Comprehensive Summary

Hydrogen bonding is a vital driving force for organizing the hierarchy of molecular structure, especially in biologic field. Due to its directionality, selectivity and moderate strength, hydrogen bonding has been extensively introduced into the molecular recognition, sensing and electronic devices. Electric measurements at single-molecule level facilitate the investigation of hydrogen bonds and provide a comprehensive understanding of the electron transport properties governed by the hydrogen bonding, which is essential for the development of self-assembled electronic systems. This review provides a detailed overview of recent advancements in constructing single-molecule junctions utilizing intramolecular and intermolecular hydrogen bonding. We first introduce the methods utilized for characterizing the electric and dynamic properties of non-covalent interactions. Next, we discuss the mechanisms of electron transport, relevant influencing factors, and typical applications utilizing electrical signals based on single-molecule junctions. Finally, we propose our perspective on the existing challenges and prospective opportunities in utilizing hydrogen bonding for electronic device applications.

Comprehensive Summary

Perovskite solar cells (PSCs) have achieved significant progress in the past decade and a certified power conversion efficiency (PCE) of 26.0% has been achieved. The widely used organic hole transport materials (HTMs) in PSCs are typically sensitive to the moisture environment and continuous light exposure. In contrast, the inorganic HTMs benefiting from their outstanding merits, such as excellent environmental stability, are considered as alternatives and have attracted much attention in PSCs. In this review, we provide a comprehensive summary of the fundamental properties and recent progress of inorganic HTMs in n-i-p and p-i-n structured PSCs. Additionally, we emphasize the importance of inorganic HTMs in the development of highly efficient and stable PSCs.

Dual functional diblock copolymer PLL₂₀-b-PBLG₂₀ was prepared by superfast and water-insensitive polymerization initiated by tetraalkylammonium carboxylate. In addition to direct antimicrobial activity, PLL₂₀-b-PBLG₂₀ also exerts a synergistic bactericidal effect against MRSA with curcumin, a plant extract with antibacterial property. Moreover, PLL₂₀-b-PBLG₂₀ successfully encapsulates curcumin to form nanoparticles via self-assembly. The combination of dual functional PLL₂₀-b-PBLG₂₀ and curcumin holds promise in combating MRSA infections.

Comprehensive Summary

The intensive use of antibiotics intensifies the development of bacterial resistance, which has become a serious problem globally. Methicillin-resistant Staphylococcus aureus (MRSA) has resulted in significant morbidity and mortality. Therefore, it is an urgent need to develop new antimicrobial drugs and administration methods. Herein, we report a dual functional diblock copolymer PLL₂₀-b-PBLG₂₀, which was prepared by superfast and water-insensitive polymerization on N-carboxyanhydrides (NCA) initiated by tetraalkylammonium carboxylate. In addition to direct antimicrobial activity, PLL₂₀-b-PBLG₂₀ also exerts a synergistic bactericidal effect against MRSA with curcumin, a plant extract with antibacterial property. Moreover, PLL₂₀-b-PBLG₂₀ successfully encapsulates curcumin to form nanoparticles via self-assembly. The combination of dual functional PLL₂₀-b-PBLG₂₀ and curcumin holds promise in combating MRSA infections.

Comprehensive Summary

Fused polycyclic N-heterocycles are very important scaffolds in biomedicinal chemistry and materials science. Intramolecular alkyne hydroamination is a powerful method for the construction of N-heterocycles. In the last two decades, copper-catalyzed domino reactions based on intramolecular alkyne hydroamination has emerged as a robust strategy for assembling various fused polycyclic N-heterocycles. Great progress has been achieved in this area. This short review covers the advances made in copper-catalyzed domino synthesis of fused polycyclic N-heterocycles based on this strategy from 2008 to 2023, and will hopefully serve as an inspiration towards the exploration of new copper-catalyzed versions of the transformation. The domino transformations are introduced and discussed from five aspects according to the different key processes involved in these reactions.

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Comprehensive Summary

Metallacyclopentadienes are important metallacycles and regarded as intermediates in many reactions, therefore, new methods to achieve them are anticipated. In this study, a formal [3+2] method, through the reactions of an osmapentalyne with benzyl carbanions, was developed. The reactions underwent a nucleophilic attack of carbanions to the Os≡C bond, followed by C–H activation to form the five-membered osmacyclopentadiene ring. Most of the reactions were carried out at room temperature, the substituents on the aromatic rings of benzyl carbanions are diverse, and the resulting products contain an Os–H bond, representing a novel type of 10C-carbolong complexes. This work provides a new convenient route to construct metallacyclopentadienes, which is expected to further promote the development of such a type of substances.

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In this study, we successfully synthesized a highly soluble, self-doping perylene imide-based ionene polymer (PNPDIN). By using it as a CIL material in inverted Perovskite Solar Cells (PerSCs), the power conversion efficiency (PCE) remarkably increased from 10.05% (without a CIL) to 16.97% (with PNPDIN). Moreover, a synergistic effect was achieved by combining PNPDIN with Bphen as a mixed CIL, leading to an outstanding PCE of 21.28% due to the favorable morphology and energy level alignment. Furthermore, the device's performance displayed excellent tolerance towards varying thicknesses of the mixed CIL, which was attributed to PNPDIN's high conductivity. Even at a film thickness of up to 37 nm, the optimized PCE remained at a high level of 20.46%. This superior mixed CIL materials may open promising avenues for efficient roll-to-roll processing of inverted PerSCs.

Comprehensive Summary

Inverted perovskite solar cells (PerSCs) are a highly promising candidate in the photovoltaic field due to their low-temperature fabrication process, negligible hysteresis, and easy integration with Si-based solar cells. A cathode interlayer (CIL) is necessary in the development of inverted devices to reduce the trap density and energy barrier between the electron transport layer (ETL) and the electrode. However, most CILs are highly thickness-sensitive due to low conductivity and poor film-forming. In this study, we report on a self-doping perylene imide-based ionene polymer (PNPDIN) used as CIL material to modify electrode in inverted PerSCs. PNPDIN exhibits high conductivity and a good solubility in polar solvent, which results in an improved power conversion efficiency (PCE) from 10.05% (device without a CIL) to 16.97%. When the blend of PNPDIN and Bphen was used as a mixed CIL, the PCE of PerSCs can be further increased to 21.28% owing to the excellent morphology and matched energy level. More importantly, the PCE of the device is highly tolerant to the thickness of the mixed CIL, which benefited from the high conductivity of PNPDIN. This development is expected to provide an excellent mixed CIL material for roll-to-roll processing efficient and stable inverted PerSCs.

An in situ injectable Tetra-PEG hydrogel bioadhesive based on tetra-armed poly(ethylene glycol) amine (Tetra-PEG-NH₂) and tetra-armed poly(ethylene glycol) succinimidyl succinate (Tetra-PEG-SS) with rapid gelation speed, excellent biocompatibility, and suitable degradability is developed for the sutureless repair of gastrointestinal perforations. The Tetra-PEG hydrogel can provide fluid-tight sealing and effective repair of gastrointestinal defects with neglectable postoperative adhesion, suppressed long-term inflammation, and enhanced angiogenesis.

Comprehensive Summary

Hydrogel bioadhesives represent promising and efficient alternatives to sutures or staples for gastrointestinal (GI) perforation management. However, several concerns remain for the existing bioadhesives including slow and/or weak adhesive, poor mechanical strength, low biocompatibility, and poor biodegradability, which largely limit their clinical application in GI perforation repair. In this work, we introduce an in situ injectable Tetra-PEG hydrogel bioadhesive (SS) composed of tetra-armed poly(ethylene glycol) amine (Tetra-PEG-NH₂) and tetra-armed poly(ethylene glycol) succinimidyl succinate (Tetra-PEG-SS) for the sutureless repair of GI defects. The SS hydrogel exhibits rapid gelation behavior and high burst pressure and is capable of providing instant robust adhesion and fluid-tight sealing in the ex vivo porcine intestinal and gastric models. Importantly, the succinyl ester linkers in the SS hydrogel endow the bioadhesive with suitable in vivo degradability to match the new GI tissue formation. The in vivo evaluation in the rat GI injured model further demonstrates the successful sutureless sealing and repair of the intestine and stomach by the SS hydrogel with the advantages of neglectable postsurgical adhesion, suppressed inflammation, and enhanced angiogenesis. Together, our results support potential clinical applications of the SS bioadhesive for the high-efficient repair of GI perforation.

C/N leads to the weakened adsorption ability of the oxygen-containing intermediates, facilitating the reduction of energy barrier, thus, NiFeCoCN MEA has excellent OER activity in pH-universal electrocatalyst.

Comprehensive Summary

The kinetic process of a slow oxygen evolution reaction (OER) always constrains the efficiency of overall water electrolysis for H₂ production. In particular, nonprecious metal electrodes for the OER have difficulty in possessing excellent electrocatalytic activity and stability in pH-universal media simultaneously. In this work, urea is first used as a pore-forming agent and active C/N source to fabricate a nanoporous NiFeCoCN medium-entropy alloy (MEA) by high-temperature sintering based on the nanoscale Kirkendall effect. The NiFeCoCN MEA achieves an overpotential of 432 mV at a current density of 10 mA·cm^–2 and a lower Tafel slope of 52.4 mV·dec^–1 compared to the IrO₂/Ti electrode (58.6 mV·dec^–1) in a 0.5 mol/L H₂SO₄ solution. In a 1 mol/L KOH solution, the NiFeCoCN MEA obtains an overpotential of 175 mV for 10 mA·cm^–2 and a Tafel slope of 40.8 mV·dec^–1, which is better than IrO₂/Ni foam. This work proves a novel strategy to design and prepare nanoporous MEA materials with desirable C/N species, which provides promising prospects for the industrial production of H₂ energy.

Comprehensive Summary

Fuel-driven dissipative self-assembly, which is a well-established concept in recent years, refers to out-of-equilibrium molecular self-assembly initiated and supported by the addition of active molecules (chemical fuel). It widely exists in nature since many temporary, active micro- or nanostructures in living bodies are generated by the dissipative self-assembly of biomolecules. Therefore, the study on dissipative self-assembly provides a good opportunity to have an insight into the microscopic mechanism of living organisms. In the meantime, dissipative assembly is thought to be a potential pathway to achieve dynamic, temporary supramolecular materials. Recently, a number of temporary materials have been developed with the aid of strategies for realizing dissipative self-assembly. Some of their properties, including solubility, stiffness, turbidity, color, or self-healing ability, change upon the addition of chemical fuel but spontaneously restore with chemical fuel consumption. The dynamic of these materials brings them various unprecedented functions. In this review, the principles of fabricating a fuel-driven temporary material are first reviewed. Subsequently, recent examples of fuel-driven temporary materials are emphatically summarized, including gels, self-erased inks, nanoreactors, self-healing materials, nanochannels, and droplets. Finally, the challenges of developing fuel-driven temporary materials and some perspectives on the function and application of such kind of materials are discussed.

Comprehensive Summary

Carbonyl compounds have attracted considerable attention due to their extensive applications in drug discovery. Furthermore, they are important synthetic intermediates for the construction of carbon-carbon and carbon-heteroatom bonds. Transition-metal-catalyzed carbonylation via the insertion of CO is one of the most efficient and straightforward strategies to access carbonyl compounds. However, most of the transition-metal-catalyzed carbonylative reactions require expensive and toxic noble-metal catalysts. Therefore, there is a growing demand for the exploration of nickel-catalyzed carbonylative reactions via the insertion of CO due to the earth abundance and low cost of nickel. Compared with the well-established palladium-catalyzed carbonylative reactions, nickel-catalyzed analogous transformations have been relatively underdeveloped. This is primarily because CO strongly binds to nickel, often resulting in catalyst poisoning. In recent years, some research groups have focused on using CO surrogates or NN₂ pincer nickel catalyst to circumvent the formation of Ni(CO)₄. Nickel-catalyzed carbonylation has been applied in the construction of carbonyl-containing compounds, such as ketones, carboxylic acids, thioesters, acyl chloride and carboxamides.

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