Suppressing metal corrosion through identification of optimal crystallographic plane for Zn batteries.

Direct use of metals as battery anodes could significantly boost the energy density, but suffers from limited cycling. To make the batteries more sustainable, one strategy is mitigating the propensity for metals to form random morphology during plating through orientation regulation, e.g., hexagonal Zn platelets locked horizontally by epitaxial electrodeposition or vertically aligned through Zn/electrolyte interface modulation. Current strategies center around obtaining (002) faceted deposition due to its minimum surface energy. Here, benefiting from the capability of preparing a library of faceted monocrystalline Zn anodes and controlling the orientation of Zn platelet deposits, we challenge this conventional belief. We show that while monocrystalline (002) faceted Zn electrode with horizontal epitaxy indeed promises the highest critical current density, the (100) faceted electrode with vertically aligned deposits is the most important one in suppressing Zn metal corrosion and promising the best reversibility. Such uniqueness results from the lowest electrochemical surface area of (100) faceted electrode, which intrinsically builds upon the surface atom diffusion barrier and the orientation of the pallets. These new findings based on monocrystalline anodes advance the fundamental understanding of electrodeposition process for sustainable metal batteries and provide a paradigm to explore the processing-structure-property relationships of metal electrodes.

Single-Site Pd Regulated by π-π Stacking for High-Selectivity Cyclopropanation Reaction.

Cyclopropane-based high-energy fuels possess high intramolecular energy and density, and their precise synthesis is a critical challenge. However, owing to the highest strain in the cyclopropane structure (compared to other four- or five-membered rings, etc.), metal-carbene intermediates form with difficulty, resulting in poor catalytic selectivity for its synthesis. Herein, through rational design of π-π stacking between the Pd organic complex and graphene, we report a single-site Pd catalyst for precise synthesis of multicyclopropane-based high-energy fuels. It is discovered that π-π stacking enhanced the electrophilicity of Pd through a weak metal-support interaction, thus promoting the formation of Pd═C carbene active intermediates. Meanwhile, the adsorption between the active centers and intermediates was enhanced via π-π stacking. These two respects led to almost twice selectivity for cyclopropanation reaction up to 80.5% as that without π-π stacking. This work provides an effective strategy of π-π noncovalent interactions for regulating C-C coupling reaction selectivity.

Fluorine Domains Induced Ultrahigh Nitrogen Solubility in Ionic Liquids.

Fluorinated ionic liquids (ILs) are well-known as electrolytes in the nitrogen (N2) electroreduction reaction due to their exceptional gas solubility. However, the influence of fluorinated functional group on N2 solvation and solubility enhancement remains unclear. Massive molecular dynamics simulations and free energy perturbation methods are conducted to investigate the N2 solubility in 11 traditional and 9 fluorinated ILs. It shows that the fluorinated IL of 1-Ethyl-3-methylimidazolium tris(pentafluoroethyl) trifluorophosphate ([Emim]FAP) exhibits ultrahigh solubility, 4.844 × 10-3, approximately 118 times higher than that of traditional IL 1-Ethyl-3-methylimidazolium nitrate ([Emim]NO3). Moreover, fluorinated ILs with more than 10 C-F bonds possess higher N2 solubility than others and show an exothermic nature during solvation. As the C-F bonds number in ILs decreases, the N2 solubility decreases significantly and displays the opposite endothermic behavior. To understand the ultrahigh N2 solubility in fluorinated ILs, we propose a concept of fluorine densification energy (FDE), referring to the average strength of interaction between atoms per unit volume in ILs with fluorine domains, demonstrating a linear relationship with C-F bonds. Physically, lower FDE results in lower N2-anion pair dissociation energy and higher free volume, finally enhancing the N2 solubility. Consequently, medium to long alkyl fluorine tails within a polar environment defines a distinct fluorine domain, emphasizing FDE's role in enhancing N2 solubility. Overall, these quantitative results will not only deepen the understanding of N2 solvation in ILs but may also shed light on the rational design of IL-based high-performance N2 capture and conversion technologies.

Ionic Liquid Gating Induces Anomalous Permeation through Membrane Channel Proteins.

Membrane channel proteins (MCPs) play key roles in matter transport through cell membranes and act as major targets for vaccines and drugs. For emerging ionic liquid (IL) drugs, a rational understanding of how ILs affect the structure and transport function of MCP is crucial to their design. In this work, GPU-accelerated microsecond-long molecular dynamics simulations were employed to investigate the modulating mechanism of ILs on MCP. Interestingly, ILs prefer to insert into the lipid bilayer and channel of aquaporin-2 (AQP2) but adsorb on the entrance of voltage-gated sodium channels (Nav). Molecular trajectory and free energy analysis reflect that ILs have a minimal impact on the structure of MCPs but significantly influence MCP functions. It demonstrates that ILs can decrease the overall energy barrier for water through AQP2 by 1.88 kcal/mol, whereas that for Na+ through Nav is increased by 1.70 kcal/mol. Consequently, the permeation rates of water and Na+ can be enhanced and reduced by at least 1 order of magnitude, respectively. Furthermore, an abnormal IL gating mechanism was proposed by combining the hydrophobic nature of MCP and confined water/ion coordination effects. More importantly, we performed experiments to confirm the influence of ILs on AQP2 in human cells and found that treatment with ILs significantly accelerated the changes in cell volume in response to altered external osmotic pressure. Overall, these quantitative results will not only deepen the understanding of IL-cell interactions but may also shed light on the rational design of drugs and disease diagnosis.

Mussel and Cobweb Inspired High Areal Capacity SPAN Electrode.

Lithium-sulfur batteries (LSBs) with superior energy density are among the most promising candidates for next-generation energy storage techniques. Sulfurized polyacrylonitrile (SPAN) exhibits competitive advantages in terms of cycle stability, rate performance as well as cost. However, the preparation of high-loading SPAN electrodes is still challenging. Herein, inspired by mussel and cobweb, a high-loading SPAN electrode is enabled by the combination of polydopamine (PDA) coating and a bimodal distributed single-wall carbon nanotubes (SWCNT) slurry dispersed in polyvinylpyrrolidone (PVP), their synergistic effect not only constructs effective electron percolating networks within the electrode but also make high active material (AM) ratio possible. High areal capacity PDA@SPAN electrode (18.40 mAh cm-2 in the initial cycle) with negligible specific capacity attenuation as the mass loading increasement is realized through the facile slurry casting process. The dynamic N─H…O hydrogen bond is formed between PDA and PVP and the electrode integrity during charge/discharge is greatly strengthened. The battery with an areal AM loading of 7.16 mg cm-2 (5.16 mAh cm-2) retains 92.0% of capacity in 80 cycles and 87.18% in 160 cycles, and it also shows stable cycle performances even with a high loading of 19.79 mg cm-2 and lean electrolyte (3.28 µL mg-1).

Effect of Interlayer Spaces and Interfacial Structures on High-Performance MXene/Ionic Liquid Supercapacitors: A Molecular Dynamics Simulation.

The combination of high-capacitance MXenes and wide-electrochemical-window ionic liquids (ILs) has exhibited bright prospects in supercapacitors. Several strategies, such as surficial functionalization and interlayer spacing tuning, have been used to enhance the electrochemical performance of supercapacitors. However, the lack of theoretical guidance on these strategies, including the effects of the microenvironment in the interlayer of confined ILs, hindered the further exploration of such devices. Herein, we performed molecular dynamics simulations to comprehensively investigate the effects of the interlayer space and surface terminations of MXene electrodes on capacity. The results show that the electrical double layer (EDL) structure was found to form on the interface between the MXene electrode and ILs electrolyte by analyzing the ion number density and charge density in the nanometer confined spaces. Under the same potential, the -OH terminations significantly impact the ion orientation in the EDL, particularly near the electrode surface, where cations tend to align vertically, allowing the retention of more cations at the electrode surfaces. Interestingly, such an orientation distribution was decisively from the hydrogen bonds expressed by O-H···O between the -OH termination of MXene and -OH groups of ILs. The differential capacitances of the supercapacitors were calculated by the surficial electron density, and it showed that the capacitance is a nearly one-quarter increase in the 14 Å interlayer spacing compared with that of 10 Å under an applied potential of 2 V. At the same time, the Ti3C2(OH)2 electrode had a higher differential capacitance than the Ti3C2O2 electrode, which possibly originates from the stronger hydrogen bonds to contribute to the vertical aggregation of the cations. Our results highlighted the roles of the interlayer spacing distance and surface terminations of the MXene on the performance of the type of supercapacitor.

Ionic liquids revolutionizing biomedicine: recent advances and emerging opportunities.

Ionic liquids (ILs), due to their inherent structural tunability, outstanding miscibility behavior, and excellent electrochemical properties, have attracted significant research attention in the biomedical field. As the application of ILs in biomedicine is a rapidly emerging field, there is still a need for systematic analyses and summaries to further advance their development. This review presents a comprehensive survey on the utilization of ILs in the biomedical field. It specifically emphasizes the diverse structures and properties of ILs with their relevance in various biomedical applications. Subsequently, we summarize the mechanisms of ILs as potential drug candidates, exploring their effects on various organisms ranging from cell membranes to organelles, proteins, and nucleic acids. Furthermore, the application of ILs as extractants and catalysts in pharmaceutical engineering is introduced. In addition, we thoroughly review and analyze the applications of ILs in disease diagnosis and delivery systems. By offering an extensive analysis of recent research, our objective is to inspire new ideas and pathways for the design of innovative biomedical technologies based on ILs.

Precise Helium Sieving from Hydrogen Using Fluorine-Decorated Carbon Hollow Fiber Membranes.

Separating helium (He) and hydrogen (H2), two gases that are extremely similar in molecular size and condensation properties, presents a formidable challenge in the helium industry. The development of membranes capable of precisely differentiating between these gases is crucial for achieving large-scale, energy-efficient He/H2 separation. However, the limited selectivity of current membranes has hindered their practical application. In this study, we propose a novel approach to overcome this challenge by engineering submicroporous membranes through the fluorination of partially carbonized hollow fibers. We demonstrate that the fluorine substitution on the inner rim of the micropore walls within the carbon hollow fibers enables tunability of the microporous architecture. Furthermore, it enhances interactions between H2 molecules and the micropore walls through the polarization and hydrogen bonding induced by C-F bonds, resulting in simultaneous improvements in both He/H2 diffusivity and solubility selectivities. The fluorinated HFM-550-F-1 min membrane exhibits exceptional mixed-gas separation performance, with a binary mixed-gas He/H2 selectivity of 10.5 and a ternary mixed-gas He/(H2+CO2) selectivity of 20.8, at 40 bar feed pressure and 35 °C, surpassing all previously reported polymer-based gas separation membranes, and remarkable plasticization resistance and long-term continuous stability over 30 days.

Efficient Capture and Low Energy Release of NH3 by Azophenol Decorated Photoresponsive Covalent Organic Frameworks.

In NH3 capture technologies, the desorption process is usually driven by high temperature and low pressure (such as 150-200 °C under vacuum), which accounts for intensive energy consumption and CO2 emission. Developing light responsive adsorbent is promising in this regard but remains a great challenge. Here, we for the first time designed and synthesized a light responsive azophenol-containing covalent organic framework (COF), COF-HNU38, to address this challenge. We found that at 25 °C and 1.0 bar, the cis -COF exhibited a NH3 uptake capacity of 7.7 mmol g-1 and a NH3/N2 selectivity of 158. In the adsorbed NH3, about 29.0 % could be removed by vis-light irradiated cis-trans isomerization at 25 °C, and the remaining NH3 might be released at 25 °C under vacuum. Almost no decrease in adsorption capacity was observed after eight adsorption-desorption cycles. As such, an efficient NH3 capture and low energy release strategy was established thanks to the multiple hydrogen bond interactions (which are strong in total but weak in individuals) between NH3 and the smart COF, as well as the increased polarity and number of hydrogen bond sites after the trans-cis isomerization.

Ingenious Artificial Leaf Based on Covalent Organic Framework Membranes for Boosting CO2 Photoreduction.

Covalent organic frameworks (COFs) hold the potential in converting CO2 with water into value-added fuels and O2 to save the deteriorating ecological environment. However, reaching high yield and selectivity is a grand challenge under metal-, photosensitizer-, or sacrificial reagent-free conditions. Here, inspired by microstructures of natural leaves, we designed triazine-based COF membranes with the integration of steady light-harvesting sites, efficient catalytic center, and fast charge/mass transfer configuration to fabricate a novel artificial leaf for the first time. Significantly, a record high CO yield of 1240 µmol g-1 in a 4 h reaction, approximately 100% selectivity, and a long lifespan (at least 16 cycles) were achieved under gas-solid conditions without using any metal, photosensitizer, or sacrificial reagent. Unlike the existing knowledge, the chemical structural unit of triazine-imide-triazine and the unique physical form of the COF membrane are predominant for such a remarkable photocatalysis. This work opens a new pathway to simulating photosynthesis in leaves and may motivate relevant research in the future.

Superior Rate Capability of Small Regenerated Graphite Particles Induced by Homogeneously Distributed Current Density Derived from Cracks and Intrinsic Defects.

As spent batteries can be considered as alternative raw sources of electrode materials; the development of regeneration techniques for spent graphite becomes key to realizing economic and environmental sustainability. Herein, the reutilization of small spent graphite particles is domonstrated due to their special structural characteristics, which may directly contribute to the improvement of lithiation kinetics and high-rate charging during long-term cycling. Such intrinsic defects and external cracked channels may be introduced by the aging of intrinsic bulk structure and exfoliation of surface structure. On account of these potential advantages, a carbonized polypyrrole layer on sieved small graphite particles is developed to obtain superior rate performance. The coated amorphous/graphitic layer could repair the exposed edge and basal plane, and significantly facilitate Li ion diffusion during fast charging. Moreover, the enhanced performance may favor the improved homogeneity of current density distribution during fast charging, which is confirmed by a porous electrode model. The regenerated graphite with a disorder/order coating layer could effectively regulate the Li+ transport channel, exhibiting a high specific capacity at high-rate charging (102.7 mAh g-1 at 4 C after 500 cycles) without severe Li plating. This work provides an opportunity to utilize spent graphite in fast-charging batteries.

Modelling toluene sorption in ionic liquid/metal organic framework composite materials.

Toluene is a prevalent pollutant in indoor environments and its removal is essential to maintain a healthy environment. Adsorption is one of the best alternatives for organic vapours removal, specially at low indoor concentrations. Metal Organic Frameworks (MOFs) and Ionic Liquids (ILs) are potential materials for this mean. In this work, the synthesis and application of IL/MOF composite materials for toluene removal is reported. Loading [BMIM][CH3COO] ionic liquid into MIL101 porous structure improves parent materials affinity towards toluene capture by two orders of magnitude (as Henry's constants, attesting to their synergy). MIL101(Cr) and absorption in [BMIM][CH3COO] IL is best described by Henry's Law, while the Langmuir adsorption model predicts toluene adsorption on [BMIM][CH3COO]/MIL101(Cr) better than Freundlich and Toth equations. Diffusional and kinetics models revealed that toluene diffusion is the rate limiting step for pristine MIL101. Kinetic and diffusion rates were systematically improved upon the incorporation of the ionic liquid due to shorter toluene hops with the adsorbed IL and the increased hydrophobicity in the composites making the sorption more favourable. This study provides a systematic analysis and modelling of the toluene capture process in IL/MOF composites aiding a better understanding of the sorption process in these novel materials.

Enhanced Electrochemical Nitrate-to-Ammonia Performance of Cobalt Oxide by Protic Ionic Liquid Modification.

Electrochemical conversion of nitrate to ammonia is an appealing way for small-scale and decentralized ammonia synthesis and waste nitrate treatment. Currently, strategies to enhance the reaction performance through elaborate catalyst design have been well developed, but it is still of challenge to realize the promotion of reactivity and selectivity at the same time. Instead, a facile method of catalyst modification with ionic liquid to modulate the electrode surface microenvironment that mimic the role of the natural MoFe protein environment is found effective for the simultaneous improvement of NH3 yield rate and Faradaic efficiency (FE) at a low NaNO3 concentration of 500 ppm. Protic ionic liquid (PIL) N-butylimidazolium bis(trifluoromethylsulfonyl)imide ([Bim]NTf2 ) modified Co3 O4-x is fabricated and affords the NH3 yield rate and FE of 30.23±4.97 mg h-1 mgcat. -1 and 84.74±3.43 % at -1.71 and -1.41 V vs. Ag/AgCl, respectively, outperforming the pristine Co3 O4-x . Mechanistic and theoretical studies reveal that the PIL modification facilitates the adsorption and activation of NO3 - as well as the NO3 - -to-NH3 conversion and inhibits hydrogen evolution reaction competition via enhancing the Lewis acidity of the Co center, shuttling protons, and constructing a hydrogen bonded and hydrophobic electrode surface microenvironment.

Robust Electrocatalytic Li2 S Redox of Li-S Batteries Facilitated by Rationally Fabricated Dual-Defects.

The commercialization of lithium-sulfur batteries with ultra-high theoretical energy density is restricted mainly by the notorious polysulfides "shuttle effect" and slow Li2 S redox reaction kinetics. A sulfur host material with high catalytic activity and high conductivity is greatly desired to improve its electrochemical performance. Herein, a sulfur host material, etched cotton@petroleum asphalt carbon (eCPAC), with high specific surface area and excellent catalytic activity, is demonstrated based on a synergistic strategy of introducing intrinsic lattice defects and composite carbon structure. Benefiting from in situ coupling of amorphous and crystalline materials, eCPAC exhibits high conductivity and high sulfur adsorbability. Furthermore, eCPAC containing dual intrinsic defect sites can catalyze the bidirectional sulfur chemistry of Li2 S and capture polysulfides, which is also demonstrated by systematic density functional theory calculations and the potential intermittent titration technique. S@eCPAC/Li cells exhibit excellent cycling stability and rate performance, with an average capacity decay rate of only 0.05% over 1000 cycles at 0.5 C and even 0.03% over 600 cycles at 5 C. Meanwhile, the practicality of eCPAC is proven in high-load batteries and pouch batteries. eCPAC provides a reliable strategy for achieving a win-win situation of capturing polysulfides and accelerating Li2 S redox kinetics.

Robust Multiscale Electron/Ion Transport and Enhanced Structural Stability in SiOx Semi-Solid Anolytes Enabled by Trifunctional Artificial Interfaces for High-Performance Li-Ion Slurry Flow Batteries.

SiOx suspension is regarded as an attractive anolyte for high-energy-density Li-ion slurry flow batteries. However, the poor electronic conductivity and non-negligible volume variation of SiOx greatly hinder its practical applications. Herein, these issues are successfully addressed by rationally designing a trifunctional interface with mixed electron/ion and hard/soft modulated properties on SiOx surface via H-bonding interactions. The interface comprises a lithiated polymer layer (LiPN) interfused with functionalized single-walled carbon nanotubes. Carbon nanotubes work as electrical tentacles to enhance the multiscale electron conduction. The LiPN layer with transferable Li-ions facilitates ion transport. In addition, the LiPN layer employs lithiated rigid polyacrylic acid as a framework to provide mechanical support and soft nafion as a buffer to accommodate volume change, which maintains the structural integrity of SiOx . Hence, SiOx @LiPN/S anolytes exhibit significantly improved rate and cycle performances. Specially, the interface enables the anolytes to load more active particles (30 wt%) or less conductive additives (0.4 wt%). The semi-solid pouch cells based on high-active-content anolytes with stable cyclability are first demonstrated and the flow cell using low-conductive-content anolytes displays a high volumetric capacity of 207 Ah L-1 . This strategy paves a novel approach for optimizing semi-solid electrodes for high-performance Li-ion slurry flow batteries.

Highly Efficient Electrocatalytic CO2 Reduction to C2+ Products on a Poly(ionic liquid)-Based Cu0 -CuI Tandem Catalyst.

Electroreduction of CO2 on a polymer-modified Cu-based catalyst has shown high multi-electron reduction (>2 e- ) selectivity, however, most of the corresponding current densities are still too small to support industrial applications. In this work, we designed a poly(ionic liquid) (PIL)-based Cu0 -CuI tandem catalyst for the production of C2+ products with both high reaction rate and high selectivity. Remarkably, a high C2+ faradaic efficiency (FE C 2 + ) of 76.1 % with a high partial current density of 304.2 mA cm-2 is obtained. Mechanistic studies reveal the numbers and highly dispersed Cu0 -PIL-CuI interfaces are vital for such reactivity. Specifically, Cu nanoparticles derived Cu0 -PIL interfaces account for high current density and a moderate C2+ selectivity, whereas CuI species derived PIL-CuI interfaces exhibit high activity for C-C coupling with the local enriched *CO intermediate. Furthermore, the presence of the PIL layer promotes the C2+ selectivity by lowering the barrier of C-C coupling.

Understanding Structural and Transport Properties of Dissolved Li2 S8 in Ionic Liquid Electrolytes through Molecular Dynamics Simulations.

Lithium-sulfur batteries with high energy density are considered as one of the most promising future energy storage devices. However, the parasitic lithium polysulfides shuttle phenomenon severely hinders the commercialization of such batteries. Ionic liquids have been found to suppress the lithium polysulfides solubility, diminishing the shuttle effect effectively. Herein, we performed classical molecular dynamics simulations to explore the microscopic mechanism and transport behaviors of typical Li2 S8 species in ionic liquids and ionic liquid-based electrolyte systems. We found that the trifluoromethanesulfonate anions ([OTf]- ) exhibit higher coordination strength with lithium ions compared with bis(trifluoromethanesulfonyl)imide anions ([TFSI]- ) in static microstructures. However, the dynamical characteristics indicate that the presence of the [OTf]- anions in ionic liquid electrolytes bring faster Li+ exchange rate and easier dissociation of Li+ solvation structures. Our simulation models offer a significant guidance to future studies on designing ionic liquid electrolytes for lithium-sulfur batteries.

Anti-electrostatic hydrogen bonding between anions of ionic liquids: a density functional theory study.

Hydrogen bonds (HBs) play a crucial role in the physicochemical properties of ionic liquids (ILs). To date, HBs between cations and anions (Ca-An) or between cations (Ca-Ca) in ILs have been reported extensively. Here, we provided DFT evidence for the existence of HBs between anions (An-An) in the IL 1-(2-hydroxyethyl)-3-methylimidazolium 4-(2-hydroxyethyl)imidazolide [HEMIm][HEIm]. The thermodynamic stabilities of anionic, cationic, and H2O dimers together with ionic pairs were studied using potential energy scans. The results show that the cation-anion pair is the most stable one, while the HB in the anionic dimer possesses similar thermodynamic stability to the water dimer. The further geometric, spectral and electronic structure analyses demonstrate that the inter-anionic HB meets the general theoretical criteria of traditional HBs. The strength order of four HBs in complexes is cation-anion pair > H2O dimer ≈ cationic dimer > anionic dimer. The energy decomposition analysis indicates that induction and dispersion interactions are the crucial factors to overcome strong Coulomb repulsions, forming inter-anionic HBs. Finally, the presence of inter-anionic HBs in the ionic cluster has been confirmed by a global minimum search for a system containing two ionic pairs. Even though hydroxyl-functionalized cations are more likely to form HBs with anions, there are still inter-anionic HBs between hydroxyl groups in the low-lying structures. Our studies broaden the understanding of HBs in ionic liquids and support the recently proposed concept of anti-electrostatic HBs.

Inorganic Synthesis Based on Reactions of Ionic Liquids and Deep Eutectic Solvents.

Ionic liquids and deep eutectic solvents are of growing interest as solvents for the resource-efficient synthesis of inorganic materials. This Review covers chemical reactions of various deep eutectic solvents and types of ionic liquids, including metal-containing ionic liquids, [BF4 ]- - or [PF6 ]- -based ionic liquids, basic ionic liquids, and chalcogen-containing ionic liquids. Cases in which cations, anions, or both are incorporated into the final products are also included. The purpose of this Review is to raise caution about the chemical reactivity of ionic liquids and deep eutectic solvents and to establish a guide for their proper use.

Insight into the formation and permeability of ionic liquid unilamellar vesicles by molecular dynamics simulation.

Unilamellar vesicles in solution could open up new horizons for reaction and material delivery, but the formation mechanism especially for the permeability of the small molecule through the vesicle membrane is still unknown. In this study, the formation and permeability of the unilamellar vesicles formed by the ionic liquid 1-dodecyl-3-methylimidazolium salicylate ([C12mim][Sal]) have been investigated by molecular dynamics simulation. Starting from a random distribution of ionic liquids, the entire process of vesicle formation could be observed on a nanosecond time scale, during which planar and cup-like structures are formed at the intermediate stage. Energy analysis reveals that the electrostatic interactions between cations and anions play a dominant role in forming and stabilizing the vesicle. Radial density distribution functions indicate that the final stable vesicle is a spherical bilayer structure. Besides, it was found that the structure of vesicles is maintained with the increase of temperature, while the water molecules in the vesicles could be completely exchanged quickly. These results suggest that vesicles may be beneficial for the enrichment or release of molecules.