Organic electrosynthesis is a versatile and evergreen tool for constructing chemical compounds. However, the study of highly active electrodes has not received enough attention, which limits the further development of organic electrosynthesis. This work introduces a bottom-up route to prepare chitin-derived composite carbon aerogel electrodes (CCAEs), which can be directly used as electrodes in organic electrosynthesis systems. Various metal nanoparticles, such as Pt, Pd, RuO2, Cu and Ni, are well confined in these free-standing and porous CCAEs (M-CCAEs). The linear sweep voltammetry and in-situ Raman tests under electrochemical conditions show that RuO2-CCAEs possess good electrochemical oxidation ability for chlorine anions and good stabilizing effect on the generated chlorine radicals, which can serve as a mediator for the electrochemical C(sp3)-H activation. The combination of M-CCAEs with mediators achieves a series of electrochemical oxidative C(sp3)-H chlorination, bromination, nitration and etherification. Moreover, M-CCAEs promote the electrochemical hydrogen isotope exchange reaction of some important drug molecule structures, such as Ibuprofen, Diclofenac and Zolpidem.

Abstract N-alkylamines serve as essential structural units in pharmaceuticals, agrochemicals, bioactive molecules, etc. Nevertheless, their conventional syntheses predominantly rely on metal-based catalysts, which frequently encounter challenges including metal leaching, easy poisoning, and poor recyclability. Herein, starting from the biomass resource chitosan, we engineered a series of chitosan carbon microspheres (CCMs) with high surface area and tunable N heteroatoms via sol−gel synthesis followed by facile calcination. Under relatively mild conditions, a metal-free catalytic system that achieved efficient N-alkylation of alcohols and amines using chitosan-derived N-doped carbon materials has been realized. The optimal CCM-800 exhibited activity advantages over many commercial and reported metal-based catalysts, along with high cycling stability (30 cycles) and broad substrate scope (103 compounds). Combined with theoretical calculations, it revealed that these cooperative pyridinic/pyrrolic-N sites enhanced their adsorption and activation capabilities for the key intermediate Ph-CH2OK in the rate-determining step (RDS) through their synergistic electronic structure and spatial configuration, thereby promoting the entire reaction. This work achieves efficient N-alkylation reaction using biomass-derived carbon materials under metal-free catalysis, providing a viable route for the efficient synthesis of N-alkylamines.

Although significant developments are made in non-noble metal catalysts for N-alkylation of nitroarenes with alcohols via borrowing hydrogen strategy, obtaining catalysts with superior activity, reusability and broad substrate scope under mild reaction conditions remains challenging. Single-atom catalysts (SACs) hold unique coordination/electron structures, to be the potential candidates for this reaction. In this study, we firstly and creatively fabricate bio-inspired Zn SACs with asymmetric Zn-N2O2 sites by utilizing the natural skeleton of biomass chitosan (denoted as Zn/CS), and achieve the first instance of heterogeneous Zn SACs in borrowing hydrogen reaction between nitroarenes and alcohols. The results reveal that the asymmetric Zn-N2O2 sites induced by natural skeleton (like ligands) and nanoporous structure of Zn/CS significantly promote the N-alkylation efficiency of nitroarenes with alcohols. Notably, the Zn/CS exhibits the highest turnover frequency (TOF) among the reported heterogeneous catalysts, as well as wide substrate scope (56 examples) and excellent reusability. Furthermore, the catalytic pathway/mechanism is investigated by combing theoretical calculations, which reveals that the asymmetric Zn-N2O2 sites with electron-deficient character can facilitate the formation of Zn-H and Zn-O bonds between Zn/CS and Ph-CH2O-, thus easily generating the transition state Ph-CH2O* and driving the whole reaction.

ABSTRACT Bacterial infections are one of the greatest threats to wound healing, and microbial resistance has increased the demand for new antimicrobial dressings. Artificial nanozymes possess myriad considerable advantages, including low cost and high activity, for targeted biological treatments. Despite significant efforts made in nanozyme engineering, significant challenge remains that their catalytic performance is far from satisfactory in wound treatment. Herein, based on biowaste valorisation, we propose a sustainable and efficient strategy to synthesize an ultrafine‐Mn‐loaded (3.0 ± 1 nm) N,O‐doped porous nanocarbons (Mn‐PNCs) nanozyme via the Mott−Schottky effect. The nanozyme achieves mid‐temperature (45.8°C) and superior photothermal conversion efficiency (77.62%), photothermally enhanced peroxidase‐like activity that contributes to the effective treatment of methicillin‐resistant Staphylococcus aureus‐infected wounds. The photo‐enzyme platform further reduced the inflammatory response, normalized epidermal tissue regeneration, and accelerated wound healing. Notably, the mechanism demonstrated that this Mott−Schottky catalyst can trigger the rapid transfer of electrons to release reactive oxygen species (ROS) species, as a heterojunction system is strongly capable of changing the electron density within the metal. Under photothermal induction, the Mott–Schottky contact can be used to fabricate other polysaccharide‐derived nanozymes in tissue engineering, or on the high‐value application of biomass resources.

Deuterium incorporation in organic compounds has been widely applied in medicinal chemistry and materials science. Specifically, fully deuterated aromatic compounds are frequently applied in organic light-emitting diodes. For this application, there is a growing interest in the development of methods for perdeuteration. Herein, a general and scalable method for constructing perdeuterated (hetero)arenes using carbon materials via hydrogen isotope exchange reaction is described. Defective porous carbon material is generated by pyrolyzing cellulose, which permits perdeuteration of arenes and heteroarenes using inexpensive and easy-handling D2O as the deuterium source. Materials characterization and mechanistic studies reveal that vacancy-defect O-doped porous-carbon is generated after pyrolyze cellulose and D species in pores could be formed under continuous flow. This methodology represents a cost-effective methodology for scalable deuteration and enables efficient labeling in a straightforward manner.

The presence of carbon dioxide in natural gas leads to reductions in the CH 4 calorific value and to corrosion of transportation pipelines, making it necessary for the CO 2 concentration to be reduced below 2 %. In this study, a porous organic polymer (POP) named BDA-TG (Cl⁻) was synthesized via an aqueous method using the dialdehyde 4,4′-biphenyldicarboxaldehyde and triaminoguanidine hydrochloride as reagents. The BDA-TG (Cl⁻) COF–C material was synthesized by carbonization of BDA-TG (Cl⁻) at T = 900 °C for 4 h under an atmosphere of CO 2 . Experimental results demonstrated that the as-prepared carbon material exhibits outstanding CO 2 adsorption and separation performance, with a specific surface area of 783 m 2 g −1 and a CO 2 adsorption capacity of 3.57 mmol g −1 at T = 273 K. The CO 2 /CH 4 adsorption selectivity was calculated based on the IAST model, ranging from 7.03 to 8.88. In the gas breakthrough experiment, the breakthrough time of CO 2 was prolonged by 25 min relative to CH 4 , demonstrating excellent CO 2 adsorption and separation performance.

Biomass valorization is a way to promote the 'waste-to-wealth' concept, which is a pre-requisite condition for a future sustainable lifestyle. The direct utilization of natural polymer for value-added materials should be prioritized. With this object, we demonstrate a facile and economical method to prepare chitin-derived supramolecular nanowires-stabilized single-atom sites Pt catalysts (SS-Pt-CSNs). A comprehensive characterization shows the structure of single-atom Pt coordinated with the organic supramolecular (ligand-type) entity, which is both flexible (like in homogenous catalyst) and robust (like in heterogenous catalyst). Such hybrid characteristics of these SS-Pt-CSNs materials exhibit excellent catalytic performance for chemo-selective hydrogenation of various unsaturated bonds with a selectivity of more than 90:1 and a high turnover number (TON) of 121,350. Mechanistic studies demonstrate that both empty coordination sites of Pt and dynamic B-doping are the key factors for exceptional efficiency and high selectivity.

Amines represent fundamental motifs in various chemical contexts and are widely used in agro-chemicals and pharmaceuticals.The development of earth-abundant metal-based heterogeneous catalysts for the synthesis amines remains an important goal in terms of chemical research and industrial application/manufacture.Herein,we developed an efficient and highly selective nitro-gen-doped nickel catalyst enriched with Lewis acid sites,which has been applied for to the hydro-genative coupling of nitriles and amines with molecular hydrogen for the synthesis of a train of functionalised and structurally diverse secondary and tertiary amines.Furthermore,catalytic hy-drogenation and deuteration of nitriles were achieved under milder conditions,yielding a series of primary amines and deuterated amines with high deuterium incorporation.

This study examines the interaction between phospholipids (PL) and proteins during the reconstitution of milk fat globule membranes (MFGM) and their effects on structure, properties, and fat crystallization behavior. Adding 0-0.45 % PL altered the MFGM composition, reduced interfacial protein concentration (27.49-37.88 × 10-4 g/m2), interfacial tension (11.05-15.23 mN/m), and droplet sizes (1.53-2.16 μm), while increasing viscosity (20.39-25.11 mPa s), thus enhancing emulsion stability. High PL concentrations caused skin-like folding, increasing interfacial protein content (29.23-29.52 × 10-4 g/m2) and droplet aggregation (1.68-1.71 μm). PL acted as a non-homogeneous nucleating agent, increasing microcrystal formation and nucleation sites but reducing initial crystallization temperature. The reduced mechanical strength of the MFGM decreased cream churning time and overrun, while higher viscosity reduced serum loss and increased hardness. These findings provide insights for improving aerated emulsion quality.

The energy crisis is a significant issue that the world is facing in the 21st century. Thermoelectric energy transfer emerges as a promising solution that can convert heat energy into electric energy. However, there remains a big challenge that the efficient utilization of light energy to achieve continuous electricity ultimately. The red emitting carbon dots (RCDs) could self-assemble into the aggregates (ARCDs) via cooperative solvophobic effect combined with hydrogen bonding interaction, which exhibits considerably enhanced absorption with excellent photothermal conversion effect (PCE ti 62%) compared to its dispersed state. Moreover, these aggregates were then loaded onto semiconductors to create solar-driven photothermoelectric generator (LHE), with unprecedented output efficiency (Voutput ti 5000 mV, Ioutput ti 25 mA, and Poutput ti 123 mW), which can easily charge smartphones outdoors. This work offers a supramolecular chemistry perspective for the construction of CDs aggregates and presents an sustainable approach towards achieving continuous photothermoelectric energy transfer.

In response to the problem that traditional supported metal catalysts face challenges in green and efficient synthesis of N-alkylation compounds. In this work, three highly dispersed chitin microspheres loaded with silver catalysts (denoted as Ag/chitin) were constructed using renewable bio-waste resource chitin through different activation methods, and the structural and property differences of these catalysts were investigated. The results revealed that the chitin microspheres with unique nanofibrous structure and abundant functional groups, facilitated the anchoring and uniform dispersion of the Ag nanoparticles (NPs), and regulated the coordination environment and electronic structure of Ag. These synthesized Ag/chitin catalysts were applied to the N-alkylation of alcohols with amines by a borrowing hydrogen strategy. The results indicated that the best Ag/chitin-Ar catalyst could synthesize N-alkylation compounds in a green and efficient way, demonstrating good stability and broad applicability of substrates (59 examples), and the relevant catalytic mechanism was studied by combining density functional theory (DFT). This study provides new theoretical experience for green and efficient synthesis of N-alkylation compounds and contributes to the high-value utilization of biomass resources.

The reduction of aromatic compounds constitutes a fundamental and ongoing area of investigation. The selective reduction of polycyclic aromatic compounds to give either fully or partially reduced products remains a challenge, especially in applications to complex molecules at scale. Herein, we present a selective electrochemical hydrogenation of polycyclic arenes conducted under mild conditions. A noteworthy achievement of this approach is the ability to finely control both the complete and partial reduction of specific aromatic rings within polycyclic arenes by judiciously varying the reaction solvents. Mechanistic investigations elucidate the pivotal role played by in situ proton generation and interface regulation in governing reaction selectivity. The reductive electrochemical conditions show a very high level of functional-group tolerance. Furthermore, this methodology represents an easily scalable reduction (demonstrated by the reduction of 1 kg scale starting material) using electrochemical flow chemistry to give key intermediates for the synthesis of specific drugs.

The incorporation of deuterium to organic molecules have widespread applications in medicinal chemistry and material science1,2. For example, deuterated drugs e.g. Austedo3, Donafenib4 and Sotyktu5 have been approved, recently. Because of all these applications, developing methodologies for the synthesis of deuterated compounds with high deuterium ratios is highly desirable6. However, reductive deuteration of aromatic hydrocarbons, which are ubiquitous skeletal features in inert chemical feedstocks, to saturated cyclic compounds, including heterocyclic skeletons has been rarely achieved. So far, only few methods have been reported for direct reductive deuteration using stoichiometric strong reducing agents or D2. Here, we describe a scalable and general electrocatalytic method for the reductive deuteration and deuterodefluorination of (hetero)arenes using a prepared nitrogen doped electrode and D2O, giving perdeuterated and saturated deuterocarbons. This protocol has been successfully applied to the high incorporation of deuterium in 13 drugs.

The fabrication of reliable, reusable and efficient catalyst is crucial for the conversion of nitroaromatic compounds into more chemically valuable amine-based molecules. In this study, a series of chitin supported platinum (Pt) catalysts with high catalytic activity, stability, and reusability were developed by using chitin derived from seafood waste as raw materials. The catalytic performance differences among these catalysts activated by different methods were investigated by hydrogenation of nitroaromatic compounds. The results showed that the multilayer hierarchical pore structure and abundance of hydroxyl and acetamido groups in chitin provided ample anchoring sites for Pt nanoparticles (NPs), ensuring the high dispersion of Pt NPs. Moreover, the interconnected channels between chitin nanofibrous microspheres facilitated rapid transport of reaction substrates. The best Pt/Chitin catalyst exhibited excellent catalytic activity and broad substrate applicability in hydrogenation of nitroaromatic compounds. Significantly, even after 20 runs, no discernible deactivation of activity was observed, demonstrating exceptional catalytic reusability. The application of seafood waste-based catalysts is conducive to the development of a green/sustainable society.

Under the background of green chemistry, the synthesis of N-heterocycles using efficient, stable and long-life catalysts has still faced great challenges. Herein, we used biomass resource chitosan to fabricate a nanoporous chitosan carbon microsphere (CCM), and successfully designed a stable and efficient Pd nano-catalyst (CCM/Pd). Various physicochemical characterizations provided convincible evidences that the palladium nanoparticles (NPs) were tightly and evenly dispersed on the CCM with a mean diameter of 2.28 nm based on the nanoporous structure and abundant functional N/O groups in CCM. Importantly, the graphitized constructure, the formed defects and larger surface area in CCM were able to promote the immobilization of Pd NPs and the electron transfer between Pd and CCM, thereby significantly improving the catalytic activity. The CCM/Pd catalyst was applied for hydrogenation of quinoline compounds, which showed excellent catalytic activity and durability, as well as good substrate applicability. The application of renewable biomass-based catalysts contributes to the progression of a green/sustainable society.

During the production of plant-based meat analogues (PBMA), a significant loss of flavor characteristic compounds in meat-flavor essences could be observed. Pickering emulsion-based encapsulation is an effective method to improve their stability. Therefore, a soy protein isolate (SPI)/chitosan (CS) complex Pickering emulsion was fabricated to encapsulate roast beef flavor (RBF) and further applied in the processing of PBMA. Our results indicated that the network structure of emulsions was dominated by elasticity, while hydrogen and covalent bonding interactions played important roles in the encapsulation process. The release rate of flavor compounds gradually increased with the increase of pH value, glutamine transaminase, NaCl content, heating temperature or heating time, while encapsulation significantly reduced the loss of characteristic aroma compounds. In addition, the releasing characteristics of aroma compounds and textural properties of PBMA were greatly improved by treating with RBF-loaded emulsions. Consequently, the emulsions were promising to improve the flavor quality of PBMA.

Under the background of green/sustainable chemistry, it is still a challenge to synthesize green, efficient and stable catalysts for important chemical products. Herein, we reported a series of Pd nano-catalysts supported on chitosan nanoporous carbon microspheres (CNCM) derived from renewable resource chitosan, and used them for one-pot reductive amination of amines with aldehydes. Various physicochemical characterizations provided reliable evidences that the Pd nanoparticles (NPs) were uniformly dispersed on these CNCM with mean diameters from about 2.29-9.74 nm. As the carrier, CNCM had a nanoporous structure, which was conducive to the adhesion and dispersion of Pd NPs. Meanwhile, the inherent N/O-containing groups in CNCM and the formed defect interfaces during calcination process could anchor the Pd NPs firmly. These CNCM supported catalysts were utilized in the reaction of one-pot reductive amination, which showed excellent catalytic activity compared to various commercial Pd catalysts, as well good cyclic stability and broad substrate suitability.

BACKGROUND: This study aimed to conduct a bibliometric analysis of the literature on hydrogel therapy for spinal cord injury to visualize the research status, identify hotspots, and explore the development trends in this field. METHODS: Web of science Core Collection database was searched for relevant studies published between January 1991 and December 2023. Data such as journal title, author information, institutional affiliation, country, citation, and keywords were extracted. Bibliometrix, CiteSpace, and VOSviewer were used to perform bibliometric analysis of the retrieved data. RESULTS: A total of 1099 articles pertaining to hydrogel therapy for spinal cord injury were retrieved, revealing an - pward trajectory in both annual publication volume and cumulative publication volume. Biomaterials emerged as the journal with the highest number of publications and the most rapid cumulative publication growth, contributing 84 articles. Among authors, Shoichet MS stood out with the highest number of publications and citations, totaling 66 articles. The University of Toronto led in institutional contributions with 65 publications, while China dominated in country-specific publications, accounting for 374 articles. However, to foster significant academic achievements, it is imperative for diverse authors, institutions, and countries to enhance collaboration. Current research in this field concentrates on scaffold architecture, nerve growth factor, the fibrotic microenvironment, and guidance channels. Simultaneously, upcoming research directions prioritize 3D bioprinting, injectable hydrogel, inflammation, and nanoparticles within the realm of hydrogel therapy for spinal cord injuries. CONCLUSIONS: In summary, this study provided a comprehensive analysis of the current research status and frontiers of hydrogel therapy for spinal cord injury. The findings provide a foundation for future research and clinical translation efforts of hydrogel therapy in this field.

Single-atom catalysts, characterized by transition metal-(N/O)(4) units on nanocarbon (M-(N/O)(4)-C), have emerged as efficient performers in water electrolysis. However, there are few guiding principles for accurately controlling the ligand fields of single atoms to further stimulate the catalyst activities. Herein, using the Ni-(N/O)(4)-C unit as a model, we develop a further modification of the P anion on the outer shells to modulate the morphology of the ligand. The catalyst thus prepared possesses high activity and excellent long-term durability, surpassing commercial Pt/C, RuO2, and currently reported single-atom catalysts. Notably, mechanistic studies demonstrated that the pseudocapacitive feature of multiscale anion-hybrid nanocarbon is considerable at accumulating enough positive charge [Q], contributing to the high oxygen evolution reaction (OER) order (beta) through the rate formula. DFT calculations also indicate that the catalytic activity is decided by the suitable barrier energy of the intermediates due to charge accumulation. This work reveals the activity origin of single atoms on multihybrid nanocarbon, providing a clear experiential formula for designing the electronic configuration of single-atom catalysts to boost electrocatalytic performance.