Abstract Nonaqueous rechargeable magnesium–oxygen (Mg–O2) and magnesium–carbon dioxide (Mg–CO2) batteries are emerging as highly competitive candidates for next-generation energy storage, by virtue of their ultrahigh volumetric energy density, inherent dendrite-free safety, low cost, and unique capability for reversible CO2 utilization. Nevertheless, their practical implementation is still plagued by unresolved key issues, including ambiguous reaction mechanisms, sluggish cathode redox kinetics, severe passivation caused by insulating discharge products, and poor interfacial compatibility among key components. This review focuses on the mechanistic understanding and rational design of nonaqueous Mg–O2/Mg–CO2 batteries, with particular emphasis on the comparative analysis of the two Mg-based metal–gas systems, the regulation of discharge product pathways, and the synergistic roles of catalysts, redox mediators (RMs), and electrolytes. We first elaborate the fundamental reaction pathways and core bottlenecks of Mg–O2 and Mg–CO2 batteries, emphasizing the critical differences in discharge product evolution (MgO, MgCO3, MgC2O4) and kinetic constraints. We then comprehensively overview recent advances in catalyst development (covering structural design, heteroatom doping, composite construction, and interface engineering) and RM strategies (including monofunctional OER mediation, bifunctional ORR/OER synergy, shuttle effect suppression, and discharge product pathway induction). Distinct from existing reviews that focus on single metal–gas systems, this review highlights the importance of product pathway regulation in improving battery reversibility and reaction kinetics, and emphasizes the importance of catalyst–RM–electrolyte co-optimization in overcoming electrode passivation and kinetic limitations. Finally, we outline the remaining critical challenges and forward-looking perspectives for bridging the gap between laboratory research and practical applications of Mg–O2/Mg–CO2 batteries. This review aims to fill the knowledge gap of integrated understanding for Mg-based metal-gas batteries and provide targeted guidance for the rational design of high-performance and practical Mg–O2/Mg–CO2 battery systems.
Abstract 3′-O-amino-deoxyribonucleoside triphosphates (3′-ONH2-dNTPs) are crucial reversible terminators for template-independent DNA synthesis. Owing to the structural complexity of purine bases, here we propose a chemo-enzymatic process for the synthesis of purine-type 3′-ONH2-dNTPs. First, the aminoalkoxyl group was introduced into commercially available dA and dG via a chemical catalytic process, affording yields of 24.9% and 27.3%, respectively. Subsequently, to establish a green and scalable enzymatic cascade for phosphorylation of the substrates, we engineered two key phosphorylation enzymes (Dm-dNK and MrPPK2), improving the rate-limiting monophosphorylation of 3′-ONH2-dG from 26% to 97.8% and achieving 59.9% conversion to the corresponding triphosphate. Lastly, the produced nucleotides exhibit performance equivalent to commercial counterparts in terminal deoxynucleotidyl transferase (TdT)-mediated DNA synthesis, supporting the construction of 120-nt strands with ∼99.7% stepwise accuracy. This work establishes an efficient and generalizable catalytic platform for producing modified dNTPs, advancing the practical application of enzymatic DNA synthesis technologies.
MoVNbTeO x , one of the most promising catalysts for the oxidative dehydrogenation of ethane (ODHE) process, is conventionally synthesized from metal salt solutions, which limits its application due to the high cost of precursors. In this work, we first improved the synthetic pathway of MoVNbTeO x by using metal oxides as cheap precursors and subsequently applied aqueous ammonia to treat the catalyst sample, which resulted in a fractured morphology and reduced particle size. On this basis, we found out that as the alkaline solution varied, catalytic performance correlates closely with the surface acidity of MoVNbTeO x . By modulating acidity via impregnation with a trace amount of K2CO3, ethylene peroxidation can be effectively suppressed by a 15% decrease in the ratio of ethylene peroxidation rate to primary reaction rate. Compared with the conventional MoVNbTeO x synthesized from salt solutions, this work retained the advantages of metal-oxide-synthesized MoVNbTeO x in terms of activity and cost, while substantially improving the ethylene selectivity. By using this low-cost MoVNbTeO x catalyst, ODHE process can be operated at 54% ethane conversion with 87% ethylene selectivity and a space-time yield reaching 1.42 kgC2H4 & centerdot;kgcat -1 & centerdot;h-1, demonstrating a viable synthesis route for the potential application of industrial catalysts.
Plasma-electrocatalytic cascade ammonia synthesis offers a promising route for decentralized nitrogen fixation, yet remains hindered by excessive NO3 - formation and poor energy matching between the two stages. Here, we propose a strategy that breaks this bottleneck by selectively generating NO2 - via spark-discharge plasma and efficiently reducing it over a CuRu0.5 nanoalloy. Systematic optimization of the plasma discharge and electrocatalytic interface enables synergistic energy matching, delivering a record-low specific energy consumption of 273.41 kWh/kg NH3. Mechanistic studies reveal that Ru modulates the electronic structure of Cu, enhancing NO2 - adsorption and deoxygenation while suppressing the hydrogen evolution reaction. This work establishes a generalized paradigm for low-energy, high-selectivity ammonia synthesis from air and water.
This work demonstrates a viable and attractive continuous synthesis route for spherical SBA-15 mesoporous silica particles using the aerosol-assisted evaporation-induced self-assembly (AA-EISA) technique. This approach integrates aerosol processing with a self-assembly mechanism driven by solvent evaporation, offering distinct advantages over conventional sol-gel and hydrothermal methods. The influence of ethanol content, pH, P123 template amount, and reactor temperature (T r) on the formation of SBA-15 spheres was systematically investigated using gas physisorption, thermogravimetric analysis (TGA), small-angle X-ray scattering (SAXS), and electron microscopy. In the absence of ethanol, the desired spherical morphology was not obtained; instead, the products consisted of mixed, fiber-like elongated features and bundled aggregates, highlighting ethanol's pivotal role in directing spherical particle formation. An ethanol/tetraethyl orthosilicate (TEOS) molar ratio of 1 was sufficient to maintain a spherical morphology during continuous runs up to 12 h. For production extending beyond 12 h, a ratio of 3 was required to ensure precursor stability and to balance surface area with pore volume. Adjusting the pH to 3 enabled pore expansion to similar to 20 nm and a pore volume of 1 cm3/g, with a moderate surface area of 194 m2/g. Lower ethanol and acid usage suggest a more sustainable process. A P123/TEOS molar ratio of 0.015 was sufficient to yield well-ordered mesostructures with minimal reactor fouling. Reducing T r from 400 to 200 degrees C decreased energy consumption without sacrificing quality, however, a further reduction to 120 degrees C compromised the morphology. Key parameters affecting continuous AA-EISA production are given, showing potential for a robust, energy-efficient, and environmentally conscious route to produce mesoporous silica particles.
Abstract Succinic acid is an important industrial platform chemical with broad applications, and its sustainable production has become increasingly critical. Converting carbon dioxide (CO2) into succinic acid through integrated electrothermal catalytic routes offers a promising alternative to fossil-based and biological methods while contributing to carbon mitigation. This paper summarizes emerging pathways that utilize key CO2-electrocatalytic products, including gas-phase (C2H4/CO/H2), liquid-phase (acetic acid/acetate), and gas–liquid-phase (alcohols), as intermediates for thermocatalytic upgrading to succinic acid. By establishing a unified CO2 → intermediate → succinic acid reaction framework and evaluating the feasibility, conditions, and bottlenecks of each pathway. Among the proposed pathways, the C4 route via maleic anhydride shows the highest near-term feasibility, while gas–liquid oxidative carbonylation offers strong integration potential. This work provides guidance for the development of sustainable, scalable CO2-based succinic acid production.
Graphene-based membranes can be promising platforms for organic solvent nanofiltration (OSN) due to their unique two-dimensional nanochannels, chemical robustness, and tunable transport pathways. In particular, graphene oxide (GO) and nanoporous graphene architectures offer opportunities to overcome permeability/selectivity trade-off through controlled interlayer spacing, engineered nanopores, and tailored solvent-membrane interactions. This review provides a comprehensive overview of recent advances in multilayer graphene-based OSN membranes, focusing on synthesis strategies, transport mechanisms, and structural engineering approaches that enable high-performance separation. We discuss the synergistic roles of nanopore-mediated through-plane transport and confined interlayer diffusion, highlighting how solvent affinity, swelling behavior, and interfacial slip collectively determine separation performance. Recent progress in pore structure refinement, interlayer regulation, nanosheet orientation control, and aspect-ratio control is summarized to provide key design principles for achieving ultrafast permeance while maintaining sharp molecular separation. Beyond material design, emerging industrial applications, including purification, concentration, solvent exchange, pharmaceutical processing, electronic-grade solvent polishing, and organic solvent reverse osmosis, are broadly discussed. Finally, we checked remaining challenges toward scale-up and commercialization, including stability under harsh solvents, module compatibility, and realistic performance evaluation.
Abstract With the explosive growth of global photovoltaic (PV) installed capacity, a massive wave of PV module decommissioning is imminent. Retired modules contain valuable resources, including high-purity silicon, silver, and aluminum. Improper disposal may not only lead to resource loss but also pose risks of ecotoxicity. The efficient conversion of PV waste into battery materials aligns with environmental protection requirements and represents a critical pathway to secure the strategic supply of high-performance silicon-based anode materials. However, current research predominantly focuses on isolated technological steps and lacks a systematic synthesis of the entire value chain. This paper provides a comprehensive overview of the full-chain technological pathways for the value-added utilization of PV waste in the battery sector. It offers a multidimensional analysis of the resource value, the spatiotemporal evolution of the decommissioning wave, and the associated environmental risks of PV waste. Focusing on the critical bottlenecks in the preprocessing stage for battery-grade conversion, we dissect the key technologies for silicon waste purification. Tracing the regeneration pathways for battery materials, we summarize strategies for structural design and functional modification of waste-derived silicon, and elucidate the mechanisms for mitigating volume expansion in silicon anodes. A realistic assessment of current industrial challenges is provided, alongside an outlook on the prospects for value-added utilization. By delineating the technological roadmap and transformation logic from PV waste to battery material recycling, we aim to contribute to the construction of a closed-loop green industry for “energy generation-storage”.
Controlling the internal architecture and morphology of lipid nanoparticles (LNPs) beyond their size remains a central challenge in nanoparticle engineering. Conventional micromixer-based assembly methods provide rapid mixing but lack the temporal resolution to manipulate the multiple competing kinetic processes that occur during LNP self-assembly. Here, we demonstrate kinetically controlled fabrication of Janus-structured surface nanobubble-lipid nanoparticles (SNB-LNPs) using an ultrasonic micromixer that enables independent tuning of three critical time scales: mixing time (t m), bubble generation time (t b), and LNP self-assembly time (t a). By systematically mapping these time scales, we establish an assembly kinetic zone diagram that defines the process windows for distinct nanoparticle architectures, including spherical LNPs, bleb LNPs, and the previously inaccessible SNB-LNPs. Cryogenic transmission electron microscopy and small-angle neutron scattering confirm the Janus morphology of SNB-LNPs, featuring a gas-filled nanobubble compartment (∼17 vol % gas phase) attached to a lipid-mRNA core. The assembly outcome can be further modulated by gas supersaturation and lipid shell composition, providing additional degrees of freedom for structural control. As a proof of concept, the ultrasound-responsive SNB-LNPs demonstrate enhanced mRNA delivery both in vitro and in vivo. This work establishes a process engineering framework for fabricating multicompartment nanoparticles with nonequilibrium architectures through kinetic control in continuous-flow microreactors.
Graphitic carbon nitride (CN) has emerged as a promising candidate for CO2 capture and conversion due to its structural tenability and abundant surface active sites. However, CN suffers from inherent drawbacks such as poor catalytic activity, leading to unsatisfactory utilization. In this study, a rational strategy combining organic superbases as hydrogen bond acceptors with hydrolyzed high crystallinity CN (poly-(heptazine imide), PHI) derivatives as hydrogen bond donors was developed to form ionic liquid-functionalized PHI catalysts. This design strategically integrates amino and hydrogen bond functionalities within a single polymeric framework, thereby cooperatively accelerating the coupling of epoxides with CO2. Under the conditions of 0.1 MPa CO2, 90 °C, and 6 h, [PHI-NH]-[DBUH] achieved chloropropene carbonate (CPC) in 99% yield with 99% selectivity. Based on the multifunctional structure and experimental results of the catalyst, a plausible pathway emphasizing intramolecular cooperative activation was subsequently elucidated. Furthermore, the heterogeneous nature of the catalyst enabled facile recovery and reuse via simple solid-liquid separation. This work establishes a sustainable catalytic platform that merges ionic liquid functionality with polymeric semiconductor matrices for green chemical transformations.
In pharmaceuticals, aromatic structures are common motifs, underscoring the need for efficient and sustainable functionalization of arene compounds, particularly in late-stage functionalization. This study introduces a biocatalytic cascade employing unspecific peroxygenases (UPOs; PaDa-I mutant) and halohydrin dehalogenases (HHDHs), performed under batch conditions as a proof of concept. Significant advancements were achieved in the design of our microfluidic devices, where we incorporated HPLC screw fittings to minimize leakage and enhance compatibility with conventional flow equipment. To immobilize PaDa-I, we explored three covalent methods: (i) poly dopamine (PDA) surface coating, (ii) PDA with copolymerized polyethylenimine, and (iii) carbodiimide cross-linking. Among these, carbodiimide cross-linking achieved the highest activity yield (27%) under continuous-flow conditions, representing the most efficient immobilization reported to date for PaDa-I. To circumvent UPO instability toward hydrogen peroxide, we substituted it with ascorbic acid (AscA) for the epoxidation of styrene derivatives, improving PaDa-I stability to 6 days, achieving a yield of 37%, and maintaining productivity of 17 μM/h. Using EMIN340 and EMIN510 mutants from the commercial HHDH kit of Enzymaster facilitated the conversion of styrene oxide to N-phenyl-2-oxazolidinone, achieving a 1.3% yield over two steps. Notably, the use of AscA in the epoxidation showed a higher yield of 10.9% in the epoxide opening reaction toward N-phenyl-2-oxazolidinone compared to 4% using hydrogen peroxide. These findings underscore the potential of this biocatalytic cascade for further continuous-flow applications, offering improved enzyme stability and activity, with promising prospects for further optimization and broader implementation.
The complexity of nanomedicine poses a significant challenge to traditional empirical methods. Machine learning (ML), with its ability to parse high-dimensional data and predict nonlinear interactions, is empowering AI nano fusion platforms, driving innovation in diagnostic and therapeutic evaluation paradigms. This review explores breakthrough applications of ML in core areas of nanomedicine, including intelligent diagnosis (such as ML enhanced nanosensors for high-precision noninvasive cancer early screening), precision therapy (such as closed-loop system driven rational design and delivery optimization of nanomedicine), safety assessment (such as interpretable AI prediction of biological and environmental toxicity of nanomaterials), and clinical translation (to address scientific challenges related to standardization, reproducibility, and regulatory). The paper provides an in-depth analysis of the key bottlenecks currently facing the transition from laboratory to clinical application, such as batch differences, dynamic interference, and regulatory lag. Based on recent research progress, a future path to achieve an intelligent closed-loop of "design diagnosis and treatment evaluation" is proposed, providing key insights for the development of the next generation of safe and efficient intelligent nanodiagnosis and treatment platforms.
Bioelectrocatalytic conversion of organic waste uses renewable electricity to convert organic waste into high-value chemicals and fuels under mild conditions. It is regarded as a strategic link connecting waste refinement and the green economy, providing a sustainable approach for the high-value utilization of waste resources. This article systematically reviews: (1) the basic principles and reaction mechanisms of bioelectrocatalytic conversion of organic waste; (2) the development history and key breakthroughs of organic waste biological electrochemical conversion; (3) microbial engineering strategies based on genetic engineering and synthetic biology; (4) the directions for process and reactor optimization. This review uniquely integrates advancements in biological innovation and process engineering, offering a holistic perspective on synergistic optimization across molecular, microbial, and reactor scales. By explicitly bridging microbial carbon/electron flux engineering with bioreactor design and process coupling, it aims to establish a comprehensive roadmap for accelerating the industrial-scale application of bioelectrocatalytic technologies in organic waste treatment.
The commercialization of Li metal anodes in all-solid-state lithium batteries (ASSLBs) is hindered by uncontrollable dendritic growth and nonuniform deposition during cycling. Here, we report a facile metal displacement strategy to construct a Li-Ga alloy anodic interlayer to suppress Li dendrite growth and stabilize the anode-solid-state electrolyte interface. The significantly enhanced performance originates from the dramatically improved Li diffusion kinetics, with the Li-Ga alloy modified Li (Li-Ga@Li) anode exhibiting a Li atomic diffusion coefficient twice as high as that of pristine Li metal. Consequently, the Li-Ga@Li|LPSCl|Li-Ga@Li symmetric cells deliver stable lithium stripping/plating behavior over 800 h with minimal polarization and a significantly increased critical current density. When paired with a high-loading LiNi0.8Co0.1Mn0.1O2 (NCM811) cathode active material, Li-Ga@Li|LPSCl|NCM811 ASSLBs demonstrate enhanced rate capability and prolonged cycling stability. This work provides a practical interfacial engineering strategy through diffusivity improvement toward high-performance ASSLBs.
Biomolecular condensates have emerged as a transformative paradigm in biomedical and materials sciences due to their unique capacity for molecular sequestration and dynamic adaptability. Precise modulation of their microenvironmental properties enables versatile applications including protocell engineering, targeted therapeutics, and smart bioreactor systems. Here, we demonstrate that multivalent ions, exemplified by magnesium ions (Mg2+), exert concentration-dependent regulation of condensate physicochemical properties and biological functions. Using a model system composed of cationic arginine decamer (R10) and anionic polyglutamate (PolyE), we systematically show that Mg2+ concentration gradients influence the size distribution, surface charge, viscosity, and internal polarity. Critically, we establish links between ion-induced microenvironmental changes and functional outcomes: (i) dsDNA structural stability and ssDNA hybridization kinetics are altered in an ion-dependent manner; (ii) guest molecule enrichment capacity shows selective tuning; and (iii) alkaline phosphatase (ALP) catalytic efficiency exhibits nonlinear dose-response relationships. These findings offer mechanistic insights into cellular ion homeostasis and provide design principles for ion-responsive synthetic condensates with programmable functionality. Our work bridges fundamental biophysical principles with translational applications in smart biomaterials and precision medicine.
Carbon dioxide capture is key to achieving carbon neutrality and addressing climate change. Covalent organic frameworks (COFs) with tailored pore structures have emerged as potential candidates for CO2 adsorption. However, previous postsynthetic modification methods often face an inevitable trade-off between increasing adsorption sites and maintaining pore accessibility. Herein, we report an all-dry molecular scale processing (MSP) approach that forms open pockets in COF mesopores by covalently grafting chains with Zn open metal sites and primary amine groups as dual CO2-philic sites. The resulting COF not only maintains a BET surface area up to 1180 m(2) g(-1) but also enables an ideal selectivity for CO2/N-2 of 153 at 100 kPa, which is almost 10-fold higher than the pristine COF. Mechanistic investigations reveal that micropore filling and strong binding sites contribute to enhanced CO2 adsorption. The pore engineering strategy reported here provides essential insights for developing the next generation of adsorbent materials.
Plastic packaging poses a major environmental challenge, yet most paper-based alternatives rely on unsustainable coatings and additives to achieve barrier and mechanical performance. Here, we introduce an all-cellulose bilayer barrier paper in which cellulose nanofibrils (CNFs) function as a dual-purpose coating and reinforcement. Rather than applying CNFs as a postcoating, we employ a simple filtration process combining pulp fibers and CNFs that induces spontaneous bilayer formation, yielding a dense CNF layer atop a pulp-rich substrate. This design delivers outstanding performance: oil resistance exceeds commercial standards even at 85 °C (KIT Level 12), water contact angle increases by >60°, water absorption is significantly reduced (Cobb60 decreases from 290 to 50 g·m-2), and thermal stability can hold up to 270 °C. While air permeability decreases to near zero, the material maintains a moderate oxygen transmission rate at 50% relative humidity (97 cc·m-2·day-1·atm-1). Beyond a 200% improvement in mechanical strength and wet strength suitable for food packaging applications, the bilayer structure remains robust under folding and peeling, outperforming commercial papers for hot food, refrigerated meats, and baking. Importantly, the all-cellulose composition enables over 98% fiber recovery by recycling, substantially reducing the carbon footprint relative to commercial food barrier papers with limited recyclability. By combining nanoengineering, high functionality, and circularity, this work establishes a biobased platform for sustainable food packaging with broad societal and environmental impact.
The reaction catalyzed by l-threonine aldolase (LTA) for the formation of β-hydroxy-α-amino acids is governed by both kinetic and thermodynamic control, causing the diastereoselectivity of LTA to gradually decrease as the reaction progresses. This hinders the enzyme's industrial application. To address this, we proposed a strategy to enhance kinetic control via substrate tunnel engineering, thereby mitigating the influence of thermodynamic equilibrium. We investigated hotspot amino acid residues in the substrate tunnel using the VR-3M mutant from Bacillus nealsonii. As a result, we obtained mutant N6A/Q303K, which exhibited a diastereoselectivity of up to 99.0% at maximum conversion for the synthesis of (2S,3R)-3-[4-(methylsulfonyl)-phenylserine]. The kinetic control in this mutant was significantly enhanced, maintaining a diastereomeric excess (de) value above 95% until 500 mina 340 min delay over the original VR-3M, which drops below 95% after 160 min while reaching only a 40.9% de value at 500 min. Molecular dynamics simulations suggest that increases in active center volume and substrate tunnel reshaping are key factors enhancing the kinetic control of diastereoselectivity. This study offers valuable insights into the interplay between kinetic and thermodynamic control in enzymatic catalysis.
