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The continuous solid-electrolyte interphase (SEI) accumulation has been blamed for the rapid capacity loss of carbon anodes in Na and K ethylene carbonate (EC)/diethyl carbonate (DEC) electrolytes, but the understanding of the SEI composition and its formation chemistry remains incomplete. Here, we explain this SEI accumulation as the continuous production of organic species in solution-phase reactions. By comparing the NMR spectra of SEIs and model compounds we synthesized, alkali metal ethyl carbonate (MEC, M = Na or K), long-chain alkali metal ethylene carbonate (LCMEC, M = Na or K), and poly(ethylene oxide) (PEO) oligomers with ethyl carbonate ending groups are identified in Na and K SEIs. These components can be continuously generated in a series of solution-phase nucleophilic reactions triggered by ethoxides. Compared with the Li SEI formation chemistry, the enhancement of the nucleophilicity of an intermediate should be the cause of continuous nucleophilic reactions in the Na and K cases.
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Advanced microelectronics in the future may require semiconducting channel materials beyond silicon. Two-dimensional (2D) semiconductors, with their atomically thin thickness, hold great promise for future electronic devices. One challenge to achieving high-performance 2D semiconductor field effect transistors (FET) is the high contact resistance at the metal-semiconductor interface. In this study, we develop a charge-transfer doping strategy with WSe2/α-RuCl3 heterostructures to achieve low-resistance ohmic contact for p-type monolayer WSe2 transistors. We show that hole doping as high as 3 × 1013 cm-2 can be achieved in the WSe2/α-RuCl3 heterostructure due to its type-III band alignment, resulting in an ohmic contact with resistance of 4 kΩ µm. Based on that, we demonstrate p-type WSe2 transistors with an on-current of 35 µA·µm-1 and an ION/IOFF ratio exceeding 109 at room temperature.
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When a multi-component fluid contacts arigid solid substrate, the van der Waals interaction between fluids and substrate induces a depletion/adsorption layer depending on the intrinsic wettability of the system. In this study, we investigate the depletion/adsorption behaviors of A-B fluid system. We derive analytical expressions for the equilibrium layer thickness and the equilibrium composition distribution near the solid wall, based on the theories of de Gennes and Cahn. Our derivation is verified through phase-field simulations, wherein the substrate wettability, A-B interfacial tension, and temperature are systematically varied. Our findings underscore two pivotal mechanisms governing the equilibrium layer thickness. With an increase in the wall free energy, the substrate wettability dominates the layer formation, aligning with de Gennes' theory. When the interfacial tension increases, or temperature rises, the layer formation is determined by the A-B interactions, obeying Cahn's theory. Additionally, we extend our study to non-equilibrium systems where the initial composition deviates from the binodal line. Notably, macroscopic depletion/adsorption layers form on the substrate, which are significantly thicker than the equilibrium microscopic layers. This macroscopic layer formation is attributed to the interplay of phase separation and Ostwald ripening. We anticipate that the present finding could deepen our knowledge on the depletion/adsorption behaviors of immiscible fluids.
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Dielectric materials form the foundation of many electronic devices. When connected to a circuit, these materials undergo changes in microscopic morphology, such as the demixing of dielectric mixtures through phase separation and dielectric breakdown, resulting in the formation of micro-filaments. Consequently, the macroscopic properties and lifespan of the devices are significantly altered. To comprehend the physical mechanisms behind it, we conducted a systematic investigation of the thermodynamics of multicomponent leaky dielectric materials. Beginning with the total energy functional, we derived expressions for the binodal composition, spinodal composition, and critical points. Furthermore, we constructed and validated theoretical phase diagrams for the binary leaky dielectric mixture, incorporating three crucial freedoms: composition, temperature, and electric field strength. In addition, we analyzed the equilibrium interfacial tension impacted by the electric field and studied the dynamic aspects of dielectric materials, examining two morphological transformations: electrostriction and dielectric breakdowns. Our analysis unveiled a connection between these dynamic phenomena and the electric field-induced interfacial instability. The present work is expected to be supportive of future research on multicomponent dielectric materials by offering a comprehensive understanding of their thermodynamic and kinetic behaviors.
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Invasive fungal infections, including meningitis, cause a high mortality rate due to few available antifungal drugs and frequently associated side effects and quick emergence of drug-resistant fungi. The restrictive permeability of the blood-brain barrier (BBB) further limits the efficacy of antifungal agents substantially in treating meningitis. Hereby, we design and synthesize guanidinium-functionalized poly(2-oxazoline)s by mimicking cell-penetrating peptides. The optimal polymer, PGMeOx10 bearing a methylene spacer arm, displays potent activities against the drug-resistant fungi and biofilm, negligible toxicity, and insusceptibility to antimicrobial resistance. Moreover, PGMeOx10 can break BBB retractions to exert promising antifungal functions in the brain. PGMeOx10 demonstrates potent in vivo antifungal therapeutic efficacy in mouse models including skin infection, systemic infections, and meningitis. PGMeOx10 effectively rescues infected mice and reduces fungal burden and inflammation in the brain. These results and the excellent biosafety of poly(2-oxazoline)s indicate the effectiveness and potential of our strategy to design promising antifungal agents in treating systemic infections and meningitis.
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Antifúngicos , Meningite , Animais , Camundongos , Antifúngicos/farmacologia , Antifúngicos/uso terapêutico , Antifúngicos/química , Barreira Hematoencefálica , Fungos , Peptídeos/farmacologia , Meningite/tratamento farmacológico , Testes de Sensibilidade MicrobianaRESUMO
The blue-light hazard (BLH) has raised concerns with the increasing applications of white light-emitting diodes (LEDs). Many researchers believed that the shorter wavelength or more light components generally resulted in more severe retinal damage. In this study, based on the conventional phosphor-coated white LED, we added azure (484 nm), cyan (511 nm), and red (664 nm) light to fabricate the low-hazard light source. The low-hazard light sources and conventional white LED illuminated 68 Sprague-Dawley (SD) rats for 7 days. Before and after light exposure, we measured the retinal function, thickness of retinal layers, and fundus photographs. The expression levels of autophagy-related proteins and the activities of oxidation-related biochemical indicators were also measured to investigate the mechanisms of damaging or protecting the retina. With the same correlated color temperature (CCT), the low-hazard light source results in significantly less damage on the retinal function and photoreceptors, even if it has two times illuminance and blue-light hazard-weighted irradiance ([Formula: see text]) than conventional white LED. The results illustrated that [Formula: see text] proposed by IEC 62471 could not exactly evaluate the light damage on rats' retinas. We also figured out that more light components could result in less light damage, which provided evidence for the photobiomodulation (PBM) and spectral opponency on light damage.
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Luz , Retina , Ratos , Animais , Ratos Sprague-DawleyRESUMO
Reflective phenomena often occur in the detecting process of pointer meters by inspection robots in complex environments, which can cause the failure of pointer meter readings. In this paper, an improved k-means clustering method for adaptive detection of pointer meter reflective areas and a robot pose control strategy to remove reflective areas are proposed based on deep learning. It mainly includes three steps: (1) YOLOv5s (You Only Look Once v5-small) deep learning network is used for real-time detection of pointer meters. The detected reflective pointer meters are preprocessed by using a perspective transformation. Then, the detection results and deep learning algorithm are combined with the perspective transformation. (2) Based on YUV (luminance-bandwidth-chrominance) color spatial information of collected pointer meter images, the fitting curve of the brightness component histogram and its peak and valley information is obtained. Then, the k-means algorithm is improved based on this information to adaptively determine its optimal clustering number and its initial clustering center. In addition, the reflection detection of pointer meter images is carried out based on the improved k-means clustering algorithm. (3) The robot pose control strategy, including its moving direction and distance, can be determined to eliminate the reflective areas. Finally, an inspection robot detection platform is built for experimental study on the performance of the proposed detection method. Experimental results show that the proposed method not only has good detection accuracy that achieves 0.809 but also has the shortest detection time, which is only 0.6392 s compared with other methods available in the literature. The main contribution of this paper is to provide a theoretical and technical reference to avoid circumferential reflection for inspection robots. It can adaptively and accurately detect reflective areas of pointer meters and can quickly remove them by controlling the movement of inspection robots. The proposed detection method has the potential application to realize real-time reflection detection and recognition of pointer meters for inspection robots in complex environments.
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Zinc (Zn) metal anode suffers from uncontrollable Zn dendrites and parasitic side reactions at the interface, which restrict the practical application of aqueous rechargeable zinc batteries (ARZBs). Herein, an amphoteric cellulose-based double-network is introduced as hydrogel electrolyte to overcome these obstacles. On one hand, the amphoteric groups build anion/cation transport channels to regulate electro-deposition behavior on Zn (002) crystal plane enabled by homogenizing Zn2+ ions flux. On the other hand, the strong bonding between negatively charged carboxyl groups and Zn2+ ions promote the desolvation process of [Zn(H2 O)6 ]2+ to eliminate side reactions. Based on the above two functions, the hydrogel electrolyte enables an ultra-stable cycling with a cumulative capacity of 7â Ah cm-2 at 20â mA cm-2 /20â mAh cm-2 for Zn||Zn cell. This work provides significant concepts for developing hydrogel electrolytes to realize stable anode for high-performance ARZBs.
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Interest in developing antibacterial polymers as synthetic mimics of host defense peptides (HPDs) has accelerated in recent years to combat antibiotic-resistant bacterial infections. Positively charged moieties are critical in defining the antibacterial activity and eukaryotic toxicity of HDP mimics. Most examples have utilized primary amines or guanidines as the source of positively charged moieties, inspired by the lysine and arginine residues in HDPs. Here, we explore the impact of amine group variation (primary, secondary, or tertiary amine) on the antibacterial performance of HDP-mimicking ß-peptide polymers. Our studies show that a secondary ammonium is superior to either a primary ammonium or a tertiary ammonium as the cationic moiety in antibacterial ß-peptide polymers. The optimal polymer, a homopolymer bearing secondary amino groups, displays potent antibacterial activity and the highest selectivity (low hemolysis and cytotoxicity). The optimal polymer displays potent activity against antibiotic-resistant bacteria and high therapeutic efficacy in treating MRSA-induced wound infections and keratitis as well as low acute dermal toxicity and low corneal epithelial cytotoxicity. This work suggests that secondary amines may be broadly useful in the design of antibacterial polymers.
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Aminas/química , Antibacterianos/uso terapêutico , Staphylococcus aureus Resistente à Meticilina/patogenicidade , Peptídeos/uso terapêutico , Infecções Estafilocócicas/tratamento farmacológico , Infecção dos Ferimentos/tratamento farmacológico , Animais , Antibacterianos/química , Antibacterianos/farmacologia , Peptídeos Catiônicos Antimicrobianos/química , Escherichia coli/efeitos dos fármacos , Hemólise/efeitos dos fármacos , Ceratite/tratamento farmacológico , Ceratite/microbiologia , Ceratite/patologia , Staphylococcus aureus Resistente à Meticilina/efeitos dos fármacos , Staphylococcus aureus Resistente à Meticilina/isolamento & purificação , Camundongos , Testes de Sensibilidade Microbiana , Peptídeos/química , Peptídeos/farmacologia , Polímeros/química , Infecções Estafilocócicas/microbiologia , Infecção dos Ferimentos/microbiologiaRESUMO
Microscale Janus particles have versatile potential applications in many physical and biomedical fields, such as microsensor, micromotor, and drug delivery. Here, we present a phase-field approach of multicomponent and multiphase to investigate the Janus droplet formation via thermally induced phase separation. The crucial kinetics for the formation of Janus droplets consisting of two polymer species and a solvent component via an interplay of both diffusion and convection is considered in the Cahn-Hilliard-Navier-Stokes equation. The simulation results of the phase-field model show that unequal interfacial tensions between the two polymer species and the solvent result in asymmetric phase separation in the formation process of Janus droplets. This asymmetric phase separation plays a vital role in the establishment of the so-called core-shell structure that has been observed in previous experiments. By varying the droplet size, the surface tension, and the molecular interaction between the polymer species, several novel droplet morphologies are predicted in the development process of Janus droplets. Moreover, we stress that the hydrodynamics should be reckoned as a non-negligible mechanism that not only accelerates the Janus droplet evolution but also has great impacts on the coarsening and coalescence of the Janus droplets.
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This study investigated the effects of air temperature and ventilation on the sleep quality of elderly subjects and elucidated the mechanisms involved. Sixteen subjects aged over 65 years old were exposed to four conditions in a 2 × 2 design: air temperatures of 27°C and 30°C (with a ceiling fan in operation at 30°C) and two ventilation conditions (with and without mechanical ventilation) in experimental bedrooms. Their electroencephalogram, electrooculogram, chin electromyogram, electrocardiogram, respiration, oxygen saturation, and wrist skin temperature were measured continuously during sleep. Saliva samples were collected, and blood pressure was measured both before and after sleep. The results showed that at the temperature of 30°C, the total sleep time, sleep efficiency, and duration of REM sleep of the elderly decreased by 26.3 min, 5.5%, and 5.3 min, respectively, and time awake increased by 27.0 min, in comparison with 27°C, indicating that the sleep quality of the elderly is very vulnerable to heat exposure. Even a small heat load led to an overactive sympathetic nervous system and increased wrist skin temperature, which reduced sleep quality. Improving the ventilation increased the duration of deep sleep and REM sleep by 10.3 min and 3.7 min, respectively. Higher pollutant concentrations affected the respiration and autonomous nervous systems to reduce sleep quality. The benefits of improved thermal environment and ventilation on sleep quality were found to be additive. Good ventilation and the avoidance of raised temperatures in the bedroom are thus both important for the sleep quality of the elderly.
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Poluição do Ar em Ambientes Fechados , Qualidade do Sono , Idoso , Humanos , Temperatura , Respiração , Sono/fisiologiaRESUMO
Incoherent broadband cavity-enhanced absorption spectroscopy (IBBCEAS) can achieve sensitive measurements at trace concentrations for liquid phase marine samples. The IBBCEAS system consists of a cavity-enhancement module (CEM) and a transmission hyperspectral module (THM). The CEM has cavity-enhancement factors up to 78 at 550 nm. Measurements were obtained over a wide wavelength range (420-640 nm) with a halogen lamp, and the optical cavity was formed by two concave highly reflective mirrors (R=0.99). The minimum detectable absorption coefficient αmin of 7.3×10-7cm-1 at 550 nm corresponds to a limit of detection for nutrients of 780 pM. The spectral resolution of the THM is 3 nm in the wavelength range of 400 to 750 nm. We performed the IBBCEAS measurements for biological and chemical substances, including nutrients, microalgae, and Cy5 dye. The concentrations of nutrients in a deionized water environment and artificial seawater environment were measured at nanomolar levels; the concentration of microalgae phaeocystis was detected with 3.46×104/mL, and fluorescence substances such as Cy5 dye could be measured at 0.03 mg/L. Experimental results show that the IBBCEAS system has the capability for sensitive measurements of biological and chemical substances and has strong potential forin situ ecological marine environmental monitoring function.
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Microalgas , Monitoramento Ambiental , Nutrientes , Análise Espectral/métodosRESUMO
We propose a confocal hyperspectral microscopic imager (CHMI) that can measure both transmission and fluorescent spectra of individual microalgae, as well as obtain classical transmission images and corresponding fluorescent hyperspectral images with a high signal-to-noise ratio. Thus, the system can realize precise identification, classification, and location of microalgae in a free or symbiosis state. The CHMI works in a staring state, with two imaging modes, a confocal fluorescence hyperspectral imaging (CFHI) mode and a transmission hyperspectral imaging (THI) mode. The imaging modes share the main light path, and thus obtained fluorescence and transmission hyperspectral images have point-to-point correspondence. In the CFHI mode, a confocal technology to eliminate image blurring caused by interference of axial points is included. The CHMI has excellent performance with spectral and spatial resolutions of 3 nm and 2 µm, respectively (using a 10× microscope objective magnification). To demonstrate the capacity and versatility of the CHMI, we report on demonstration experiments on four species of microalgae in free form as well as three species of jellyfish with symbiotic microalgae. In the microalgae species classification experiments, transmission and fluorescence spectra collected by the CHMI were preprocessed using principal component analysis (PCA), and a support vector machine (SVM) model or deep learning was then used for classification. The accuracy of the SVM model and deep learning method to distinguish one species of individual microalgae from another was found to be 96.25% and 98.34%, respectively. Also, the ability of the CHMI to analyze the concentration, species, and distribution differences of symbiotic microalgae in symbionts is furthermore demonstrated.
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Imageamento Hiperespectral/instrumentação , Microalgas/classificação , Microscopia Confocal/instrumentação , Animais , Aprendizado Profundo , Desenho de Equipamento , Imageamento Hiperespectral/métodos , Microalgas/isolamento & purificação , Microscopia Confocal/métodos , Análise de Componente Principal , Cifozoários , Máquina de Vetores de Suporte , SimbioseRESUMO
Currently, multiple emulsions via liquid-liquid phase separation in ternary polymer solutions have sparked considerable interest because of its remarkable potential in physical, medical, and biological applications. The transient "onion-like" multilayers are highly dependent on the evolution kinetics, which is challenging to be scrutinized in experiments and has not yet been fully understood. Here, we report a thermodynamically consistent multicomponent Cahn-Hilliard model to investigate the kinetics of multiple emulsions by tracing the temporal evolution of the local compositions inside the emulsion droplets. We reveal that the mechanism governing the kinetics is attributed to the competition between surface energy minimization and phase separation. Based on this concept, a generalized morphology diagram for different emulsion patterns is achieved, showing a good accordance with previous experiments. Moreover, combining the analysis for the kinetics and the morphology diagram, we predict new emulsion structures that provide general guidelines to discovery, design, and manipulation of complex multiphase emulsions.
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A promising alternative to classical antibiotics are antimicrobial peptides and their synthetic mimics (smAMPs) that supposedly act directly on membranes. For a more successful design of smAMPs, we need to know how the type of interaction with the membrane determines the type of membrane perturbation. How this, in turn, transfers into selectivity and microbial killing activity is largely unknown. Here, we characterize the action of two smAMPs: MM:CO (a copolymer of hydrophobic cyclooctyl subunits and charged ß-monomethyl-α-aminomethyl subunits) and the highly charged poly-NM (a homopolymer of α-aminomethyl subunits). By thorough characterization of vesicle leakage experiments, we elucidate complex membrane perturbation behavior in zwitterionic or negatively charged vesicles. Vesicle leakage data does not entirely agree with the growth inhibition of microbes. Our ensemble of advanced membrane permeabilization approaches clarifies these discrepancies. Long cumulative leakage kinetics show that the two smAMPs act either by transient leakage or by rare stochastic leakage events that occur at charge neutralization in the sample. We determine the strengths of individual leakage events induced by the smAMPs in membranes of various compositions. These strengths indicate changes in leakage mechanism over time and concentration range. Thus, our sophisticated analysis of vesicle leakage experiments reveals a fine-tuned flexibility in membrane permeabilization mechanisms. These details are indispensable in judging and designing membrane-active compounds.
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Peptídeos Catiônicos Antimicrobianos/metabolismo , Lipossomas Unilamelares/metabolismo , Peptídeos Catiônicos Antimicrobianos/química , Fluoresceínas/química , Glicerofosfatos/química , Interações Hidrofóbicas e Hidrofílicas , Permeabilidade/efeitos dos fármacos , Ligação Proteica , Eletricidade Estática , Lipossomas Unilamelares/químicaRESUMO
Biocompatible and proteolysis-resistant poly-ß-peptides have broad applications and are dominantly synthesized via the harsh and water-sensitive ring-opening polymerization of ß-lactams in a glovebox or using a Schlenk line, catalyzed by the strong base LiN(SiMe3 )2 . We have developed a controllable and water-insensitive ring-opening polymerization of ß-amino acid N-thiocarboxyanhydrides (ß-NTAs) that can be operated in open vessels to prepare poly-ß-peptides in high yields, with diverse functional groups, variable chain length, narrow dispersity and defined architecture. These merits imply wide applications of ß-NTA polymerization and resulting poly-ß-peptides, which is validated by the finding of a HDP-mimicking poly-ß-peptide with potent antimicrobial activities. The living ß-NTA polymerization enables the controllable synthesis of random, block copolymers and easy tuning of both terminal groups of polypeptides, which facilitated the unravelling of the antibacterial mechanism using the fluorophore-labelled poly-ß-peptide.
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Antibacterianos/farmacologia , Bacillus subtilis/efeitos dos fármacos , Peptídeos/farmacologia , Staphylococcus/efeitos dos fármacos , Água/química , Aminoácidos/química , Aminoácidos/farmacologia , Anidridos/química , Anidridos/farmacologia , Antibacterianos/síntese química , Antibacterianos/química , Testes de Sensibilidade Microbiana , Estrutura Molecular , Peptídeos/síntese química , Peptídeos/química , Polimerização , Compostos de Sulfidrila/química , Compostos de Sulfidrila/farmacologiaRESUMO
Cell adhesive and other functional peptides (such as RGD, KRSR, YIGSR, VAPG, and BMP-2 peptides) are extensively studied and utilized in tissue engineering scaffolds and biomedical devices to modulate cell functions. Though PEG is frequently used as the antifouling layer, it is unclear how it affects the performance of functional peptides. By analyzing the impact of PEG at short (OEG4), medium (OEG8), and long chain length (PEG2K), we reveal that PEG chain length is critical and a medium-length PEG enables functional peptides to display their optimal and genuine functions in cell adhesion, migration, and differentiation by providing excellent antifouling to minimize background noise of unwanted cell adhesion and high enough surface density of functional peptides. Our result provides new avenues for maximizing the genuine functions of peptides. This study also provides a solution to prevent the heterogeneous and even divergent results caused by inappropriate choice of antifouling PEG and provides a general guidance in identifying new functional peptides.
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Incrustação Biológica/prevenção & controle , Peptídeos/química , Peptídeos/farmacologia , Polietilenoglicóis/química , Animais , Adesão Celular/efeitos dos fármacos , Diferenciação Celular/efeitos dos fármacos , Movimento Celular/efeitos dos fármacos , Camundongos , Células NIH 3T3RESUMO
An ethylene-air diffusion flame was acoustically forced with a frequency of 100 Hz at four amplitudes ranging from 40% to 140%. The average bulk velocity of the fuel was 0.6 m/s. The soot distribution and velocity fields were measured by simultaneous two-dimensional laser-induced incandescence (LII) and stereo particle image velocimetry (PIV) at 20 kHz laser repetition rate. The LII signal was calibrated by pulse-to-pulse laser energy variation, and it was observed that the soot regions extended along the central axis of the flame and shrank radially under acoustic forcing compared with the steady flame. The volume fraction of soot in the acoustically forced flame decreased with increased acoustic driving. In addition, the PIV results revealed that the resident time was strongly associated with the formation of an oval-shaped soot region, which was induced by external acoustic forcing.
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Response of a laminar diffusion dimethyl-ether flame forced by an acoustic field is provided. A forcing frequency of 100 Hz, which is chosen based on the typical thermo-acoustic instability frequency in a practical combustor, is applied to the flame at a Reynolds number of 250. The development of the forced vortical structures present in this flame has been investigated utilizing a burst mode laser with a repetition rate of 10 kHz. Flame/vortex interaction is visualized by planar laser-induced fluorescence (PLIF) of formaldehyde, which is used to identify the early-stage fuel decomposition in the flame. The flame structure is also correlated with the velocity field, which is obtained utilizing particle imaging velocimetry (PIV). The resulting phase-resolved and time-averaged velocity and vortex images indicate that the amplitude of excitation has pronounced effects on the flame via modifying the local heat release.
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We develop a simple approach for the preparation of oil/water separation material based on the reduced graphene oxide. First, the graphene oxide (GO) is coated on the commercially available wire mesh. The treatment of O2 plasma is exploited to open the pores from the back side using the wire mesh as a ready-made mask, and the GO-coated mesh is subjected to the thermal annealing at 200 °C for 2 h to form stable superhydrophobic reduced graphene oxide (RGO) coating. The as-prepared mesh has excellent stability and reusability and the separation selectivity is above 98% for a variety of mixtures of oil and water. Meanwhile, the as-prepared RGO@mesh-300 shows stable and robust superhydrophobic properties including the stability of long-term storage, the resistance to high temperatures, high humidities, and mechanical abrasion. It is expected that this method of fabricating superhydrophobic materials can find more practical applications, especially in the oil/water separation.