Chemical Bonding Research Articles

Comparative analysis of tetravalent actinide Schiff base complexes: influence of donor and ligand backbone on molecular geometry and metal binding.

A series of isostructural early actinide AnIV complexes was synthesized in order to investigate the influence of a conjugated framework in the ligand backbone on An bonding. Therefore, the AnIV complexes [An(pyrophen)2] (An = Th, U, Np, and Pu) with the pure N-donor ligand bis(2-pyrrolecarbonylaldehyde)-o-phenylenediamine referred to as pyrophen, were synthesized and characterized. Solid state analysis via single-crystal X-ray diffraction (SC-XRD) reveals two sets of ligands binding in an almost orthogonal arrangement to the actinide center. For the larger actinides Th and U, the coordination sphere allows for additional coordination by a solvent molecule. Nuclear magnetic resonance spectroscopy (NMR) studies show the presence of highly symmetrical complexes in solution in good agreement with the solvent-free solid structures. While SC-XRD suggests mainly ionic binding, an analysis of paramagnetic NMR contributions and quantum chemical bond analysis hint towards significant covalency in the U, Np, and Pu compounds. This series of An complexes allowed for a thorough structural and theoretical comparison of a conjugated system to a closely related N-donor ligand (pyren)[1], as well as to the mixed N,O Schiff base ligands salophen (conjugated) and salen (non-conjugated).

Recent Progress on Organic Electron Donors (OEDs) Enabled Radical Reactions

Over the past few decades, organic transformations facilitated by small organic molecules have witnessed considerable advancements. Small organic molecules have been widely applied to the construction of various skeletons. However, reduction as one of the fundamental reactions is generally initiated by metal‐containing reducing agents, although the initial progress of organic electron donors (OEDs) enabled reductive cleavage of some chemical bonds had been achieved in 1990s. Due to their structural diversity and tunability, OEDs can overcome the limitations of metal‐based reducing agents, such as low selectivity and poor functional group tolerance as well as the environmental problems caused by substantial inorganic waste after reactions. Building on a brief historical overview of OED research, this review focuses on the rencent advancements of the OEDs promoted radical reactions. It covers the reduction of C‐X (X =C, O, N etc.) single bonds, radical cyclization, intermolecular radical addition to unsaturated bonds, radical coupling, functionalization of aromatics, and C‐H bond activation. Additionally, the mechanistic insights of the typical reactions are highlighted for well understanding of the reaction mode involving OEDs.

Significant temperature tunability of the band gap in two-dimensional materials

Two-dimensional (2D) materials have great attentions due to their novel physical and chemical properties. The band gap Eg plays a significant role in influencing their applications, which can be changed by the temperature. In this work, taking the Group-IV materials (graphene, silicene, germanene, and stanene) as the examples, we first study the temperature-dependent Eg by employing the state-of-the-art electron-phonon renormalization calculations. It shows that the primary Eg at K-point is almost unchanged while that at Γ-point decreases directly with temperature increase in all the systems (e.g., Eg reduction in stanene from 100 K to 500 K is 0.006 eV at K-point and 0.148 eV at Γ-point, respectively). The differences are originated from the different chemical bond characteristics at band edges, which are π-bonding at K-point but (σ*) σ (anti-) bonding at Γ-point. The latter are more sensitive to the temperature-induced vibrations, such as the out-of-plane acoustic phonon modes in the three buckling systems. The strong sensitivity of σ-bonding to the vibrations can be further examplified by another four 2D systems (P4, InSb, MgCl2, and C2F2), screening from the database MatHub-2d. This phenomenon offers the temperature tunability for the band gaps at Γ-point of 2D materials, which may have more application significances in optoelectronics.

An Electron Bridge of Shared Atoms Mediated Cs3Bi2Br9/Bi2WO6 Z‐Scheme Heterojunction for Photocatalytic CO2 Reduction

AbstractConverting clean solar energy into chemical energy through artificial photosynthesis is an effective solution to solve the energy and environmental issues. Here, we report a Cs3Bi2Br9/Bi2WO6 (CBB/BWO) Z‐scheme heterojunction constructed via electrostatic self‐assembly, which facilitates efficient separation of photogenerated carriers and ensures the corresponding redox capacity of both components. By sharing Bi atoms, a Br−Bi−O bond is established between CBB and BWO, serving as an “electron bridge”. The electrons generated by BWO are efficiently channeled to CBB through the heterojunction‐formed “electron bridge”, thereby achieving effective photocatalytic CO2 reduction. Under simulated sunlight conditions, it exhibits the highest CO yield of 72.52 μmol g−1 (without the addition of any precious metal, photosensitizers or sacrifices), which is approximately 7‐fold and 18‐fold greater than that of pure CBB and BWO, respectively. This work provides a more profound comprehension of the regulation of electron transfer through interfacial chemical bonds, thereby proposing a promising strategy for the development of efficient heterojunction photocatalysts for CO2 photoreduction.

Hyperconjugation-Driven Isodesmic Reaction of Indoles and Anilines: Reaction Discovery, Mechanism Study, and Antitumor Application.

Isodesmic reactions, in which chemical bonds are redistributed between substrates and products, provide a general and powerful strategy for both biological and chemical synthesis. However, most isodesmic reactions involve either metathesis or functional-group transfer. Here, we serendipitously discovered a novel isodesmic reaction of indoles and anilines that proceeds intramolecularly under weakly acidic conditions. In this process, the five-membered ring of the indole motif is broken and a new indole motif is constructed on the aniline side, accompanied by the formation of a new aniline motif. Mechanistic studies revealed the pivotal role of σ→π* hyperconjugation on the nitrogen atom of the indole motif in driving this unusual isodesmic reaction. Furthermore, we successfully synthesized a diverse series of polycyclic indole derivatives; among quinolines, potential antitumor agents were identified using cellular and in vivo experiments, thereby demonstrating the synthetic utility of the developed methodology.

Multielectron Reduction of Nitrosoarene via Aluminylene-Silylene Cooperation.

The cooperative effects of main-group elements pave the way for novel chemical transformations. However, the potential of bimetallic complexes featuring the most abundant aluminum and silicon elements remains largely unexplored. In this study, we present the synthesis and characterization of bis(silylene)-stabilized aluminylene 2. The cooperation between aluminylene and silylene allows for the facile cleavage of the N-O bond in nitrosoarenes, producing an aluminum imide complex 4 and tetracyclic oxazasilaalanes 5 and 6, and also promotes the dearomatization of 2-methylquinoline, yielding a silylalane 7. In addition, 2 is an effective precatalyst for the reductive coupling of nitrosoarenes to azoxyarenes. These results outline an approach for orchestrating aluminum and silicon cooperation to facilitate chemical bond activation.

Pb-N Chemically Anchors CsPbBr3 on 1D Porous Tubular g-C3N4 for Enhanced Photocatalytic CO2 Reduction.

Halide perovskite CsPbBr3 (CPB) quantum dots (QDs) are considered as a promising candidate for solar-driven CO2 conversion for their unique optoelectronic properties and suitable band structure. However, the CO2 conversion efficiency of pristine CsPbBr3 quantum dots is severely limited due to their rapid electron-hole pair recombination and insufficient active sites. In this study, by immobilizing CPB QDs onto one-dimensional (1D) porous tubular g-C3N4 (TCN), an effective 0D/1D CPB@TCN heterojunction photocatalyst for CO2 reduction is fabricated. Density functional theory (DFT) calculations combined with experimental studies demonstrate that CPB QDs are uniformly anchored on the surface of TCN through Pb-N chemical bonding, resulting in efficient separation and transfer of photogenerated carriers in CPB@TCN photocatalysts. The resultant CPB@TCN photocatalysts exhibit significantly enhanced photocatalytic activity for CO2 reduction with the highest conversion rate of 22.62 μmol·g-1·h-1, which is 5.33-times higher than that of pristine CPB QDs. This work unveils the interfacial bonding mechanism of CPB@TCN heterojunction through Pb-N chemical bond, which provides new insights for the development perovskite-based heterojunction photocatalysts.

A Series of Ultra-low Permittivity ALaP4O12 (A = Li, Na, K) Metaphosphate Microwave Dielectric Ceramics for Ultra-wideband Dielectric Resonant Antenna Application.

The employment of ultra-low permittivity materials in the configuration of antennas has been demonstrated to augment the antenna bandwidth and diminish signal delay effectively. This study presents three ultra-low permittivity metaphosphate microwave dielectric ceramics (MWDCs). The ALaP4O12 (A = Li, Na, K) metaphosphate ceramics, which all belong to the monoclinic crystal system, exhibit extremely low permittivity (εr ≈ 5) and excellent quality factor (Q·f > 10,000 GHz) at a low sintering temperature (T < 950 °C). Terahertz time-domain spectroscopy indicates that the εr of ALaP4O12 at terahertz frequencies is comparable to that observed in the microwave band and its value remains stable over an extensive frequency range. Furthermore, the relationship between the crystal structure and the dielectric properties of ALaP4O12 has been analyzed through the lens of chemical bond theory. The highest Q·f value observed for LiLaP4O12 can be attributed to the high chemical bond strength and stability of its crystal structure. The lowest ionic polarizability per unit volume is exhibited by NaLaP4O12, which results in the lowest pore-corrected permittivity. The thermal expansion of the chemical bonds within KLaP4O12 is considerable, resulting in the highest coefficient of thermal expansion. Finally, the performance of a LiLaP4O12-based dielectric resonator antenna (DRA) excited by slot-coupled microstrip lines was designed and optimized by using different ceramic radius-to-height (RH) ratios. It was found that when the RH ratio of DRA reached 1.85, both the fundamental mode (HEM11δ) and the higher-order mode (HEM12δ) of DRA were simultaneously excited. The two modes overlap significantly, resulting in an ultra-wideband (UWB) of 46.8% (bandwidth = 7.93 GHz). Concurrently, the maximum radiation efficiency and gain of the DRA, obtained from the simulation, are 97.9% and 7.92 dBi, respectively. The findings of this study may inform the investigation of ultra-low permittivity phosphorus-based MWDCs and UWB DRAs.

Zipper‐Like Dynamic Switching of Coordination Bonds Gives a Polar Bimetallic Halide toward Self‐Driven X‐ray Detection

Polar molecular crystals hold a promise for controlling bulk physical properties originated in their unique switchable polarity via structural transformation. However, the mechanisms for switching polarization are mainly limited to displacive and disorder‐order phase transitions, which rarely involve the reconstruction of chemical bonds. Here, we have switched and tuned electric polarization in a bimetallic halide, (Neopentylammonium)4AgBiBr8 (1), as verified by light‐excited pyroelectric effect. Most notably, its Ag‐Br coordination bonds show a zipper‐like dynamic switching behavior from the ‘locked’ to ‘unlocked’ state, namely, reconstruction of chemical bonds. Coupling with the dynamic ordering of organic cations, this bond‐switching transition makes a contribution to switchable polarization of 1. As expected, its polarity creates pyroelectric effect for self‐driven X‐ray detection with high sensitivity (3.8×103 μC Gy‐1 cm‐2) and low limit of detection (4.8 nGy s‐1). This work on the bond‐switching mechanism provides an avenue to design polar molecular candidate for smart optoelectronic devices.

Electrochemical Decarboxylation Coupling Reactions.

Carboxylic acids are attractive synthetic feedstocks with stable, non-toxic, and inexpensive properties that can be easily obtained from natural sources or through synthesis. Carboxylic acids have long been considered environmentally friendly coupling agents in various organic transformations. In recent years, electrochemically mediated decarboxylation reactions of decarboxylic acids and their derivatives (NHPI) have emerged as effective new methods for constructing carbon-carbon or carbon-heterocarbon chemical bonds. Compared with transition metal and photochemistry-mediated catalytic reactions, which do not require the addition of oxidants and strong bases, electrochemically-mediated decarboxylative transformations are considered a sustainable strategy. In addition, various functional groups tolerate the electrochemical decarboxylation conversion strategy well. Here, we summarize the recent electrochemical decarboxylation reactions to better elucidate the advantages of electrochemical decarboxylation reactions.

Zipper-Like Dynamic Switching ofCoordinationBonds GivesaPolar Bimetallic Halidetoward Self-Driven X-ray Detection.

Polar molecular crystals hold a promise for controlling bulk physical properties originated intheir unique switchable polarity viastructural transformation.However, the mechanisms for switching polarization are mainly limited to displacive and disorder-order phase transitions, which rarelyinvolve thereconstruction of chemical bonds. Here, we have switchedand tuned electric polarizationina bimetallic halide, (Neopentylammonium)4AgBiBr8(1), as verified by light-excited pyroelectric effect. Most notably, its Ag-Br coordination bonds show a zipper-like dynamic switching behavior from the 'locked'to 'unlocked'state, namely, reconstruction of chemical bonds.Coupling with the dynamic ordering of organic cations,this bond-switching transitionmakes a contribution to switchable polarization of 1. As expected, its polaritycreates pyroelectric effectfor self-driven X-ray detectionwithhighsensitivity (3.8×103μC Gy-1cm-2) and low limitof detection(4.8 nGy s-1). This work onthe bond-switching mechanism provides an avenue to designpolar molecularcandidatefor smart optoelectronic devices.

Sustaining 500,000 Folding Cycles through Bioinspired Stress Dispersion Design in Sodium-Ion Batteries.

Developing super-foldable electronic materials and devices presents a significant challenge, as intrinsic conductive materials are unable to achieve numerous true-folding operations (super-foldable) due to limitations from short-range forces of chemical bonds. Consequently, super-foldable batteries remain unexplored. This work focused on sodium-ion batteries as a breakthrough point to advance super-foldable devices. By employing a "2+1" bioinspired strategy, we stepwise designed and assembled super-foldable components, from substrates to electrodes, and to ultimately device. This bioinspired approach completely disperses folding stress and thus prevents the breakage of chemical bonds, enabling the successful fabrication of the first super-foldable ion battery. This battery can withstand true-folding at any angle, in any direction, and for an unprecedented number of cycles-far outperforming current foldable phones with hinge structures. Remarkably, after 500,000 true-folding cycles, the battery's microstructure remains intact with no significant degradation of electrochemical performance. Real-time dynamic folding observations reveal an M-shaped folding structure within the bioinspired materials, which effectively disperses stress via bulged layers, dispersed arcs, and slidable microgrooves that work together across different directions and dimensions to achieve super-foldability. Mechanical simulations vividly verify this principle. This work represents a breakthrough in super-foldable devices, offering valuable insights and promoting practical application for future super-foldable devices.

Formation of coatings from accelerated ions of fluorinated fullerene C&lt;sub&gt;60&lt;/sub&gt;(CF&lt;sub&gt;3&lt;/sub&gt;)&lt;sub&gt;12&lt;/sub&gt;

The first results of the deposition of coatings from accelerated ions of fluorinated fullerene C60(CF3)12 are presented. The coatings were formed at room temperature on Si substrates from a beam of singly charged C60(CF3)+12 ions with an energy of 5 keV, as well as from an ion beam, which also contained doubly charged C60(CF3)122+ ions and a certain amount of ionized fragments of molecules. The properties and structure of coatings obtained from accelerated ions of fluorinated fullerene are compared with the properties and structure of coatings obtained from accelerated C60 fullerene ions under the same conditions. According to X-ray photoelectron spectroscopy, fluorinated fullerene coatings contain about 4% fluorine. Investigations of the coatings structure and chemical bonds by X-ray photoelectron spectroscopy and Raman scattering showed that the presence of fluorine leads to decrease in the content of sp3 bonds and the formation of graphite-like sp2 structures. Coating hardness (H) and Young's modulus (E) compared to C60 ion coatings decrease from 36 to 18 GPa and from 245 to 133 GPa, respectively. The H/E ratio remained the same (~0.14). Tribological tests have shown for all coatings a friction coefficient close to 0.1. Also, all coatings are characterized by very low wear, less than 10–7 mm3/N∙m for coatings obtained from C60(CF3)12 ions, the contact angle is ~76°–78°. In the absence of fluorine, for the coating obtained from C60 ions, it is ~90°.

Energy Dissipation and Toughening of Covalent Networks via a Sacrificial Conformation Approach.

Covalent polymer networks find wide utility in diverse engineering applications owing to their desirable stiffness and resilience. However, the rigid covalent chemical structure between crosslinking points imposes limitations on enhancing their toughness. Although the incorporation of sacrificial chemical bonds has shown promise in improving toughness through energy dissipation, composite networks struggle to maintain both rapid recovery and stiffness. Consequently, a significant challenge persists in achieving a covalent network that combines high strength, stiffness, toughness, and fast recovery performance. To address this challenge, we propose a novel sacrificial structure termed "sacrificial conformation." In this approach, β-cyclodextrin is covalently embedded into the network skeleton as the sacrificial conformation element. Compared to traditional covalent networks (LCN), well-designed cyclodextrin-embedded covalent network (CCN) exhibit a 100-fold increase in Young's modulus and a 60-fold increase in toughness. Importantly, CCN maintains excellent elasticity, ensuring swift recovery after deformation. This sacrificial conformational strategy enables efficient energy dissipation without necessitating the rupture of chemical bonds, thereby overcoming the limitations of traditional approaches. This advancement holds great promise for the design and fabrication of advanced elastomers and hydrogels with superior mechanical properties and dynamic behavior.

Energy Dissipation and Toughening of Covalent Networks via a Sacrificial Conformation Approach

Covalent polymer networks find wide utility in diverse engineering applications owing to their desirable stiffness and resilience. However, the rigid covalent chemical structure between crosslinking points imposes limitations on enhancing their toughness. Although the incorporation of sacrificial chemical bonds has shown promise in improving toughness through energy dissipation, composite networks struggle to maintain both rapid recovery and stiffness. Consequently, a significant challenge persists in achieving a covalent network that combines high strength, stiffness, toughness, and fast recovery performance. To address this challenge, we propose a novel sacrificial structure termed "sacrificial conformation." In this approach, β‐cyclodextrin is covalently embedded into the network skeleton as the sacrificial conformation element. Compared to traditional covalent networks (LCN), well‐designed cyclodextrin‐embedded covalent network (CCN) exhibit a 100‐fold increase in Young's modulus and a 60‐fold increase in toughness. Importantly, CCN maintains excellent elasticity, ensuring swift recovery after deformation. This sacrificial conformational strategy enables efficient energy dissipation without necessitating the rupture of chemical bonds, thereby overcoming the limitations of traditional approaches. This advancement holds great promise for the design and fabrication of advanced elastomers and hydrogels with superior mechanical properties and dynamic behavior.

ERL-ProLiGraph: Enhanced representation learning on protein-ligand graph structured data for binding affinity prediction.

Predicting Protein-Ligand Binding Affinity (PLBA) is pivotal in drug development, as accurate estimations of PLBA expedite the identification of promising drug candidates for specific targets, thereby accelerating the drug discovery process. Despite substantial advancements in PLBA prediction, developing an efficient and more accurate method remains non-trivial. Unlike previous computer-aid PLBA studies which primarily using ligand SMILES and protein sequences represented as strings, this research introduces a Deep Learning-based method, the Enhanced Representation Learning on Protein-Ligand Graph Structured data for Binding Affinity Prediction (ERL-ProLiGraph). The unique aspect of this method is the use of graph representations for both proteins and ligands, intending to learn structural information continued from both to enhance the accuracy of PLBA predictions. In these graphs, nodes represent atomic structures, while edges depict chemical bonds and spatial relationship. The proposed model, leveraging deep-learning algorithms, effectively learns to correlate these graphical representations with binding affinities. This graph-based representations approach enhances the model's ability to capture the complex molecular interactions critical in PLBA. This work represents a promising advancement in computational techniques for protein-ligand binding prediction, offering a potential path toward more efficient and accurate predictions in drug development. Comparative analysis indicates that the proposed ERL-ProLiGraph outperforms previous models, showcasing notable efficacy and providing a more suitable approach for accurate PLBA predictions.

Self‐healing polymers in rigid and flexible perovskite photovoltaics

AbstractOver the past 10 years, perovskite solar cell (PSC) device technologies have advanced remarkably and exhibited a notable increase in efficiency. Additionally, significant innovation approaches have improved the stability related to heat, light, and moisture of PSC devices. Despite these developments in PSCs, the instability of PSCs is a pressing problem and an urgent matter to overcome for practical application. Recently, polymers have been suggested suggestion has been presented to solve the instability issues of PSCs and increase the photovoltaic parameters of devices. Here, first, the fundamental chemical bond types of self‐healing polymers are presented. Then, a comprehensive presentation of the ability of self‐healing polymers in rigid and flexible PSCs to enhance the various physical, mechanical, and optoelectronic properties is presented. Furthermore, valuable insights and innovative solutions for perovskite‐based optoelectronics with self‐healing polymers are provided, offering guidance for future optoelectronic applications.image

Eradicating the Photogenerated Holes in a Photocatalyst-Microbe Hybrid System: A Review.

Finding advanced technologies to store solar energy in chemical bonds efficiently is of great significance for the sustainable development of our society. The recently reported photocatalyst-microbe hybrid (PMH) system couples photocatalysts intimately with microbes and endows heterotrophic microbes with light-harvesting capacity. Generally, when PMH systems are exposed to light, photocatalytic reactions occur on the surface of photocatalysts and the photogenerated electrons enter microbial cells to promote the generation of energy carriers (such as nicotinamide adenine dinucleotide phosphate hydrogen and adenosine triphosphate) and the following chemical synthesis. PMH system applications have expanded from synthesizing value-added products (chemicals, fuels, and polymers) to treating pollutants. However, the successful operation of the PMH system relies on the timely eradication of the photogenerated holes as they recombine with the photogenerated electrons and cause the photocorrosion of the photocatalyst. This review summarizes the strategies for scavenging the photogenerated holes in PMH systems and provides insight into the current gaps and outlooks for future opportunities in this field.

On the osteogenic differentiation of dental pulp stem cells by a fabricated porous nano-hydroxyapatite substrate loaded with sodium fluoride

In the present study, nano-hydroxyapatite (n-HA) powder was extracted from carp bone waste to fabricate porous n-HA substrates by a molding and sintering process. Subsequently, the substrates were loaded with different amounts of sodium fluoride (NaF) through immersion in NaF suspensions for 10, 7.5, and 5 min. The NaF-loaded n-HA substrates were then examined for their structural and physical properties, chemical bonds, loading and release profile, pH changes, cytotoxicity, and osteogenic effect on dental pulp stem cells (DPSCs) at the level of RNA and protein expression. The results showed that the n-HA substrates were porous (> 40% porosity) and had rough surfaces. The NaF could be successfully loaded on the substrates, which was 6.43, 4.50, and 1.47 mg, respectively for n-HA substrates with immersion times of 10, 7.5, and 5 min in the NaF suspensions. It was observed that the NaF release rate was rather fast during the first 24 h in all groups (39.06%, 36.43%, and 39.57% for 10, 7.5, and 5 min, respectively), and decreased dramatically after that, indicating a slow detachment of NaF. Furthermore, the pH of the medium related to all materials was changed during the first 4 days of immersion (from 7.38 to pH of about 7.85, 7.84, 7.63, and 7.66 for C0, C5, C7.5, and C10, respectively). The pH of media associated with the C7.5, and C10 increased up to 4 days and remained relatively constant until day 14 (pH = 7.6). The results of the cytotoxicity assay rejected any toxicity of the fabricated NaF-loaded n-HA substrates on DPSCs, and the cells could adhere to their surfaces with enlarged morphology. The results showed no effect on the osteogenic differentiation at the protein level. Nevertheless, this effect was observed at the gene level.

A Review on the Effect of Wood Surface Modification on Paint Film Adhesion Properties

Wood surface treatment aims to improve or reduce the surface activity of wood by physical treatment, chemical treatment, biological activation treatment or other methods to achieve the purpose of surface modification. After wood surface modification, the paint film adhesion performance, gluing performance, surface wettability, surface free energy and surface visual properties would be affected. This article aims to explore the effects of different modification methods on the adhesion of wood coating films. Modification of the wood surface significantly improves the adhesion properties of the paint film, thereby extending the service life of the coating. Research showed that physical external force modification improved the hydrophilicity and wettability of wood by changing its surface structure and texture, thus enhancing the adhesion of the coating. Additionally, high-temperature heat treatment modification reduced the risk of coating cracking and peeling by eliminating stress and moisture within the wood. Chemical impregnation modification utilized the different properties of organic and inorganic substances to improve the stability and durability of wood. Organic impregnation effectively filled the wood cell wall and increased its density, while inorganic impregnation enhanced the adhesion of the coating by forming stable chemical bonds. Composite modification methods combined the advantages of the above technologies and significantly improved the comprehensive properties of wood through multiple modification treatments, showing superior adhesion and durability. Comprehensive analysis indicated that selecting the appropriate modification method was key for different wood types and application environments.