2,5-Dimethylfuran (2,5-DMF), a renewable biofuel with promising properties, highlights the importance of biomass conversion as a key strategy for sustainable energy production. In this study, we report a facile synthesis of 2,5-DMF from 5-chloromethylfurfural (CMF) using polymer-supported nano-composite material (Pd@PS) as a catalyst at 35°C in 3 h under a H2 atmosphere. The developed methodology provides an excellent tentative carbon conversion efficiency percentage (90%), high atom economy (64%), and low environmental factor (E-factor) (1.15, normalized value 50%), indicating sustainability and a green chemistry matrix. These studies also aligned with the UN Sustainable Development Goals 7 and 12, contributing to the global transition toward cleaner and more sustainable chemical manufacturing by valorizing biomass-based feedstocks. Additionally, the CMF has been synthesized from raw biomass sources, like banana peel waste, sugarcane bagasse, rice straw, and corn cobs, with yields ranging from 8 to 15 wt% and carbon conversion efficiency (tentative) between 25% and 54%. Furthermore, the developed protocol offered an efficient and scalable process (up to 5.0 g) for the production of biofuel, with superior catalytic activity and high recyclability up to six cycles. Moreover, total turnover and turnover frequency numbers were found to be 59.89 and 59.89 h-1, respectively.
Hydrogen-bonded organic frameworks (HOFs), self-assembled from organic building blocks via hydrogen bonding and other weak interactions such as π-π interactions, represent a distinct class of crystalline porous materials. Through rational framework design and functionalization, exceptional intrinsic luminescent and photoelectric properties can be integrated into these structures. Coupled with their unique advantages of solution processability, facile recyclability, and biocompatibility, HOFs emerge as an ideal platform for developing next-generation high-performance sensors. This review systematically summarizes recent advancements in HOF-based materials for luminescent and photoelectric sensing. We elucidate the underlying signal transduction mechanisms, highlighting how specific intermolecular interactions induce detectable changes in optical or electrical signals. The discussion of applications ranges from the detection of hazardous gases, organic pollutants, and chemical warfare agents to the monitoring of antibiotics and biomarkers, as well as temperature sensing and chiral recognition. Finally, we critically assess the current landscape, identifying key challenges to guide the development of HOF-based luminescent and photoelectric sensors.
One-pot synthesis of asymmetric alkyl methyl carbonates from CO2, methanol (MeOH), and various alcohols was demonstrated using CeO2 and 2-cyanopyridine as a heterogeneous catalyst and dehydrating agent, respectively. The molar ratio of MeOH to the other alcohol and structure of the latter alcohol governed the distribution of three organic carbonates, that is, asymmetric alkyl methyl carbonate, dimethyl carbonate (DMC), and dialkyl carbonate. For primary alcohols such as ethanol, 1-propanol, and 1-butanol, an equimolar ratio of MeOH to the other alcohol afforded the highest distribution of the asymmetric alkyl methyl carbonate. In contrast, the low reactivity of 2-propanol due to steric hindrance from its bulky alkyl moiety enabled the preferential formation of isopropyl methyl carbonate (iPMC) with >80% distribution among the three carbonates of iPMC, DMC, and diisopropyl carbonate. The time-course study indicated the involvement of two reaction routes for synthesizing asymmetric organic carbonates: (i) direct cross-carboxylation of MeOH, the other alcohol, and CO2 and (ii) transesterification between DMC, which is formed via homo-carboxylation of MeOH and CO2, and the other alcohol. In the case of iPMC synthesis, the indirect route (ii) became dominant because of the low reactivity of 2-propanol.
Owing to its high energy density, environmental friendliness, and low cost, the high-voltage Ni-Mn-based oxides material has emerged as a highly promising cathode candidate. Nevertheless, such kind of material faces significant limitations including hydrofluoric acid (HF) corrosion, transition metal dissolution, and the Jahn-Teller effect, which substantially hinder its large-scale commercialization. This review comprehensively introduces the fundamental characteristics and limitations of LiNi0.5Mn1.5O4 (LNMO) and LiNixCoyMnzO2 (NCM), followed by state-of-the-art mitigation approaches of CEI regulation encompassing electrolyte additives, synergistic additive combinations, doping modifications, surface coating engineering, and particle design optimization. Future research could explore the synergistic combination of these modification approaches, potentially sparking novel research avenues.
The practical deployment of rechargeable aluminum-ion batteries (AIBs) is hindered by the absence of electrolytes that concurrently offer low cost, efficient ion transport, and stable interfacial electrochemistry. While hydrated deep eutectic electrolytes (HEEs) present a promising avenue, their advancement has been limited by high viscosity and poorly controlled interfacial reactions. This work establishing anion engineering, rather than solely focusing on ligand modulation, as a critical yet previously underappreciated design strategy. We systematically elucidate how the identity of the anion governs the coordination architecture within an ethylene glycol (EG)-based HEE. Crucially, the NO3 - anion induces the formation of a homogeneous, inner‑sphere Al3+ solvation complex, which simultaneously reduces the dynamic viscosity, improves interfacial wettability, and elevates the cathodic stability limit. This tailored solvation structure lowers the desolvation energy barrier. As a result, the NO3 -‑HEE enables exceptional aluminum anode reversibility, evidenced by a high exchange current density and stable, dendrite‑free plating/stripping over 400 h. Full cells coupled with a CuHCF cathode deliver a specific capacity of ∼123 mAh·g-1 and demonstrate outstanding capacity retention over 500 cycles. This study provides a foundational anion‑centric design principle for next‑generation, high‑performance eutectic electrolytes.
The reactivity of the orthometalated [(N^C)AuCl2] complex (N^C-pyridyl-benzothiophene) toward a series of terminal alkynes has been investigated. The reactions afford products containing a C-coordinated benzo[4,5]thieno[2,3-a]quinolizin-5-ium aromatic fragment bound to an Au(I) center. The obtained aromatic systems can be isolated in the free state through reaction of the Au(I) complexes with a protonated phosphonium cation. The studied reaction sequence may be considered a novel strategy for expansion of condensed aromatic systems via 1,4-addition of alkynes to an orthometalated N^C ligand bound to an Au(III) center. The mechanism of this transformation in the gold coordination sphere was investigated theoretically by application of the Double Anharmonic Downward Distortion Following methodology, revealing the details of the coordinated ligands transformations and confirming the key role of the solvent in determining the reaction pathway. Isolation and characterization of the Au(I) complex shed light on the mechanism of related catalytic reactions. The results obtained are of a general nature and pave the way for further development of this chemistry with the wider range of N^C and alkyne ligands, enabling the directed synthesis of new condensed aromatic systems.
Room-temperature afterglow materials with emission wavelengths over 650 nm are rarely reported due to the fact that low-energy excitons are extremely susceptible to nonradiative transitions caused by the environment. This work designs green emissions with ultralong phosphorescence lifetimes and strong quantum efficiencies as the internal excitation light sources. Through the Förster-resonance energy transfer (FRET) mechanism, phosphorescence emission is transferred to the fluorescence emission of commercial fluorescent molecules, successfully achieving the maximum delayed emission wavelengths of 646 nm-702 nm for red afterglow. The organic two-component doped room-temperature phosphorescence material using diphenyl sulfoxide as host molecule and rigid benzo[a]carbazole derivative as guest molecule emits strong green phosphorescence with the afterglow time of 20 s and the phosphorescence quantum efficiency of 27%, which is proven to be an excellent internal phosphorescence excitation light. Three-component ultralong red afterglow materials are acquired with common red fluorescence dyes such as Eosin B, Erythritol B sodium salt, Rhodamine B, and Rhodamine 6G as energy receptors. The results indicate that red ultralong afterglow materials with long emission wavelengths and high luminescence efficiencies can be easily constructed based on the FRET mechanism through appropriate molecular design.
Stimuli-responsive solid-state photochromic materials are attractive for information encryption and smart displays, yet purely organic systems often suffer from high water solubility, while fully inorganic counterparts are constrained by cost-effective and scalable fabrication. These limitations highlight the challenge of developing water-stable, water-operable photochromic materials for underwater information writing and wet-environment anti-counterfeiting. Herein, we report a water-stable 1D perovskite-like lead chloride hybrid, (AeBpy)2Pb3Cl10, constructed with a viologen-based organic dication (AeBpy2+: N-(2-aminoethyl)-4,4'-bipyridinium). The structure features a negatively charged 1D inorganic backbone electrostatically balanced by AeBpy2+, a structural motif characteristic of low-dimensional organic-inorganic perovskite-like materials. Upon light irradiation, efficient photoinduced electron transfer enables rapid photochromism, with coloration occurring within 10 s and complete thermal decoloration achieved at 160°C within 10 min, supporting robust photo-writing/erasing cycles. Importantly, the photochromic response remains operable directly in water, enabling aqueous information writing and on-demand thermal erasing. This work provides a viable materials design strategy to address the challenge of water-stable and water-operable photochromic systems, enabling underwater information writing, wet-environment anti-counterfeiting, and rewritable displays.
Internal transesterification is a fundamental chemical process underlying both spontaneous RNA degradation and biologically regulated RNA cleavage by RNases and ribozymes. Although Mg2 + and ribose conformation are known to influence this reaction, the mechanistic role of nucleobases remains poorly understood. Here, by combining density functional theory calculations with kinetic and NMR experiments, we demonstrate that Mg2 + promotes RNA cleavage through synergistic tridentate coordination with the nucleobase, the 2'-hydroxyl group, and the phosphate moiety. This coordination drives the ribose toward the South conformation, enabling activation of the 2'-OH nucleophile and stabilization of the transition state during internal transesterification. Notably, O2 of rU coordinates Mg2 + more strongly than N3 of rA, leading to lower activation barriers and faster cleavage kinetics, thereby rationalizing the preferential alkali-catalyzed RNA cleavage at pyrimidine sites. These findings uncover a previously unrecognized mechanistic role of nucleobases in RNA backbone scission and provide new insights into spontaneous RNA degradation and RNase- and ribozyme-catalyzed RNA cleavage.
Carbon nanothreads (CNThs) are one-dimensional saturated carbon nanomaterials with exceptional mechanical properties. Polycyclic aromatic hydrocarbons (PAHs) are anticipated to form thicker, multi-ring CNThs with improved mechanical performance under high-pressure. Herein, we systematically investigated the high-pressure polymerization of naphthalene, the simplest PAH, using multiple cutting-edge methods. Naphthalene molecules adopt a herringbone stacking along the a-b direction, and underwent reactions along this stacking direction above 20 GPa, affording one-dimensional unsaturated CNThs with the [4+2] cycloaddition reaction as the dominant reaction path. In contrast to the formation of many reported CNThs, the nucleation of the naphthalene-derived CNThs occurs during compression while their growth proceeds during decompression; this behavior is likely common among aromatics with a herringbone structure. The unit cell of the as-obtained CNTh crystal was determined, and a possible structure of the CNTh product was proposed. Our research reveals the polymerization characteristics of naphthalene under high-pressure, highlighting that the slip-angle and herringbone-angle play an important role in governing the polymerization pathway.
Gas-sensing technology is indispensable in fields such as environmental monitoring, industrial safety, food quality control, and medical diagnostics. Template-assisted synthesis can be employed to construct hierarchical structures in gas-sensing materials, enabling precise multiscale control over morphology, porosity, and intrinsic electronic properties, thereby paving the way for developing next-generation gas sensors with enhanced sensitivity and selectivity. Continuous innovations in the synthesis of hierarchical materials like metal oxide semiconductors (MOS) and metal-organic frameworks (MOFs) have significantly enhanced gas sensing performance in stability, response speed, sensitivity, and selectivity. However, a systematic analysis linking hierarchical structures built via different templating methods to sensing performance remains lacking. This review systematically summarizes the design principles, control mechanisms, and functional applications of three primary templating approaches. Furthermore, this work examines how tailored templating strategies can balance structural precision, synthetic complexity, and environmental impact. Finally, we offer forward-looking perspectives on future development pathways, as well as the challenges and opportunities for practical applications.
In this study, we conduct a comprehensive analysis of the energy storage and release of water-soluble 2,5-norbornadiene-2,3-dicarboxylic acid (DC-NBD) integrating spectroscopic characterization, pH-dependent speciation, and photochemical response analysis. We evaluate protonation and dimerization equilibria using potentiometric and 1H-NMR techniques, revealing three well-defined pH intervals that affect the reactivity and stability of the system. The photoinduced conversion of DC-NBD to DC-QC was investigated at different pH conditions, while the catalytic back-conversion of the most stable quadricyclane species (DC-QC2-) was evaluated on Au(111) and Pt(111) single-crystal surfaces by time-resolved photochemical infrared reflection absorption spectroscopy (PC-IRRAS) and density functional theory. Our findings demonstrate that photoisomerization and catalytic back-conversion can be efficiently conducted in an aqueous environment, eliminating the need for organic solvents. This study advances the development of water-soluble MOST systems, offering key insights into the molecular design and optimization of sustainable photoactive materials. Future research should focus on enhancing photochemical efficiency, improving long-term stability, searching for more active catalysts and scaling these systems for practical solar energy storage applications.
Exploiting atomic-precision metal nanoclusters as an electrochemical sensor for environmental detection is a significant application in the field of cluster chemistry. However, the development of cluster-based sensors is still in its infancy. Herein, we successfully fabricate a three-layer KBE-CS/Au25@MLG/GC electrode (KBE = kidney bean enzyme, CS = chitosan, MLG = multilayer graphene, GC = glassy carbon), in which Au25@MLG and CS serve to adsorb and protect the plant esterase of KBE, respectively. The optimized Au25-based sensor demonstrates an excellent linear relationship between the mass concentration of profenofos (lgC) and the inhibition rate (Inh %) within the range of 1∼2000 µg/L with a detection limit of 0.137 µg/L. Furthermore, this biosensor presents excellent reproducibility, anti-interference, and stability for the detection of profenofos in real samples. This study paves an avenue to construct a cluster-based detection platform with high performance in electrochemical sensing, facilitating the practical application of metal nanoclusters in pesticide detection.
Living microbial therapeutics have arisen as a novel category of medications that extend beyond traditional small molecules and biologics. Advancements in synthetic biology have facilitated the rational engineering of microorganisms to detect host or disease-related signals and administer therapeutic chemicals in situ. In contrast to conventional pharmaceuticals, these live biotherapeutic agents engage in dynamic interactions with both the host and its microbiota, allowing context-specific, self-regulating therapies. This review emphasizes the progression of the field from conventional probiotics to advanced, designed living therapeutics. We examine principal microbiological platforms, including bacteria, yeasts, and alternative systems such as phages and archaea, delineating their relative benefits and constraints as therapeutic hosts. Key design principles, genetic logic circuits, quorum-sensing-based regulation, and synthetic memory devices that enable microorganisms to possess context-dependent and self-adjusting therapeutic capabilities, are discussed alongside present and emerging therapeutic applications in infectious diseases, metabolic disorders, inflammatory illnesses, and cancer immunotherapy, where engineered microorganisms have demonstrated significant preclinical effectiveness and first clinical promise. Despite these advancements, obstacles remain, including biosafety, biocontainment, regulatory approval, and patient acceptability. Engineered living microbial therapeutics signify a swiftly evolving domain in medicine, set to transform treatment paradigms via intelligent, flexible, and sustainable methodologies for human health.
The pursuit of high-performance cathode materials is essential for advancing aqueous zinc-ion hybrid capacitors (ZIHCs). However, conventional porous carbons often suffer from limited capacity and unsatisfactory rate capability due to insufficient active sites, mismatched pores, and low nitrogen-doping levels. Herein, we propose a novel strategy for synthesizing nitrogen-doped porous carbon (NPC) with a hierarchical pore structure using graphitic carbon nitride (g-C3N4) as a dual-function soft template and nitrogen source and potassium citrate as a combined carbon precursor and activating agent. The optimal material, NPC-0.5 (with a g-C3N4/potassium citrate mass ratio of 1:3), exhibits a high specific surface area (805 m2 g-1), a well-defined hierarchical pore network, and a nitrogen content of 7.94 at% dominated by graphitic-N species, which collectively enhance Zn2+ storage and facilitate rapid ion transport. When employed as a cathode for ZIHCs, the NPC-0.5 delivers a high specific capacity of 172 mAh g-1 at 0.1 A g-1, excellent rate capability (41% capacity retention at 20 A g-1), and outstanding long-term cycling stability (86% capacity retention after 65,000 cycles at 10 A g-1). This work provides an efficient and scalable approach for fabricating high-performance nitrogen-doped carbon cathodes for advanced ZIHCs.
Statine [(3S,4S)-4-amino-3-hydroxy-6-methylheptanoic acid (Sta)] is a γ-amino acid produced by several microorganisms, including actinomycetes and cyanobacteria. Sta-containing natural products are known to inhibit cathepsin D, a promising therapeutic target for cancer and neurodegenerative diseases. In this study, three new Sta-containing natural products, abastatins A-C, were isolated from a marine Okeania sp. cyanobacterium collected in Japan. Their structures were unambiguously elucidated by spectroscopic analyses combined with derivatization and degradation reactions. To date, Sta-containing natural products have been discovered mainly from marine cyanobacteria; among them, abastatins A-C exhibit the most potent cathepsin D inhibitory activities reported thus far with IC50 values in the picomolar range. In addition, we propose plausible docking poses for abastatins A-C bound to cathepsin D and describe a new structure-activity relationship that can enhance inhibitory potency against this enzyme.
We explore two approaches for preparing supported catalysts based on volcanic ash (VA) as support for effective Fenton heterogeneous catalysis. Firstly, the plasma deposition of FeOOH (goethite) on VA activated chemically by HCl (AM-FeOOH-30/0C) was performed. Secondly, the plasma-activation of VA and -deposition of FeOOH (VA-FeOOH-30/0) were carried out simultaneously, taking advantage of the gliding-arc-plasma acidic and oxidizing properties. Prepared materials were characterized by X-ray diffraction (XRD), Fourier-transform infrared spectroscopy (FT-IR), thermogravimetric analysis (TGA), N2 physisorption, and scanning electron microscopy coupled energy-dispersive X-ray spectroscopy (SEM/EDX). Performing chemical activation of VA using HCl induces a better microstructure's modification (specific surface area and porosity) and allows a better plasma-deposition of FeOOH (AM-FeOOH-30/0C) compared to performing both processes simultaneously by plasma (VA-FeOOH-30/0) which did not change its microstructure but slightly improved the texture. Otherwise, aging (plasma post-discharge treatment) of AM-FeOOH-30/0C material induces crystallite's nucleation, thus an increase of the specific surface area (AM-FeOOH-30/4C). Fenton catalytic degradation of Rhodamine-6G (25 mg/L) for 20 min revealed elimination degrees of 22%, 87%, 78%, and 82%, respectively, for VA-FeOOH-30/0, AM-2C, AM-FeOOH-30/0C, and AM-FeOOH-30/4C materials. The recyclability tests confirmed the higher catalytic stability of AM-FeOOH-30/0C compared to VA-FeOOH-30/0 material after 4 cycles, thus highlighting the necessity to perform the activation and deposition separately.
Lithium iron phosphate (LiFePO4) batteries are widely used in electric vehicles and energy storage systems due to high safety, long cycle life, and low cost. However, severe low-temperature performance fade limits their deployment in cold climates. To address this challenge, this study focuses on electrolyte design and interface engineering, proposing a novel low-temperature composite electrolyte system. This system simultaneously optimizes the low-temperature ion transport properties and interface stability of the electrolyte through the combination of fluorinated solvents and low-viscosity carbonate solvents with high ionic conductivity, along with rationally selected functional additives. Raman spectroscopy analysis revealed that the modified electrolyte can effectively modulate the electrolyte solvation structure and facilitate the formation of an anion-dominated solvation configuration. This structure not only lowers the energy barrier for lithium ion desolvation but also promotes the formation of a uniform, LiF-rich, and stable composite interface layer on LiFePO4. As a result of these synergistic effects, the Li||LiFePO4 battery with this electrolyte exhibits excellent low-temperature performance at -20°C, delivering a discharge specific capacity of about 120 mAh/g. This study offers a potential material design strategy for addressing the low-temperature performance bottleneck of LiFePO4 batteries through electrolyte structure design and interface chemical regulation.
In the course of studying control reactions for photocatalytic hydrophosphination, several key discoveries have been made, most notably that ambient photoexcitation cannot be ignored in future synthetic work. In this study, catalyst-free photolytic hydrophosphination is demonstrated for vinyl arenes. These reactions are less efficient than many catalyzed examples, indicating that (photo)catalysis is still highly enabling and necessary for challenging substrates. Nevertheless, these reactions appear to be closed-shell, affirming that even ambient light can impact a reaction-a potentially broad influence on even mundane reactions. Counterintuitively, polar protic solvents facilitate these reactions under thermal and photolytic conditions. An effort to extend that discovery to more classically facile substrates has revealed Click-like efficiency in polar protic (alcohol) solvents for activated alkenes, regardless of irradiation. The photochemistry and catalysis help reconcile some divergent observations in the literature. Overall, these results avail new considerations for reactions in which nucleophilic reactivity is enhanced in protic solvent, which is possible due to the absence of a discrete anion. Alcohol solvents may provide greater reactivity than aprotic polar solvents, contrary to conventional wisdom, and even ambient light may be accelerating reactions through unanticipated substrate activation.
Aqueous zinc-iodine batteries (AZIBs) are promising for grid-scale energy storage yet face challenges of polyiodide shuttling and sluggish kinetics in the iodine cathode. Nitrogen-doped porous carbons are widely used as host materials to mitigate these issues. However, the potential roles of different nitrogen configurations and their synergy with trace oxygen doping in the iodine conversion process remain unclear. Herein, a hierarchical N/O codoped porous carbon (ONC) is synthesized through a simple citrate-assisted pyrolysis method and utilized as an advanced host. The codoping strategy modulates the electronic structure of the carbon surface, significantly enhancing the chemical adsorption and catalytic conversion of iodine species, while the multi-scale pores provide effective confinement. This synergy, combined with abundant surface defects, reduces the charge transfer barrier and facilitates ion transport, resulting in rapid surface conversion kinetics. Consequently, the ONC/I2 cathodes deliver a high capacity of 205.8 mAh g-1 at 0.1 A g-1 and excellent stability, retaining 59% of their initial capacity over 10,000 cycles at 1 A g-1. This work provides deep insights into the synergistic mechanisms of heteroatom codoping in carbon hosts, guiding the rational design of high-performance iodine cathodes through the integration of pore engineering and interfacial chemistry.