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Developing surfaces that effectively repel low-surface-tension liquids with tunable adhesive properties remains a pivotal challenge. Micronano hierarchical re-entrant structures emerge as a promising solution, offering a robust structural defense against liquid penetration, minimizing area fraction, and creating narrow gaps that generate substantial upward Laplace pressure. However, the absence of an efficient, scalable, and tunable construction method has impeded their widespread applications. Here, drawing inspiration from springtail epidermal structures, octopus suckers, and rose petals, we present a scalable manufacturing strategy for artificial micronano hierarchical T-shaped structures. This strategy employs double-transfer UV-curing nanoimprint lithography to form nanostructures on microstructured surfaces, offering high structural tunability. This approach enables precise control over topography, feature size, and arrangement of nano- and microscale sections, resulting in superamphiphobic surfaces that exhibit high contact angles (>150°) and tunable adhesive forces for low-surface-energy liquids. These surfaces can be applied to droplet-based microreactors, programmable droplet-transfer systems, and self-cleaning surfaces suitable for various liquids, particularly those with low surface tension. Remarkably, we have also succeeded in fabricating the hierarchical structures on flexible and transparent substrates. We demonstrate the advantages of this strategy in the fabrication of hierarchical micronanostructures, opening up a wide range of potential applications.

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Microstructured reactors offer fast chemical engineering transfer and precise microfluidic control, enabling the determination of reactions' kinetic parameters. This review examines recent advancements in measuring microreaction kinetics. It explores kinetic modeling, reaction mechanisms, and intrinsic kinetic equations pertaining to two types of microreaction: esterification and transesterification reactions involving acids, bases, or biocatalysts. The utilization of a micro packed-bed reactor successfully achieves a harmonious combination of the micro-dispersion state and the reaction kinetic characteristics. Additionally, this review presents micro-process simulation software and explores the advanced integration of microreactors with spectroscopic analyses for reaction monitoring and data acquisition. Furthermore, it elaborates on the control principles of the micro platform. The superiority of online measurement, automation, and the digitalization of the microreaction process for kinetic measurements is highlighted, showcasing the vast prospects of artificial intelligence applications.

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Ferroelectric catalysts are known for altering surface catalytic activities by changing the direction of their electric polarizations. This study demonstrates polarization-switchable electrochemistry using layered bismuth oxyselenide (L-Bi2O2Se) bifunctional microreactors through ferroelectric modulation. A selective-area ionic liquid gating is developed with precise control over the spatial distribution of the dipole orientation of L-Bi2O2Se. On-chip microreactors with upward polarization favor the oxygen evolution reaction, whereas those with downward polarization prefer the hydrogen evolution reaction. The microscopic origin behind polarization-switchable electrochemistry primarily stems from enhanced surface adsorption and reduced energy barriers for reactions, as examined by nanoscale scanning electrochemical cell microscopy. Integrating a pair of L-Bi2O2Se microreactors consisting of upward or downward polarizations demonstrates overall water splitting in a full-cell configuration based on a bifunctional catalyst. The ability to modulate surface polarizations on a single catalyst via ferroelectric polarization switching offers a pathway for designing catalysts for water splitting.

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We construct a compartmentalized nanoarchitecture to regulate bioenergy level. Glucose dehydrogenase, urease and nicotinamide adenine dinucleotide are encapsulated inside through liquid-liquid phase separation. ATPase and glucose transporter embedded in hybrid liposomes are attached at the surface. Glucose is transported and converted to gluconic acid catalyzed by glucose dehydrogenase, resulting in an outward proton gradient to drive ATPase for ATP synthesis. In parallel, urease catalyzes hydrolysis of urea to generate ammonia, which leads to an inward proton gradient to drive ATPase for ATP hydrolysis. These processes lead to a change of the direction of proton gradient, thus achieving artificial ATP oscillation. Importantly, the frequency and the amplitude of the oscillation can be programmed. The work explores nanoarchitectonics integrating multiple components to realize artificial and precise oscillation of bioenergy level.

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Janus particles are popular in recent years due to their anisotropic physical and chemical properties. Even though there are several established synthesis methods for Janus particles, microfluidics-based methods are convenient and reliable due to low reagent consumption, monodispersity of the resultant particles and efficient control over reaction conditions. In this work a simple droplet-based microfluidic technique is utilized to synthesize magnetically anisotropic TiO2-Fe2O3 Janus microparticles. Two droplets containing reagents for Janus particle were merged by using an asymmetric device such that the resulting droplet contained the constituents within its two hemispheres distinct from each other. The synthesized Janus particles were observed under the optical microscope and the scanning electron microscope. Moreover, a detailed in vitro characterization of these particles was completed, and it was shown that these particles have a potential use for biomedical applications.

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The Belousov-Zhabotinsky (BZ) reaction has long been a paradigmatic system for studying chemical oscillations. Here, we experimentally studied the synchronization control within photochemically coupled star networks of BZ oscillators. Experiments were carried out in wells performed in soda-lime glass constructed using novel laser technologies. Utilizing the inherent oscillatory nature of the BZ reaction, we engineered a star network of oscillators interconnected through photochemical inhibitory coupling. Furthermore, the experimental setup presented here could be extrapolated to more complex network architectures with both excitatory and inhibitory couplings, contributing to the fundamental understanding of synchronization in complex systems.

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A highly efficient complex emulsion microreactor has been successfully developed for multiphasic water-labile reactions, providing a powerful platform for atom economy and spatiotemporal control of reaction kinetics. Complex emulsions, composing a hydrocarbon phase (H) and a fluorocarbon phase (F) dispersed in an aqueous phase (W), are fabricated in batch scale with precisely controlled droplet morphologies. A biphasic esterification reaction between 2-bromo-1,2-diphenylethane-1-ol (BPO) and perfluoro-heptanoic acid (PFHA) is chosen as a reversible and water-labile reaction model. The conversion reaches up to 100 % under mild temperature without agitation, even with nearly equivalent amounts of reactants. This efficiency surpasses all reported single emulsion microreactors, i. e., 84~95 %, stabilized by various emulsifiers with different catalysts, which typically necessitate continuous stirring, a high excess of one reactant, and/or extended reaction time. Furthermore, over 3 times regulation threshold in conversion rate is attained by manipulating the droplet morphologies, including size and topology, e. g., transition from completely engulfed F/H/W double to partially engulfed (F+H)/W Janus. Addition-esterification, serving as a model for triple phasic cascade reaction, is also successfully implemented under agitating-free and mild temperature with controlled reaction kinetics, demonstrating the versatility and effectiveness of the complex emulsion microreactor.

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Epilepsy designates a group of chronic brain disorders, characterized by the recurrence of hypersynchronous, repetitive activity, of neuronal clusters. Epileptic seizures are the hallmark of epilepsy. The primary goal of epilepsy treatment is to eliminate seizures with minimal side effects. Nevertheless, approximately 30% of patients do not respond to the available drugs. An imbalance between excitatory/inhibitory neurotransmission, that leads to excitotoxicity, seizures, and cell death, has been proposed as an important mechanism regarding epileptogenesis. Recently, it has been shown that microreactors composed of platinum nanoparticles (Pt-NP) and glutamate dehydrogenase possess in vitro and in vivo activity against excitotoxicity. This study investigates the in vivo effects of these microreactors in an animal model of epilepsy induced by the administration of the GABAergic antagonist bicuculline. Male Wistar rats were administered intracerebroventricularly (i.c.v.) with the microreactors or saline and, five days later, injected with bicuculline or saline. Seizure severity was evaluated in an open field. Thirty min after behavioral measurements, animals were euthanized, and their brains processed for neurodegeneration evaluation and for neurogenesis. Treatment with the microreactors significantly increased the time taken for the onset of seizures and for the first tonic-clonic seizure, when compared to the bicuculline group that did not receive the microreactor. The administration of the microreactors also increased the time spent in total exploration and grooming. Treatment with the microreactors decreased bicuculline-induced neurodegeneration and increased neurogenesis in the dorsal and ventral hippocampus. These observations suggest that treatment with Pt-NP-based microreactors attenuates the behavioral and neurobiological consequences of epileptiform seizure activity.

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A novel class of diazonium salts is introduced for the photochemical aryl-aryl coupling to produce (substituted) biphenyls. As common diazonium tetrafluoroborate salts fail, soluble and safe aryl diazonium trifluoroacetates are applied. In this mild synthesis route no catalysts are required to generate an aryl-radical by irradiation with UV-A light (365 nm). This reactive species undergoes direct C-H arylation at an arene, forming the product in reasonable reaction times. With the implementation of a continuous flow setup in a capillary photoreactor 13 different biphenyl derivatives are successfully synthesized. By integrating an inline 19F-NMR benchtop spectrometer, samples are reliably quantified as the fluorine-substituents act as a probe. Here, real-time NMR spectroscopy is a perfect tool to monitor the continuously operated system, which produces fine chemicals of industrial relevance even in a multigram scale.

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The Intergovernmental Panel on Climate Change (IPCC) recognises the pivotal role of renewable energies in the future energy system and the achievement of the zero-emission target. The implementation of renewables should provide major opportunities and enable a more secure and decentralised energy supply system. Renewable fuels provide long-term solutions for the transport sector, particularly for applications where fuels with high energy density are required. In addition, it helps reducing the carbon footprint of these sectors in the long-term. Information on biomass characteristics feedstock is essential for scaling-up gasification from the laboratory to industrial-scale. This review deals with the transformation biogenic residues into a valuable bioenergy carrier like biomethanol as the liquid sunshine based on the combination of modified mature technologies such as gasification with other innovative solutions such as membranes and microchannel reactors. Tar abatement is a critical process in product gas upgrading since tars compromise downstream processes and equipment, for this, membrane technology for upgrading syngas quality is discussed in this paper. Microchannel reactor technology with the design of state-of-the-art multifunctional catalysts provides a path to develop decentralised biomethanol synthesis from biogenic residues. Finally, the development of a process chain for the production of (i) methanol as an intermediate energy carrier, (ii) electricity and (iii) heat for decentralised applications based on biomass feedstock flexible gasification, gas upgrading and methanol synthesis is analysed.

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A novel experimental approach for the rapid online monitoring of the enantiomeric ratio of chiral analytes in solution is presented. The charged analyte is transferred to the gas phase by electrospray. Diastereomeric complexes are formed with a volatile chiral selector in a buffer-gas-filled ion guide held at room temperature, mass-selected, and subsequently spectrally differentiated by cryogenic ion trap vibrational spectroscopy. Based on the spectra of the pure complexes in a small diastereomer-specific spectral range, the composition of diastereomeric mixtures is characterized using the cosine similarity score, from which the enantiomeric ratio in the solution is determined. The method is demonstrated for acidified alanine solutions and using three different chiral selectors (2-butanol, 1-phenylethanol, 1-amino-2-propanol). Among these, 2-butanol is the best choice as a selector for protonated alanine, also because the formation ratio of the corresponding diastereomeric complexes is found to be independent of the nature of the enantiomer. Subsequently, a microfluidic chip is implemented to mix enantiomerically pure alanine solutions continuously and determine the enantiomeric ratio online with minimal sample consumption within one minute and with competitive accuracy.

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Microfluidic devices have attracted much attention in the current day owing to the unique advantages they provide. However, their application for industrial use is limited due to manufacturing limitations and high cost. Moreover, the scaling-up process of the microreactor has proven to be difficult. Three-dimensional (3D) printing technology is a promising solution for the above obstacles due to its ability to fabricate complex structures quickly and at a relatively low cost. Hence, combining the advantages of the microscale with 3D printing technology could enhance the applicability of microfluidic devices in the industrial sector. In the present work, a 3D-printed single-channel immobilized enzyme microreactor with a volume capacity of 30 µL was designed and created in one step via the fused deposition modeling (FDM) printing technique, using polylactic acid (PLA) as the printing material. The microreactor underwent surface modification with chitosan, and ß-glucosidase from Thermotoga maritima was covalently immobilized. The immobilized biocatalyst retained almost 100% of its initial activity after incubation at different temperatures, while it could be effectively reused for up to 10 successful reaction cycles. Moreover, a multi-channel parallel microreactor incorporating 36 channels was developed, resulting in a significant increase in enzymatic productivity.

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Tumor hypoxia and acidity, two general features of solid tumors, are known to have negative effect on cancer immunotherapy by directly causing dysfunction of effector immune cells and promoting suppressive immune cells inside tumors. Herein, a multifunctional colloidosomal microreactor is constructed by encapsulating catalase within calcium carbonate (CaCO3 ) nanoparticle-assembled colloidosomes (abbreviated as CaP CSs) via the classic double emulsion method. The yielded CCaP CSs exhibit well-retained proton-scavenging and hydrogen peroxide decomposition performances and can thus neutralize tumor acidity, attenuate tumor hypoxia, and suppress lactate production upon intratumoral administration. Consequently, CCaP CSs treatment can activate potent antitumor immunity and thus significantly enhance the therapeutic potency of coloaded anti-programmed death-1 (anti-PD-1) antibodies in both murine subcutaneous CT26 and orthotopic 4T1 tumor xenografts. In addition, such CCaP CSs treatment also markedly reinforces the therapeutic potency of epidermal growth factor receptor expressing chimeric antigen receptor T (EGFR-CAR-T) cells toward a human triple-negative breast cancer xenograft by promoting their tumor infiltration and effector cytokine secretion. Therefore, this study highlights that chemical modulation of tumor acidity and hypoxia can collectively reverse tumor immunosuppression and thus significantly potentiate both immune checkpoint blockade and CAR-T cell immunotherapies toward solid tumors.

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Excessive CO2 and food shortage are two grand challenges of human society. Directly converting CO2 into food materials can simultaneously alleviate both, like what green crops do in nature. Nevertheless, natural photosynthesis has a limited energy efficiency due to low activity and specificity of key enzyme D-ribulose-1,5-bisphosphate carboxylase/oxygenase (RuBisCO). To enhance the efficiency, many prior studies focused on engineering the enzymes, but this study chooses to learn from the nature to design more efficient reactors. This work is original in mimicking the stacked structure of thylakoids in chloroplasts to immobilize RuBisCO in a microreactor using the layer-by-layer strategy, obtaining the continuous conversion of CO2 into glucose precursor at 1.9 nmol min-1 with enhanced activity (1.5 times), stability (≈8 times), and reusability (96% after 10 reuses) relative to the free RuBisCO. The microreactors are further scaled out from one to six in parallel and achieve the production at 15.8 nmol min-1 with an energy conversion efficiency of 3.3 times of rice, showing better performance of this artificial synthesis than NPS in terms of energy conversion efficiency. The exploration of the potential of mass production would benefit both food supply and carbon neutralization.

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In this article, a new system employing an ultrasonic microreactor coupled with a tubular reactor is presented for the continuous generation of polymer nanoparticles. The continuous generation of cross-linked polymer nanoparticles utilizing the monomer butyl methacrylate and the cross-linker ethylene glycol dimethacrylate is demonstrated. Firstly, the miniemulsion polymerization of a monomer-in-water miniemulsion is studied in a batch system. Secondly, a coiled tubular reactor is employed for the continuous polymerization of the miniemulsion generated by an ultrasonic microreactor. Finally, the influence of monomer volume fraction and surfactant concentration on the synthesized polymer nanoparticles is studied. Polymer particles in a size range of 50-250 nm are synthesized and a high polymerization conversion is achieved utilizing the system demonstrated in this article.

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Lipid and polymer vesicles provide versatile means of creating systems that mimic the architecture of cells. However, these constructs cannot mimic the adaptive compartmentalization observed in cells, where the assembly and disassembly of subcompartments are dynamically modulated by environmental cues. Here, we describe a fully polymeric microreactor with a coacervate-in-vesicle architecture that exhibits an adaptive response to pH. The system was fabricated by microfluidic generation of semipermeable biomimetic polymer vesicles within 1 min using oleyl alcohol as the oil phase. The polymersomes allowed for the diffusion of protons and substrates acting as external signals. Using this method, we were able to construct adaptive microreactors containing internal polyelectrolyte-based catalytic organelles capable of sequestering and localizing enzymes and reaction products in a dynamic process driven by an external stimulus. This approach provides a platform for the rapid and efficient construction of robust adaptive microreactors that can be used in catalysis, biosensing, and cell mimicry.

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It has long been pursued to develop polymer microspheres with various special morphologies and structures for better results in applications such as catalysis, drug delivery, and bioscaffolds. However, it remains a challenge to develop a facile method to produce poly(vinyl alcohol) (PVA) microspheres with special morphologies. Herein, a micron-sized marigold-like poly(vinyl alcohol) (CE-PVATPA) microsphere was engineered and fabricated by a feasible strategy, that is, emulsification-cross-linking, freeze-drying, and secondary acetal reaction steps. The morphological evolution of microspheres was systematically investigated under different conditions, and the procedure of constructing PVA microspheres with stabilizing marigold-like structures was proposed. More importantly, a specially structured PVA microsphere microreactor synergistically loading palladium metal nanoparticles (CE-PVATPA@Pd) for the heterogeneous catalyst 4-nitrophenol (4-NP) could be further demonstrated, which indicated high catalytic activity and excellent recyclability. The resultant stabilized fabricating method is promising to provide valuable guidance for the design and fabrication of a high-performance PVA microsphere microreactor.

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Industrial and disinfection wastewater typically contains high levels of organic pollutants and residue hydrogen peroxide, which have caused environmental concerns. In this work, dual-asymmetric MnO2 @polymer microreactors are synthesized via pollutant polymerization for self-driven and controlled H2 O2 decomposition. A hollow and asymmetric MnO2 nanotube is derived from MnO2 nanorods by selective acid etching and then coated by a polymeric layer from an aqueous phenolic pollutant via catalytic peroxymonosulfate (PMS)-induced polymerization. The evolution of particle-like polymers is controlled by solution pH, molar ratios of PMS/phenol, and reaction duration. The polymer-covered MnO2 tubing-structured micromotors presented a controlled motion velocity, due to the reverse torque driven by the O2 bubbles from H2 O2 decomposition in the inner tunnels. In addition, the partially coated polymeric layer can regulate the exposure and population of Mn active sites to control the H2 O2 decomposition rate, thus avoiding violent motions and massive heat caused by vigorous H2 O2 decomposition. The microreactors can maintain the function of mobility in an ultra-low H2 O2 environment (<0.31 wt.%). This work provides a new strategy for the transformation of micropollutants to functional polymer-based microreactors for safe and controlled hydrogen peroxide decomposition for environmental remediation.

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A microdroplet co-culture system is useful for the parallel assessment of numerous possible cell-cell interactions by generating isolated subcommunities from a pool of heterogeneous cells. However, the integration of single-cell sequencing into such analysis has been limited due to the lack of effective molecular identifiers for each in-droplet subcommunity. Herein, we present a strategy for generating in-droplet subcommunity identifiers using DNA-functionalized microparticles encapsulated within microdroplets. These microparticles serve as initial information carriers, where their combinations act as distinct identifiers for in-droplet subcommunity. Upon optical trigger, DNA barcoding molecules encoding the microparticle information are once released in the microdroplets and then tag cell membranes. The tagged DNA molecules then serve as a second information carrier readable by single-cell sequencing to reconstitute the community in silico in the single-cell RNA sequencing data space.

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Industrial biocatalysis plays an important role in the development of a sustainable economy, as enzymes can be used to synthesize an enormous range of complex molecules under environmentally friendly conditions. To further develop the field, intensive research is being conducted on process technologies for continuous flow biocatalysis in order to immobilize large quantities of enzyme biocatalysts in microstructured flow reactors under conditions that are as gentle as possible in order to realize efficient material conversions. Here, monodisperse foams consisting almost entirely of enzymes covalently linked via SpyCatcher/SpyTag conjugation are reported. The biocatalytic foams are readily available from recombinant enzymes via microfluidic air-in-water droplet formation, can be directly integrated into microreactors, and can be used for biocatalytic conversions after drying. Reactors prepared by this method show surprisingly high stability and biocatalytic activity. The physicochemical characterization of the new materials is described and exemplary applications in biocatalysis are shown using two-enzyme cascades for the stereoselective synthesis of chiral alcohols and the rare sugar tagatose.

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