorption of biosurfactants on surfaces are also possible, eliminating micro-organisms in the vicinity. This review will focus on the physical and chemical characteristics of biosurfactants, their antimicrobial activity, antimicrobial/antibiofilm approaches, and finally on their structure–activity relationship. [ABSTRACT FROM AUTHOR]

Although hydrofluoric acid (HF) surface treatment is known to enhance the joining of metals with polymers, there is limited information on its effect on the joining of AZ31 alloy and carbon-fiber-reinforced plastics (CFRPs) through laser-assisted metal and plastic direct joining (LAMP). This study uses the LAMP technique to produce AZ31-CFRP joints. The joining process involves as-received AZ31, HF-pretreated AZ31, and thermally oxidized HF-pretreated AZ31 alloy sheets. Furthermore, the bonding strength of joints prepared with thermally oxidized AZ31 alloy sheets is examined to ascertain the combined effect of HF treatment and thermal oxidation on bonding strength. The microstructures, surface chemical interactions, and mechanical performances of joints are investigated under tensile shear loading. Various factors, such as bubble formation, CFRP resin decomposition, and mechanical interlocking considerably affect joint strength. Additionally, surface chemical interactions between the active species on metal parts and the polar amide along with carbonyl groups of polymer play a significant role in improving joint strength. Joints prepared with surface-pretreated AZ31 alloy sheets show significant improvements in bonding strength.

Si is an important semiconductor material in the development of modern industry. With the miniaturization trend of semiconductor devices, the size of Si has reached the cluster size. The search for stable Si clusters is an important issue. In this work, the electronic structures and stability mechanism of the W@Si12 cluster are calculated by the first-principle calculations. Different from a C2v hexacapped trigonal prism structure of Si12, the W@Si12 cluster presents an embedded hexagonal prism structure with D6h symmetry. The addition of W atom leads to a higher stability. The molecular orbitals show obvious superatomic characteristics for the W@Si12 cluster, and their energy levels are more degenerate than that of the Si12 cluster. The population analysis indicates that a total charge of 2.21e is transferred from Si atoms to the center W atom, which suggests an ionic bond for W-Si. The electron localization function further proves a covalent bond for Si–Si. The enhanced stability of the W@Si12 cluster is attributed to the combination of the ionic and covalent bonds. [ABSTRACT FROM AUTHOR]

Metal oxides containing La, Mn, and Co cations can catalyze oxygen reduction reactions (ORRs) in electrochemical processes. However, these materials require carbon support and optimal interactions between both compounds to be active. In this work, two approaches to prepare composites of La-Mn-Co-based compounds over carbon xerogel were developed. Using sol-gel methods, either the metal-based material was deposited on the existing carbon xerogel or vice versa. The metal oxide selected was the LaMn0.7Co0.3O3 perovskite, which has good catalytic behavior and selectivity towards direct ORRs. All the as-prepared composites were tested for ORRs in alkaline liquid electrolytes and characterized by diverse physicochemical techniques such as XRD, XPS, SEM, or N2 adsorption. Although the perovskite structure either decomposed or failed to form using those in situ methods, the materials exhibited great catalytic activity, which can be ascribed to the strengthening of the interactions between oxides and the carbon support via C-O-M covalent bonds and to the formation of new active sites such as the MnO/Co heterointerfaces. Moreover, Co-Nx-C species are formed during the synthesis of the metal compounds over the carbon xerogel. These species possess a strong catalytic activity towards ORR. Therefore, the composites formed by synthesizing metal compounds over the carbon xerogel exhibit the best performance in the ORR, which can be ascribed to the presence of the MnO/Co heterointerfaces and Co-Nx-C species and the strong interactions between both compounds. Moreover, the small nanoparticle size leads to a higher number of active sites available for the reaction. [ABSTRACT FROM AUTHOR]

Exfoliated graphite (ExG) embedded in a polymeric matrix represents an accessible, cost-effective, and sustainable method for generating nanosized graphite-based polymer composites with multifunctional properties. This review article analyzes diverse methods currently used to exfoliate graphite into graphite nanoplatelets, few-layer graphene, and polymer-assisted graphene. It also explores engineered methods for small-scale pilot production of polymer nanocomposites. It highlights the chemistry involved during the graphite intercalation and exfoliation process, particularly emphasizing the interfacial interactions related to steric repulsion forces, van der Waals forces, hydrogen bonds, π-π stacking, and covalent bonds. These interactions promote the dispersion and stabilization of the graphite derivative structures in polymeric matrices. Finally, it compares the enhanced properties of nanocomposites, such as increased thermal and electrical conductivity and electromagnetic interference (EMI) shielding applications, with those of neat polymer materials. [ABSTRACT FROM AUTHOR]

Achieving a harmonious balance between strength and plasticity is a long-standing problem in single-phase face-centered-cubic (fcc) high-entropy alloys (HEAs). Herein, in-situ TiC ceramic particle reinforced fcc-structured Fe 1.4 Co 0.8 Ni 0.8 Cr HEAs is designed and investigated by combining the experiments and first-principate calculations. The results show that the y (TiC)–Fe 1.4 Co 0.8 Ni 0.8 Cr (y = 0, 2.5, 5.0, 7.5 and 10.0 %, y: volume fraction) composites consist of fcc phase with submicron/micron TiC after the co-addition of Ti and C element, and the formation of TiC facilitates to refine the microstructure of the composites. Such microstructural evolutions significantly enhance the mechanical performances of the composites. Particularly, the 7.5 % (TiC)–Fe 1.4 Co 0.8 Ni 0.8 Cr composite exhibits a high yield strength of ∼562.7 ± 7.7 MPa and tensile strength of ∼971.3 ± 5.4 MPa, which are respectively increased by 169.0 % and 88.3 % as compared with the Fe 1.4 Co 0.8 Ni 0.8 Cr based alloy, yet with the fracture elongation decreases to 35.9 ± 0.3 %. The increment in yield strength is mainly driven from the combined effect of the grain refinement strengthening, dislocation strengthening and precipitation strengthening. Density functional theory (DFT) results reveal that the increase of C –Ti bonds and the formation of covalent bonds in the 7.5 % (TiC)–Fe 1.4 Co 0.8 Ni 0.8 Cr composite lead to relatively higher strength and lower ductility, which are well agreed with the experimental results. [ABSTRACT FROM AUTHOR]

Microflow catalysis is a cutting-edge approach to advancing chemical synthesis and manufacturing, but the challenge lies in developing efficient and stable multiphase catalysts. Here we showcase incorporating amine-containing metal-organic cages into automated microfluidic reactors through covalent bonds, enabling highly continuous flow catalysis. Two Fe4L4 tetrahedral cages bearing four uncoordinated amines were designed and synthesized. Post-synthetic modifications of the amine groups with 3-isocyanatopropyltriethoxysilane, introducing silane chains immobilized on the inner walls of the microfluidic reactor. The immobilized cages prove highly efficient for the reaction of anthranilamide with aldehydes, showing superior reactivity and recyclability relative to free cages. This superiority arises from the large cavity, facilitating substrate accommodation and conversion, a high mass transfer rate and stable covalent bonds between cage and microreactor. This study exemplifies the synergy of cages with microreactor technology, highlighting the benefits of heterogenous cages and the potential for future automated synthesis processes Microflow catalysis represents a cutting-edge method for advancing chemical synthesis and manufacturing, though developing efficient and stable multiphase catalysts remains challenging. Here the authors demonstrate the incorporation of amine-containing metal-organic cages into automated microfluidic reactors through covalent bonds, facilitating highly continuous flow catalysis. [ABSTRACT FROM AUTHOR]

[Display omitted] Compared with layered materials such as graphite and transition metal disulfide compounds with highly anisotropic in-plane covalent bonds, it is inherently more challenging to obtain independent metallic two-dimensional films with atomic thickness. In this study, PtNi layered metallene nanobowls (LMBs) with multilayer atomic-scale nanosheets and bowl-like structures have been synthesized in one step using structural and electronic effects. The material has the advantage of catalyzing pH-universal hydrogen evolution reaction (HER). Compared with Pt/C, PtNi LMBs exhibited excellent HER activity and stability under all pH conditions. The overpotentials of 10 mA cm−2 at 0.5 M H 2 SO 4 , 1.0 M phosphate buffer and 1.0 M KOH were 14.8, 20.3, and 34.0 mV, respectively. Under acidic, neutral and alkaline conditions, the HER Faraday efficiencies reach 98.97%, 98.85%, and 99.04%, respectively. This study provides an example for the preparation of unique multilayer nanobowls, and also provides a basic research platform for the development of special HER materials. [ABSTRACT FROM AUTHOR]

Cross-linked polymers with covalent adaptable networks (CANs) can be reprocessed under external stimuli owing to the exchangeability of dynamic covalent bonds. Optimization of reprocessing conditions is critical since increasing the reprocessing temperature costs more energy and even deteriorates the materials, while reducing the reprocessing temperature via molecular design usually narrows the service temperature range. Exploiting CO2 gas as an external trigger for lowering the reprocessing barrier shows great promise in low sample contamination and environmental friendliness. Herein, we develop a type of CANs incorporated with ionic clusters that achieve CO2-facilitated recyclability without sacrificing performance. The presence of CO2 can facilitate the rearrangement of ionic clusters, thus promoting the exchange of dynamic bonds. The effective stress relaxation and network rearrangement enable the system with rapid recycling under CO2 while retaining excellent mechanical performance in working conditions. This work opens avenues to design recyclable polymer materials with tunable dynamics and responsive recyclability. Cross-linked polymers with covalent adaptable networks are reprocessed under external stimuli at high temperatures which might deteriorate their performance. Here, the authors introduce carbon dioxide responsive ionic clusters into covalent adaptable polymer networks to facilitate the exchange of dynamic bonds providing materials with a rapid recycling and good mechanical performance. [ABSTRACT FROM AUTHOR]

Organic molecules with dynamic covalent-bonding characteristics have attracted much attention for their important role in constructing stimulus-responsive smart materials. However, it is difficult to realize sensitive and reversible covalent bond cleavage/formation through external stimuli in the aggregated state of molecules. Herein, a series of 2,3-diphenylmaleonitriles (DPMNs) with photoinduced π-bond cleavage properties have been designed and synthesized to construct the dynamic covalent bond materials. The cis-form 2,3-diphenylmaleonitriles (Z-DPMNs) exhibit significant photochromism in both solid and solution states under ultraviolet light and visible light. The photochromism stems from the photoinduced π-bond splitting of Z-DPMNs, resulting in a transition from the closed-shell to open-shell structure. Moreover, the twisted structure and molecular stacking of Z-DPMNs, the push-pull electron effect of substituents, and the external factors including temperature and solvent polarity have important effects on the dynamic conversion of π-bonds. Based on the sensitive and reversible optical performance transformation, Z-DPMNs can be applied as safety ink in anti-counterfeiting, information encryption and storage systems. This work not only provides an approach for constructing dynamic covalent bonds but also greatly enriches stimulus-responsive materials. Dynamic covalent bonding can be useful in preparation of stimuli responsive materials, but this is challenging in the aggregated state. Here, the authors report the development of compounds with photoinduced π-bond cleavage to prepare dynamic covalent bond materials. [ABSTRACT FROM AUTHOR]

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Herein, we investigated hydrogels composed of boronic-acid-functionalized alginate and blended with polyvinyl alcohol (PVA) of different molecular weights to control the release of metoclopramide hydrochloride as a function of pH and shear stress. The functionalization of alginate introduced dynamic covalent bonding and pH-responsive properties that can modulate network connectivity. The study investigated the viscoelastic properties of the hydrogels, their drug release profiles, and their responsiveness to changes in pH and shear forces. The results showed that a higher PVA molecular weight and alkaline pH conditions increased hydrogel viscosity and stiffness due to a more stable and interconnected network structure than acidic pH. Metoclopramide release revealed that the hydrogels exhibited pH-responsive drug release behavior. The drug was more readily released under acidic conditions due to the instability of sp2-hybridized boronate ester bonds. The influence of shear forces on the release of metoclopramide was also investigated at shear rates of 1, 10, and 100 s−1, revealing their effect on matrix stiffening. Research shows that AlgBA/PVA hydrogels have unique properties, such as dynamic covalent bonding, that make them sensitive to external mechanical forces. This sensitivity makes them ideal for applications where physiological conditions trigger drug release. [ABSTRACT FROM AUTHOR]

Rotaxanes are typically prepared using covalent bonds to trap a wheel component onto an axle molecule, and rotaxane-type wheel–axle assembly using only noncovalent interactions has been far less explored. Here we show that a dinickel(II) metallomacrocycle forms two different types of wheel–axle assemblies with a dibenzylammonium axle molecule based only on noncovalent interactions. The non-threaded assembly was obtained by introduction of Ni2+ into the macrocycle before the complexation with the axle molecule (metal-first method). The non-threaded assembly was in rapid equilibrium with each of the components in solution. The threaded assembly was obtained by introduction of Ni2+ after the formation of a pseudorotaxane from the non-metalated wheel and the axle molecule (axle-first method). The threaded assembly was not in equilibrium with the dissociated species even though it was maintained only by noncovalent interactions. Thus, formation of one of the non-threaded and threaded wheel–axle assemblies over the other is governed by the assembly pathway. Mechanically interlocked rotaxanes are typically prepared using covalent bonds to trap a wheel component onto an axle molecule, and rotaxane-type wheel–axle assembly using only noncovalent interactions has been far less explored. Here, a dinickel(II) metallomacrocycle is found to form two different types of wheel–axle assemblies, with a dibenzylammonium axle molecule forming both non-threaded and rotaxane-type threaded assemblies, based only on noncovalent interactions, with formation of one over the other governed by the assembly pathway. [ABSTRACT FROM AUTHOR]

Boric acid, H3BO3, is a molecular solid made up of layers held together by weak van der Waals forces. It can be considered a pseudo "2D" material, like graphite, compared to graphene. The key distinction is that within each individual layer, the molecular units are connected not only by strong covalent bonds but also by hydrogen bonds. Therefore, classic liquid exfoliation is not suitable for this material, and a specific method needs to be developed. Preliminary results of exfoliation of boric acid particles by combination of ultrasound and the use of surfactants are presented. Ultrasound provides the system with the energy needed for the process, and the surfactant can act to keep the crystalline flakes apart. A system consisting of a saturated solution and large excess solid residue of boric acid was treated in this way for a few hours at 40 °C in the presence of various sodium stearate, proving to be very promising, and an incipient exfoliation was achieved. [ABSTRACT FROM AUTHOR]

Dynamic bonds can facilitate reversible formation and dissociation of connections in response to external stimuli, endowing materials with shape memory and self-healing capabilities. Temperature is an external stimulus that can be easily controlled through heat. Dynamic covalent bonds in response to temperature can reversibly connect, exchange, and convert chains in the polymer. In this review, we introduce dynamic covalent bonds that operate without catalysts in various temperature ranges. The basic bonding mechanism and the kinetics are examined to understand dynamic covalent chemistry reversibly performed by equilibrium control. Furthermore, a recent synthesis method that implements dynamic covalent coupling based on various polymers is introduced. Dynamic covalent bonds that operate depending on temperature can be applied and expand the use of polymers, providing predictions for the development of future smart materials. [ABSTRACT FROM AUTHOR]

Acylhydrazone bonds can participate in dynamic exchange reactions under acid-stimulated conditions, and disulfide bonds can participate in dynamic exchange reactions under thermally stimulated conditions. It is of great significance to prepare epoxy vitrimer that can rapidly self-repair under acid and thermal stimulation conditions. In this paper, vanillin was used as raw material, and monomer (VAN-AD) containing acylhydrazone bond was synthesized by reaction with adipic dihydrazide. Then, VAN-AD and 4-aminophenyl disulfide (SS) were cured together with glycerol triglycidyl ether to prepare an epoxy vitrimer with acylhydrazone and disulfide dual dynamic covalent bonds. Where VAN-AD provides some of the flexible chain segments and acylhydrazone bonds and SS provides the aromatic phenyl and disulfide bonds. The material was prepared in a simple process and under mild condition, and the properties of the material were optimized by changing the ratio of VAN-AD to SS. The Tg of the material was 50 °C when the ratio of SS was the highest, the thermal stability was enhanced with the increase of the ratio of SS, and the maximum tensile strength up to 50.9 MPa, and the material can be completely degraded by DMF with 5% HCl. It is worth noting that the material shows rapid self-healing properties under acid-heat conditions, self-healing rates up to 97.37%, and the tensile strength can reach 26 MPa after repair. The material can be successfully remodeled by hot pressing for 1 h at 140 °C and 10 MPa. [ABSTRACT FROM AUTHOR]

CeO2 has high elastic modulus and thermal stability, as well as good surface effects, making it ideal as a reinforcement for aluminum matrix composites. In this paper, the interfacial relationships between Al and CeO2 was studied by first-principles calculation, and the nucleation mechanism of aluminum matrix growth on CeO2 substrate was discussed. First, the Al/CeO2 interface matching crystal surface was identified as the Al(111)/CeO2(111) interface. Then, the surface work function was calculated for all surfaces constituting the Al(111)/CeO2(111) interface, and the results showed that the Al(111) loses charge more easily than CeO2(111). Subsequently, the interface energy and work of adhesion of the Al(111)/CeO2(111) interface were calculated, and the results showed that the interface energy of O1–Al was the smallest (0.07 J/m2), the work of adhesion of O2 interface energy of O1–Al was the smallest (0.07 J/m2), the work of adhesion of O2–Al was the largest (9.36 J/m2)Al was the largest (9.36 J/m2). Finally, the combined properties of the Al(111)/CeO2(111) interface were analyzed by the electronic properties at the interface, and the results showed that The Al(111)/CeO2(111) interface is a mixture of ionic and covalent bonds. Therefore, the calculated results confirm that the effectiveness of CeO2 as a heterogeneous nucleation substrate for Al. This study provides a theoretical basis for the nucleation mechanism of the heterogeneous nucleation interface between CeO2 and aluminum matrix. [ABSTRACT FROM AUTHOR]

The proton exchange membrane water electrolyzer (PEMWE), crucial for green hydrogen production, is challenged by the scarcity and high cost of iridium‐based materials. Cobalt oxides, as ideal electrocatalysts for oxygen evolution reaction (OER), have not been extensively applied in PEMWE, due to extremely high voltage and poor stability at large current density, caused by complicated structural variations of cobalt compounds during the OER process. Thus, the authors sought to introduce chromium into a cobalt spinel (Co3O4) catalyst to regulate the electronic structure of cobalt, exhibiting a higher oxidation state and increased Co–O covalency with a stable structure. In‐depth operando characterizations and theoretical calculations revealed that the activated Co–O covalency and adaptable redox behavior are crucial for facilitating its OER activity. Both turnover frequency and mass activity of Cr‐doped Co3O4 (CoCr) at 1.67 V (vs RHE) increased by over eight times than those of as‐synthesized Co3O4. The obtained CoCr catalyst achieved 1500 mA cm−2 at 2.17 V and exhibited notable durability over extended operation periods – over 100 h at 500 mA cm−2 and 500 h at 100 mA cm−2, demonstrating promising application in the PEMWE industry. [ABSTRACT FROM AUTHOR]

The preparation of mechanical robust organic room‐temperature phosphorescence (RTP) materials especially with white afterglow is attractive but rarely reported. Herein, a method to produce mechanical robust colorful RTP transparent wood (PTW) by infiltrating delignified wood with poly (vinyl alcohol) solutions containing arylboronic acids with various π conjugations is reported. The doubly rigid environment provided by the B─O covalent bonds and hydrogen bonds can stabilize the triplet excitons, leading to a ultralong lifetime of up to 2.13 s and excellent RTP emission stability (without obviously quenching over a month) of the target PTW. Besides, as a promising structural material for optical applications, the PTW shows combined advantages of multicolored persistent luminescence (from blue to green and then to red), good optical transmittance (≈90%), and striking mechanical strength (≈154 MPa). More importantly, by introducing appropriate amount of fluorescent dye rhodamine 6 G to the PTW with blue afterglow, white afterglow with a lifetime of 1.85 s is successfully achieve through triplet‐to‐singlet Förster resonance energy transfer. The PTW can function as afterglow window, anticounterfeiting label, and time delay lighting. This success paves the way for the development of mechanical robust, ecofriendly, and practical RTP materials. [ABSTRACT FROM AUTHOR]

A covalently bonded WO3/PEDOT hybrid nanorods array has been prepared through solvothermal, oil bath, and electrochemical deposition methods using KH57 as a coupling agent. The obtained WO3/PEDOT shows substantially increased electrochromic performance with an increased response speed (3.4 s for coloring and 1.2 s for bleaching), excellent optical modulation (86.7% at 633 nm), high coloration efficiency (122.0 cm2/C at 633 nm), and distinguished cyclic stability. It was found that the covalent bond interaction between WO3 and PEDOT plays an essential role in property enhancement. The covalently bonded inorganic/organic hybrid nanorods array may promise great potential in developing smart-display and energy-efficient materials and devices featuring low energy consumption, cost effectiveness, and environmental protection. [ABSTRACT FROM AUTHOR]

[Display omitted] Carbonyl or imine-based compounds have received a great deal of attention due to their high specific capacity and designability as cathodes for aqueous rechargeable organo-aluminum batteries. However, the inherent low conductivity and high solubility of carbonyl and imine-based compounds severely affect the cycling stability of aluminum batteries. Therefore, it is urgent to find an organic cathodes material with low solubility and good cycling performance. In this work, dibenzo[ a , c ]dibenzo[5,6:7,8]quinoxalino[2,3-i]phenazine-10,21-dione (DDQP) were synthesized by simple dehydration condensation to form new imine covalent bonds, which led to the synthesis of imine-conjugated backbone structures with carbonyl, extended π-conjugation planes, and increased active sites, resulting in increased specific capacities. Its storage mechanism with Al(OTF) 2 + has also been confirmed. This monovalent ion usually possesses a lower coulombic interaction, which leads to a reduced solubility of DDQP during redox processes and improves its cyclic stability. The specific capacity of DDQP is 252.22 mAh/g at a current density of 400 mA g−1. After cycling, the discharge specific capacity remains at 219 mAh/g. Surprisingly, the conductivity of the battery also is improved by this structure of multiple active sites. And it can be further confirmed by theoretical calculations that the synthesis of DDQP realigns the arrangement of the electron cloud, enhances the electron affinity, and reduces the energy gap. This study provides a new reference for improving the performance of aqueous organic aluminum batteries. [ABSTRACT FROM AUTHOR]

The orthopedic application of Mg alloys suffers from excessive degradation. In this study, hydroxyapatite (HAP) nanoparticles are doped with MgO by high-energy ball milling, and then the obtained powders are compounded with WE43 powders and prepared into implants by laser powder bed fusion. During milling process, Mg2+ ions on MgO exchange some Ca2+ in HAP by mechanical collision and friction, which forms covalent bonds on the MgO/HAP interface. Subsequently, TEM observation showed that MgO on HAP forms semi-coherent interfaces with α-Mg, contributing to good bonding on the Mg/MgO interface. In this manner, strong bonding interfaces between ceramic particles and α-Mg were established, thereby preventing the agglomeration of nanoparticles. The well-dispersed ceramic particles provided more nucleation sites for apatite deposition, which benefits the formation of the passivation layer and thereby improves corrosion resistance. As a consequence, the composite exhibited a low corrosion density (20.1 ± 1.3 μA/cm2), high corrosion resistance (752.8 ± 19.7 Ω cm2), and low carrier concentration (1.28 ± 0.01 cm−3), indicating the formation of a more protective passivation layer. These findings suggested that the mHAP incorporated Mg composite may be a potential candidate for orthopedic implant. [ABSTRACT FROM AUTHOR]

• AZ31 alloy/CFRP joints were produced by laser joining with/without HF treatment. • NEXAFS technique demonstrated that HF treatment imparted reactive sites on the alloy surface for chemical bonding. • H-F bond through the interaction of MgF 2 and polar amide group of polymer resulted in high adhesion strength. Although hydrofluoric acid (HF) surface treatment is known to enhance the joining of metals with polymers, there is limited information on its effect on the joining of AZ31 alloy and carbon-fiber-reinforced plastics (CFRPs) through laser-assisted metal and plastic direct joining (LAMP). This study uses the LAMP technique to produce AZ31-CFRP joints. The joining process involves as-received AZ31, HF-pretreated AZ31, and thermally oxidized HF-pretreated AZ31 alloy sheets. Furthermore, the bonding strength of joints prepared with thermally oxidized AZ31 alloy sheets is examined to ascertain the combined effect of HF treatment and thermal oxidation on bonding strength. The microstructures, surface chemical interactions, and mechanical performances of joints are investigated under tensile shear loading. Various factors, such as bubble formation, CFRP resin decomposition, and mechanical interlocking considerably affect joint strength. Additionally, surface chemical interactions between the active species on metal parts and the polar amide along with carbonyl groups of polymer play a significant role in improving joint strength. Joints prepared with surface-pretreated AZ31 alloy sheets show significant improvements in bonding strength. [Display omitted] [ABSTRACT FROM AUTHOR]

Nanobiocatalysts (NBCs), which merge enzymes with nanomaterials, provide a potent method for improving enzyme durability, efficiency, and recyclability. This review highlights the use of eco-friendly synthesis methods to create sustainable nanomaterials for enzyme transport. We investigate different methods of immobilization, such as adsorption, ionic and covalent bonding, entrapment, and cross-linking, examining their pros and cons. The decreased environmental impact of green-synthesized nanomaterials from plants, bacteria, and fungi is emphasized. The review exhibits the various uses of NBCs in food industry, biofuel production, and bioremediation, showing how they can enhance effectiveness and eco-friendliness. Furthermore, we explore the potential impact of NBCs in biomedicine. In general, green nanobiocatalysts are a notable progression in enzyme technology, leading to environmentally-friendly and effective biocatalytic methods that have important impacts on industrial and biomedical fields. [ABSTRACT FROM AUTHOR]

Boron-doped polycyclic aromatic hydrocarbons exhibit excellent optical properties, and regulating their photophysical processes is a powerful strategy to understand the luminescence mechanism and develop new materials and applications. Herein, an electrochemically responsive B–O dynamic coordination bond is proposed, and used to regulate the photophysical processes of boron-nitrogen-doped polyaromatic hydrocarbons. The formation of the B–O coordination bond under a suitable voltage is confirmed by experiments and theoretical calculations, and B–O coordination bond can be broken back to the initial state under opposite voltage. The whole process is accompanied by reversible changes in photophysical properties. Further, electrofluorochromic devices are successfully prepared based on the above electrochemically responsive coordination bond. The success and harvest of this exploration are beneficial to understand the luminescence mechanism of boron-nitrogen-doped polyaromatic hydrocarbons, and provide ideas for design of dynamic covalent bonds and broaden material types and applications. Boron-doped polycyclic aromatic hydrocarbons with dynamic covalent bonds have interesting optical properties, but electricity-responsive bonds are less studied. Here, the authors report an electrochemically responsive B-O coordination bond with short switching time. [ABSTRACT FROM AUTHOR]

Covalent organic frameworks (COFs) have emerged as promising renewable electrode materials for LIBs and gained significant attention, but their capacity has been limited by the densely packed 2D layer structures, low active site availability, and poor electronic conductivity. Combining COFs with high-conductivity MXenes is an effective strategy to enhance their electrochemical performance. Nevertheless, simply gluing them without conformal growth and covalent linkage restricts the number of redox-active sites and the structural stability of the composite. Therefore, in this study, a covalently assembled 3D COF on Ti3C2 MXenes (Ti3C2@COF) is synthesized and serves as an ultralong cycling electrode material for LIBs. Due to the covalent bonding between the COF and Ti3C2, the Ti3C2@COF composite exhibits excellent stability, good conductivity, and a unique 3D cavity structure that enables stable Li+ storage and rapid ion transport. As a result, the Ti3C2-supported 3D COF nanosheets deliver a high specific capacity of 490 mAh g−1 at 0.1 A g−1, along with an ultralong cyclability of 10,000 cycles at 1 A g−1. This work may inspire a wide range of 3D COF designs for high-performance electrode materials. [ABSTRACT FROM AUTHOR]

The regulation of topological structure of covalent adaptable networks (CANs) remains a challenge for epoxy CANs. Here, we report a strategy to develop strong and tough epoxy supramolecular thermosets with rapid reprocessability and room-temperature closed-loop recyclability. These thermosets were constructed from vanillin-based hyperbranched epoxy resin (VanEHBP) through the introduction of intermolecular hydrogen bonds and dual dynamic covalent bonds, as well as the formation of intramolecular and intermolecular cavities. The supramolecular structures confer remarkable energy dissipation capability of thermosets, leading to high toughness and strength. Due to the dynamic imine exchange and reversible noncovalent crosslinks, the thermosets can be rapidly and effectively reprocessed at 120 °C within 30 s. Importantly, the thermosets can be efficiently depolymerized at room temperature, and the recovered materials retain the structural integrity and mechanical properties of the original samples. This strategy may be employed to design tough, closed-loop recyclable epoxy thermosets for practical applications. The covalent crosslinked structure of epoxy thermosets difficult their reprocessability and recyclability. Here, the authors report a method for developing closed loop recycling of strong and tough epoxy supramolecular thermosets constructed with hyperbranched topological structure in an energy-saving and easy-to-conduct way. [ABSTRACT FROM AUTHOR]

Single-crystal X-ray diffraction analysis has emerged as the most reliable method for determining the structures of organic molecules. However, numerous analytes, such as liquid organic molecules, pose challenges in crystallization, making their structures directly elusive via X-ray crystallography methods. Herein, we introduced the rapid cocrystallization of a macrocycle named phenanthrene[2]arene (PTA, host) with 15 liquid organic molecules (guests). The guest liquid organic molecules were successively cocrystallized with the aid of the PTA host. Moreover, the chemical structures of the liquid organic molecules could be determined through single-crystal X-ray diffraction analysis. PTA exhibited high adaptivity and was capable of encapsulating liquid organic molecules without forming covalent bonds or strong directional interactions. The results revealed that the adaptive crystals of PTA exhibited excellent cocrystallization capacity. Weak noncovalent interactions between the host and guest molecules were crucial for organizing the guests in an ordered pattern. [ABSTRACT FROM AUTHOR]

Cellulose detectors, as green sensors, are some of the defensive mechanisms of plants which combat environmental stresses. However, extracted cellulose struggles to fulfil these functionalities due to its rigid physical/chemical properties. In this study, a novel cellulose dual-crosslinked framework (CDCF) is proposed. This comprises a denser temporary physical crosslinking bond (hydrogen bonding) and a looser covalent crosslinking bond (N,N-methylenebisacrylamide), which create deformable spaces between the two crosslinking sites. Abundant pH-sensitive carboxyl groups and ultralight, highly porous structures make CDCF response very sensitive in acid/alkaline vapor environments. Hence, a significant shrinkage of CDCF was observed following exposure to vapors. Moreover, a curcumin-incorporated CDCF exhibited dual shape and color changes when exposed to acid/alkaline vapors, demonstrating great potential for the multi-detection of acid/alkaline vapors. [ABSTRACT FROM AUTHOR]

Bridgmanite, the most abundant mineral in the lower mantle, can play an essential role in deep-Earth hydrogen storage and circulation processes. To better evaluate the hydrogen storage capacity and its substitution mechanism in bridgmanite occurring in nature, we have synthesized high-quality single-crystal bridgmanite with a composition of (M g 0.88 F e 0.05 2 + F e 0.05 3 + A l 0.03) (S i 0.88 A l 0.11 H 0.01) O 3 at nearly water-saturated environments relevant to topmost lower mantle pressure and temperature conditions. The crystallographic site position of hydrogen in the synthetic (Fe,Al)-bearing bridgmanite is evaluated by a time-of-flight single-crystal neutron diffraction scheme, together with supporting evidence from polarized infrared spectroscopy. Analysis of the results shows that the primary hydrogen site has an OH bond direction nearly parallel to the crystallographic b axis of the orthorhombic bridgmanite lattice, where hydrogen is located along the line between two oxygen anions to form a straight geometry of covalent and hydrogen bonds. Our modeled results show that hydrogen is incorporated into the crystal structure via coupled substitution of Al3+ and H+ simultaneously exchanging for Si4+, which does not require any cation vacancy. The concentration of hydrogen evaluated by secondary-ion mass spectrometry and neutron diffraction is ~0.1 wt% H2O and consistent with each other, showing that neutron diffraction can be an alternative quantitative means for the characterization of trace amounts of hydrogen and its site occupancy in nominally anhydrous minerals. [ABSTRACT FROM AUTHOR]

A composite photocatalyst, denoted as rGO/NiIn2S4 (rGO/NIS), was created to facilitate the efficient destruction of crystal violet (CV) dye under visible radiation. This composite photocatalyst consists of NiIn2S4 (NIS) and reduced graphene oxide (rGO). The photocatalytic behavior of pristine NiIn2S4 for the breakdown of crystal violet (CV) in the presence of visible light was found to be significant. However, the experimental findings indicated that the material experienced substantial breakdown upon exposure to visible light. The rGO/NIS contains significantly improved visible light photocatalytic behavior compared to the hybrid material (NIS). The data on characterization indicates that there exists a chemical interaction between NiIn2S4 nanosheets and rGO sheets, resulting in the development of a band structure that may be adjusted and in an enhancement in photocatalytic performance. Significantly, the establishment of covalent bonds between NiIn2S4 and rGO holds promise for enhancing the structural integrity of the composite, thus augmenting its resistance to photocorrosion. The finding of this study has the potential to contribute to the formulation of an innovative strategy in the creation of photocatalysts that are active under visible light and resistant to degradation by sunlight. These photocatalysts can be utilized in the field of environmental remediation. [ABSTRACT FROM AUTHOR]

Exploring organic semiconductor gas sensors with high sensitivity and selectivity is crucial for the development of sensor technology. Herein, for the first time, a promising chemiresistive organic polymer P‐BNT based on a novel π‐conjugated triarylboron building block is reported, showcasing an excellent responsivity over 30 000 (Ra/Rg) against 40 ppm of NH3, which is ≈3300 times higher than that of its B‐N organic small molecule BN‐H. More importantly, a molecular induction strategy to weaken the bond dissociation energy between polymer and NH3 caused by strong acid‐base interaction is further executed to optimize the response and recovery time. As a result, the BN‐H/P‐BNT system with rapid response and recovery times can still exhibit a high responsivity of 718, which is among the highest reported NH3 chemiresistive sensors. Supported by in situ FTIR spectroscopy and theoretical calculations, it is revealed that the N‐H fractions in BN‐H small molecule promoted the charge distribution on phenyl groups, which increases charge delocalization and is more conducive to gas adsorption in such molecular systems. Notably, these distinctive small molecules also promoted charge transfer and enhanced electron concentration of the P‐BNT sensing polymer, thus achieving superior B‐N‐containing organic molecules with excellent sensing performance. [ABSTRACT FROM AUTHOR]