Search

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 N2solvation and solubility enhancement remains unclear. Massive molecular dynamics simulations and free energy perturbation methods are conducted to investigate the N2solubility 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 N2solubility than others and show an exothermic nature during solvation. As the C–F bonds number in ILs decreases, the N2solubility decreases significantly and displays the opposite endothermic behavior. To understand the ultrahigh N2solubility 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 N2solubility. Consequently, medium to long alkyl fluorine tails within a polar environment defines a distinct fluorine domain, emphasizing FDE’s role in enhancing N2solubility. Overall, these quantitative results will not only deepen the understanding of N2solvation in ILs but may also shed light on the rational design of IL-based high-performance N2capture and conversion technologies.

Heat capacity at constant pressure (Cp) of a molecular liquid medium is not only a basic physical property applicable in the calculation of microscopic characteristics but also a crucial property in chemical engineering processes. In this work, we utilized machine learning (ML) methodologies based on an established molecular liquid database to develop predictive models for Cpof fluids. The training data for these models were sourced from the literature and densityFfunctional theory (DFT) calculations, with simplified molecular input line entry system (SMILES) strings encoded via one-hot encoding as inputs to our models. Interestingly, the traditional ML algorithm extreme gradient boosting (XGBoost) produced the most effective predictive model, achieving a Pearson correlation coefficient exceeding 0.99, a root mean squared error (RMSE) of 1.95, and a mean absolute error (MAE) of 0.89, thus providing more accurate predictions of the Cpthan those obtained from DFT calculations. Additionally, we integrated Deep Belief Networks (DBNs) with Deep Neural Networks (DNNs), using DBNs for feature extraction and DNNs for subsequent prediction tasks. This combination successfully applied deep learning algorithms to small data set predictions, achieving a Pearson correlation coefficient of 0.96, a RMSE of 5.01, and a MAE of 2.21. Furthermore, we employed the SHAP library to analyze the interpretability of our models, examining the contribution of each feature within each descriptor to the overall model. Finally, comprehensive regression diagnostics were used to assess the reliability of the model, enhancing our understanding of its predictive capabilities.

Ionic liquids (ILs) are an emerging class of media of fundamental importance for chemical engineering, especially due to their interaction with solid surfaces. Here, we explore the growth phenomenon of surface-confined ILs and reveal a peculiar structural transition behavior from order to disorder above a threshold thickness. This behavior can be explained by the variation of interfacial forces with increasing distance from the solid surface. Direct structural observation of different ILs highlights the influence of the ionic structure on the growth process. Notably, the length of the alkyl chain in the cation is found to be a determining factor for the ordering trend. Also, the thermal stability of surface-confined ILs is investigated in depth by controlling annealing treatments. It is found that the ordered monolayer ILs exhibit high robustness against high temperatures. Our findings provide new perspectives on the properties of surface-confined ILs and open up potential avenues for manipulating the structures of nanometer-thick IL films for various applications.

Abnormalities in the transition between α-helices and β-sheets (α-β transition) may lead to devastating neurodegenerative diseases, such as Parkinson's syndrome and Alzheimer's disease. Ionic liquids (ILs) are potential drugs for targeted therapies against these diseases because of their excellent bioactivity and designability of ILs. However, the mechanism through which ILs regulate the α-β transition remains unclear. Herein, a combination of GPU-accelerated microsecond molecular dynamics simulations, correlation analysis, and machine learning was used to probe the dynamical α-β transition process induced by ILs of 1-alkyl-3-methylimidazolium chloride ([Cnmim]Cl) and its molecular mechanism. Interestingly, the cation of [Cnmim]+in ILs can spontaneously insert into the peptides as free ions (n≤ 10) and clusters (n≥ 11). Such insertion can significantly inhibit the α-β, transition and the inhibiting ability for the clusters is more significant than that of free ions, where [C10mim]+and [C12mim]+can reduce the maximum β-sheet content of the peptide by 18.5% and 44.9%, respectively. Furthermore, the correlation analysis and machine learning method were used to develop a predictive model accounting for the influencing factors on the α-β transition, which could accurately predict the effect of ILs on the α-β transition. Overall, these quantitative results may not only deepen the understanding of the role of ILs in the α-β transition but also guide the development of the IL-based treatments for related diseases.

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 AQP2by 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 AQP2in 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.

Ionic liquids (ILs) have shown promising potential in membrane protein extraction; however, the underlying mechanism remains unclear. Herein, we employed GPU-accelerated molecular dynamics (MD) simulations to investigate the dynamic insertion process of ILs into cell membranes containing membrane proteins. Our findings reveal that ILs spontaneously insert into the membrane, and the presence of membrane proteins significantly decelerates the rate of IL insertion into the membrane. Specifically, the relationship between the insertion rate and inserting free energy exhibits non-monotonic changes, which can be attributed to interfacial effects. The protein–water interface acts as trap for free ions and ionic clusters, while free ions preferentially insert into the membrane from the protein-lipid interface, which limits the insertion rate due to its narrowness. Thus, the insertion rate is governed by a combination of the free energy and interfacial effects. These findings provide valuable insights into the interfacial effects of protein-lipid bilayers and have implications for various biochemical-related applications.

Porous carbon materials (PCMs) play a pivotal role in diverse applications, such as energy storage, adsorption, catalysis, environmental remediation, and microwave adsorption. The selection of carbon precursors, in particular, is crucial for tailoring porous structures with specific functionalities. Biomass, with its rich carbon feedstock, abundant availability, renewability, and versatile structures, has emerged as a promising precursor for porous carbon material synthesis. This review comprehensively summarizes the recent advances in biomass-derived porous carbon materials (BPCMs) encompassing synthetic strategy, morphology, structural composition, and multiple applications. We first review synthetic approaches aiming at regulating porosity, followed by morphological and composition features of BPCMs, with a special emphasis on elucidating the dimensional clarification and heteroatom doping effects. The discussion then extends to the wide-ranging applications of BPCMs, covering energy-related applications and CO2adsorption to environmental remediation. Finally, the review outlines the existing challenges and prospects in the field. In summary, this review systematically describes BPCMs and provides valuable guidance for researchers to select and synthesize BPCMs that meet specific functional requirements.

Abstract: Quantum chemical calculations of the structures and cation-anion interaction of 1-ethyl-3-methylimidazolium lactate ([Em-im][ LAC]) ion pair at the B3LYP/6-31++G** theoretical level were performed. The relevant geometrical characteristics, energy properties, intermolecular H-bonds (H-bonds), and calculated IR vibrations with respect to isolated ions were systematically discussed. The natural bond orbital (NBO) and atoms in molecule (AIM) analyses were also employed to understand the nature of the interactions between cation and anion. The five most stable geometries were verified by analyzing the relative energies and interaction energies. It was found that the most of the C-H…O intermolecular H-bonds interactions in five stable conformers have some covalent character in nature. The elongation and red shift in IR spectrum of C-H bonds which involve in H-bonds is proved by electron transfers from the lone pairs of the carbonyl O atom of [LAC]− to the C-H antibonding orbital of the [Emim]+. The interaction modes are more favorable when the carbonyl O atoms of [LAC]− interact with the C2-H of the imidazolium ring and the C-H of the ethyl group through the formation of triple H-bonds.

Understanding the confined structure and flow behavior is significant for the design and application of ionic liquids (ILs) in the field of chemical engineering. Herein, the molecular mechanism of interfacial structure and flow behavior of ILs confined in crystalline silica (c-SiO2) and graphene-covered crystalline silica (g@c-SiO2) nanochannels are investigated via molecular dynamics simulation. The number density and angle distribution of ILs reveal that the cations at the c-SiO2interface display a vertical conformation, while those at the g@c-SiO2interface display a parallel conformation. Meanwhile, the anions are randomly distributed on these two substrates. Interestingly, the vertical distribution of cations in the c-SiO2substrate mainly presents three morphological structures, which will hinder the ion diffusion compared to the parallel ionic conformation. Furthermore, the nanoflow of ILs driven by external pressure shows a parabolic form in the nanochannel of c-SiO2, but the plug flows in the nanochannel of g@c-SiO2. The joint analysis of the mean square displacement, self-diffusion coefficient, flow velocity, and flow rate demonstrates that the parallel conformation of the cation can significantly facilitate the nanoflow process of confined ILs. These quantitative results are meaningful for understanding the molecular mechanism of nanoflow and lay the foundation for the rational design of IL-based devices and other chemical engineering processes.

Replacing homogeneous noble-metal catalysts with supported catalysts in hydrosilylation reactions can overcome the difficulties of catalyst recovery and regeneration. Here, we report the scalable synthesis of heterogeneous Pt/ZrO2catalysts with 1–5 wt % Pt supported on commercial ZrO2nanocrystals. Pt/ZrO2can effectively catalyze the hydrosilylation of triethoxysilane (TES) with ethyne to high-value triethoxyvinylsilane, even superior to the common homogeneous catalyst (H2PtCl6). Intensive characterizations indicate that the coating of ZrOxon Pt greatly depends on the size of Pt, with more ZrOxoverlayers on smaller Pt metal particles. Among all the catalysts, 2Pt/ZrO2exhibits the highest activity, optimal selectivity, and reusability toward hydrosilylation of TES with ethyne. The unusual catalytic properties of 2Pt/ZrO2can be attributed to its more abundant surface PtOxspecies and the electron transfer between Pt and ZrO2. This change in local electronic properties promotes catalytic activity, which is also supported by the corresponding theoretical calculation. This work advances the understanding of metal–support interactions and provides a powerful approach to designing environmentally friendly heterogeneous catalysts for the industrially important hydrosilylation process.

Lignin conversion into high value-added chemicals is of great significance for maximizing the use of renewable energy. Ionic liquids (ILs) have been widely used for targeted cleavage of the C–O bonds of lignin due to their high catalytic activity. Studying the cleavage activity of each IL is impossible and time-consuming, given the huge number of cations and anions. Currently, the mainstream approach to determining the cleavage activity of one IL is to calculate the activation barrier energy (Ea) theoretically via transition state search, a process that involves the iterative determination of an appropriate “imaginary frequency”. Machine learning (ML) has been widely used for catalyst design and screening, enabling accurate mapping from specified descriptors to target properties. To avoid complicated Eacalculations and to screen potential candidates, in this study, we selected nearly 103ILs and guaiacylglycerol-β-guaiacyl ether (GG) as the lignin model and used the ML technology to train models that can rapidly predict the cleavage activity of ILs. Taking the easily accessible bond dissociation energy (BDE) of the β–O–4 bond in GG as the target, an ML model with r> 0.93 for predicting the catalytic activity of ILs was obtained. The change tendency of the BDE is consistent with the experimental yield of guaiacol, reflecting the reliability of the ML model. Finally, [C2MIM][Tyrosine] and [C3MIM][Tyrosine] as the optimal candidates for future applications were screened out. This is a novel strategy for predicting the catalytic activity of ILs on lignin without the need to calculate complicated reaction pathways while reducing time consumption. It is anticipated that the ML model can be utilized in future practical applications for targeted cleavage of lignin.

Ionic liquids (ILs) hold great promise in the fields of green chemistry, environmental science, and sustainable technology due to their unique properties, such as a tailorable structure, the various types available, and their environmentally friendly features. On the basis of multiscale simulations and experimental characterizations, two unique features of ILs are as follows: (1) strong coupling interactions between the electrostatic forces and hydrogen bonds, namely in the Z-bond, and (2) the unique semiordered structure and properties of ultrathin films, specifically regarding the quasi-liquid. In accordance with the aforementioned theoretical findings, many cutting-edge applications have been proposed: for example, CO2capture and conversion, biomass conversion and utilization, and energy storage materials. Although substantial progress has been made recently in the field of ILs, considerable challenges remain in understanding the nature of and devising applications for ILs, especially in terms of e.g. in situ/real-time observation and highly precise multiscale simulations of the Z-bond and quasi-liquid. In this Perspective, we review recent developments and challenges for the IL research community and provide insights into the nature and function of ILs, which will facilitate future applications.

Frustrated Lewis pairs (FLPs) containing sterically hindered Lewis acidic and basic sites can capture and react with N2and CO2, thus furnishing a new strategy for urea electrosynthesis. Herein, the rice-like InOOH nanoparticles coupled with the well-defined FLPs (i.e., In In-OH) were synthesized and exhibited a urea yield rate of 6.85 mmol h−1g−1and faradic efficiency of 20.97% at −0.4 V versus reversible hydrogen electrode. Systematic investigations reveal that the electron-deficient Lewis acidic In sites and electron-rich Lewis basic In-OH achieve the targeted chemisorption of the N2and CO2molecules by electronic interaction respectively. The bonding and antibonding orbitals of reactant molecules interact with the unoccupied orbitals of Lewis acid and nonbonding orbitals of Lewis base to generate the desired intermediates for urea synthesis in artificial FLPs. In addition, FLPs can further ensure the orbital-matched intermediates of ∗N=N∗ and CO proceed with the desirable C–N coupling reaction to produce ∗NCON∗ precursors.

Limited by the rare efficient extraction system in extracting hydrophobic membrane protein complexes (MPCs) without compromising the stability of protein–protein interactions (PPIs), the in-depth functional study of MPCs has lagged far behind. In this study, the first systematic screening of ionic liquids (ILs) was performed and showed that triethylammonium acetate (TEAA) IL exhibited excellent performance in stabilizing PPIs, which was further confirmed by molecular docking simulations. By combining TEAA with the conventional detergent Nonidet P-40 (NP-40), a novel IL-based extraction system, i-TAN (TEAA IL with 1% NP-40), was proposed, which demonstrated superior performance in extracting and stabilizing MPCs, attributed to its larger size, more uniform distribution, and closer-to-neutral microenvironment of micelles. Extraction of MPCs with i-TAN allowed the confident identification of more hydrophobic EGFR-interacting proteins that are easily dissociated during the extraction process. Quantitative analysis of the difference in EGFR complexes between trastuzumab-sensitive and trastuzumab-resistant breast cancer cells provided comprehensive insights to understand the drug resistance mechanism, suggesting that i-TAN has great potential in interactomics and functional analysis of MPCs. This study provides a novel strategy for MPC extraction and downstream processing.

Using biomass and renewable feedstocks to prepare high value-added products instead of conventional petrochemicals has received extensive attention recently. In this work, a facile and phosgene-free approach for synthesizing bio-based polycarbonate is developed viamelt polycondensation of isosorbide (ISB) and dimethyl carbonate (DMC), which are both derived from renewable biomass resources and CO2. Several kinds of acylamido-based anion-functionalized ionic liquids (ILs) are prepared and used as catalysts to promote the reaction of ISB and DMC. Their catalytic performances in the transesterification stage and the polycondensation stage are evaluated. Results show that acylamido-based ILs with a low anion–cation interaction energy and a high natural population analysis atomic charges of the nitrogen atom exhibited good catalytic performance. Furthermore, by using tetrabutylphosphonium phthalimide as the catalyst, the selectivity of carboxymethylation of DMC and conversion of ISB significantly increased to 99.6% and 99.0%, respectively. Quantum chemical calculations reveal that the dramatic enhancement of endo-OH reactivity originated from the interactions between the acylamido and –OH groups. Based on the NMR data and DFT calculations, a plausible synergistic catalytic mechanism involving cation–anion is proposed. This work not only provides guidance for the design and synthesis of efficient IL catalysts, but also is applicable to exploring the industrial possibilities of developing value-added bioproducts from renewable feedstocks.

Unfavorable factors such as the shuttle effect caused by soluble lithium polysulfides, insulation of S and Li2S, and large volume expansion of S have greatly hindered the practical application of lithium–sulfur batteries. Using sulfur cathodes based on metal oxide nanocomposite materials has been proven to be an effective method to overcome the abovementioned problems and accomplish long-term cycle stability, excellent conductivity, and high-rate capacity. However, there is still a lack of clear mechanism research to balance between adsorption and diffusion and speedy selection method for oxides. Herein, we systematically studied the anchoring and diffusion properties of metal oxide MO2(TiO2, SnO2, and RuO2) as cathode materials and then screened the materials through the equilibrium mechanism of adsorption and diffusion. According to the abovementioned research, due to its strong interaction with lithium polysulfides and low diffusion barrier for Li+, TiO2exhibits excellent electrochemical performance and is considered to have great potential as an anchor material for lithium–sulfur batteries. Therefore, a comprehensive metal oxide selection criterion with stronger bonding strength (3–5 eV) and a lower diffusion barrier (<0.4 eV) is proposed. This work provides general guidance for the construction and screening of cathode materials to attain high-performance batteries in the future.

Understanding the dynamic process of interfacial charge transfer prior to chemisorption is crucial to the development of electrocatalysis. Recently, interfacial water has been highlighted in transferring protons through the electrode/electrolyte interface; however, the identification of the related structural configurations and their influences on the catalytic mechanism is largely complicated by the amorphous and mutable structure of the electrical double layer (EDL). To this end, sub-nanometric Pt electrocatalysts, potentially offering intriguing activity and featuring fully exposed atoms, are studied to uncover the elusive electrode/electrolyte interface via operando X-ray absorption spectroscopy during the hydrogen evolution reaction (HER). Our results show that the metallic Pt clusters derived from the reduction of sub-nanometric Pt clusters (SNM-Pt) exhibit excellent HER activity, with an only 18 mV overpotential at 10 mA/cm2and one-magnitude-higher mass activity than commercial Pt/C. More importantly, a unique Pt-interfacial water configuration with a Pt (from Pt clusters)–O (from water) radial distance of approximately 2.5 Å is experimentally identified as the structural foundation for the interfacial proton transfer. Toward high overpotentials, the interfacial water that structurally evolves from “O-close” to “O-far” accelerates the proton transfer and is responsible for the improved reaction rate by increasing the hydrogen coverage.

ABSTRACTAerospace optical remote sensing is an effective information technology that retrieves physical characteristics of ground objects. With the development of multi-mode payloads and the fusion of multi-source information in spaceborne remote sensing technology, the demand for quantitative and accurate information has raised a series of new issues on information chain technology, and it has also shown great prospects for remote sensing applications. Optical remote sensing image is the basic carrier of feature information. The effect of remote sensing applications largely depends on the image quality. Therefore, improving the imaging quality is of great significance for remote sensing applications. In this letter, the scatter radiation transfer process of the imaging system has been analysed; working principle of scattering imaging in the earth observation process has been introduced, the influence of scatter radiation transfer on remote sensing image quality has been discussed, and the factors of image radiation accuracy has been specified.

The ability to tune structures and properties of interfacial ionic liquids (ILs) using electric fields lies at the heart of modern energy storage technologies, particularly for supercapacitors with ILs as electrolytes. Direct observation of the underlying structural change caused by charge injection is vitally important, but the data are extremely scarce. Here, we propose a general protocol to explore the dynamic structural response of interfacial ILs subjected to charge injection. The experimental results have revealed asymmetric structural evolution of interfacial ILs with a common feature of enhanced mobility during charge injection. Consequently, the surface ILs diffuse and agglomerate into various patterns, which depend critically on both the charge injection mode and initial structural feature. Slow and mild charge injection is advantageous in maintaining structural stability as well as regulating dielectric constants of interfacial ILs. Finally, we unveil the underlying energy conversion from electric energy to thermal energy that governs the structural evolution trend. Our current findings manifest a universal strategy for structural regulation of interfacial ILs via electric fields and open up opportunities for greatly accelerating charging efficiency of supercapacitors for energy storage and harvesting.

The integration of molecular design and imidazole ionic liquids produces a synergistic effect to enhance and fine-tune the molecular sieve capability of polyimide (PI) membranes. The most difficult problem was to choose the right ionic liquids and moderate polymer combination. In this work, a series of systems of CO2in [EMIM][Tf2N], [EMIM][BF4], and [EMIM][PF6] composited with 6FDA-based PI with different IL concentrations were discussed by all-atom molecular dynamics simulations. The results indicated that the CO2diffusion coefficient decreases with the compatibility of the PI structure with CO2molecules and increases with an increased IL concentration of up to 75 wt %. Therefore, this study may provide guidance for the design of PI membranes.

Implant loosening remains a major clinical challenge for osteoporotic patients. This is because osteoclastic bone resorption rate is higher than osteoblastic bone formation rate in the case of osteoporosis, which results in poor bone repair. Strontium (Sr) has been widely accepted as an anti-osteoporosis element. In this study, we fabricated a series of apatite and Sr-substituted apatite coatings via electrochemical deposition under different acidic conditions. The results showed that Ca and Sr exhibited different mineralization behaviors. The main mineralization products for Ca were CaHPO4·2H2O and Ca3(PO4)2with the structure changed from porous to spherical as the pH values increased. The main mineralization products for Sr were SrHPO4and Sr5(PO4)3OH with the structure changed from flake to needle as the pH values increased. The in vitroexperiment demonstrated that coatings fabricated at high pH condition with the presence of Sr were favorable to MSCs adhesion, spreading, proliferation, and osteogenic differentiation. In addition, Sr-substituted apatite coatings could evidently inhibit osteoclast differentiation and fusion. Moreover, the in vivostudy indicated that nano-needle like Sr-substituted apatite coating could suppress osteoclastic activity, improve new bone formation, and enhance bone-implant integration. This study provided a new theoretical guidance for implant coating design and the fabricated Sr-substituted coating might have potential applications for osteoporotic patients.

Assembling two-dimensional (2D) materials by polyelectrolyte often suffers from inhomogeneous microstructures due to the conventional mixing-and-simultaneous-complexation procedure (“mix-and-complex”) in aqueous solution. Herein a “mix-then-on-demand-complex” concept viaon-demand in situcascade anionization and ionic complexation of 2D materials is raised that drastically improves structural order in 2D assemblies, as exemplified by classical graphene oxide (GO)-based ultrathin membranes. Specifically, in dimethyl sulfoxide, the carboxylic acid-functionalized GO sheets (COOH–GOs) were mixed evenly with a cationic poly(ionic liquid) (PIL) and upon filtration formed a well-ordered layered composite membrane with homogeneous distribution of PIL chains in it; next, whenever needed, it was alkali-treated to convert COOH–GO in situinto its anionized state COO––GO that immediately complexed ionically with the surrounding cationic PIL chains. This “mix-then-on-demand-complex” concept separates the ionic complexation of GO and polyelectrolytes from their mixing step. By synergistically combining the PIL-induced hydrophobic confinement effect and supramolecular interactions, the as-fabricated nanofiltration membranes carry interface transport nanochannels between GO and PIL, reaching a high water permeability of 96.38 L m–2h–1bar–1at a maintained excellent dye rejection 99.79% for 150 h, exceeding the state-of-the-art GO-based hybrid membranes. The molecular dynamics simulations support the experimental data, confirming the interface spacing between GO and PIL as the water transport channels.

The emergence of multi-drug resistance makes bacterial infection a major threat to public health and economy. The formation of bacterial biofilms is one of the main reasons of bacterial resistance. The complexity of chemical composition and physical structure makes the elimination of mature biofilms a difficult problem. The highly antibiotic resistant property of biofilms urgently calls for potent antimicrobial agents and novel antibiofilm strategies. Researchers have made a lot of efforts in this field. Here we review the current strategies to eliminate mature biofilms and progress in related drug delivery nanosystems, with the aim of inspiring researchers to design new antibiofilm systems.

Enhancing molecular interaction is critical for improving the immobilization and stability of proteins on TiO2surfaces. In this work, mesoporous TiO2materials with varied pore geometries were decorated with phenyl phosphoric acid (PPA), followed by a thermal treatment to obtain chemically heterogeneous C–TiO2samples without changing the geometry and crystalline structure, which can keep the advantages of both carbon and TiO2. The molecular interaction force between the protein and the surfaces was measured using atomic force microscopy by decomposing from the total adhesion forces, showing that the surface chemistry determines the interaction strength and depends on the amount of partial carbon coverage on the TiO2surface (∼40–80%). Samples with 58.3% carbon coverage provide the strongest molecular interaction force, consistent with the observation from the detected friction force. Surface-enhanced Raman scattering and electrochemical biosensor measurements for these C–TiO2materials were further conducted to illustrate their practical implications, implying their promising applications such as in protein detection and biosensing.

The utilization of ionic liquids (ILs) as electrolytes in lithium-ion batteries is of great academic and industrial significance. Previous studies have shown that clusters can be formed in IL electrolytes. However, the influence of clusters on [Li] solvation and transport is still ambiguous, especially under external electric fields. The structural, dynamical, and transport properties of mixed organic compound/IL electrolytes, consisting of lithium salts ([Li][TFSI], [Li][BF4], and [Li][PF6]), organic solvents (ethylene carbonate (EC) and dimethyl carbonate (DMC)), and ILs ([EMIM][TFSI], [EMIM][BF4], [EMIM][PF6], and [PYR14][TFSI]) under external electric fields were investigated using molecular dynamics (MD) simulations. The results suggest a strong relationship between the cluster structures and the applied external electric fields. Under low electric fields, no obvious change of cluster structures was observed, but due to the electrophoretic effect, [Li] diffusion was weakened. Under high electric fields, the anions around [Li] could be partially substituted by DMC molecules, and it was found that [Li] diffusion could be increased significantly. The physical insights provided in the study demonstrate that the original larger ion clusters tend to be smaller on increasing the strength of the external electric fields, thereby enhancing the transport of [Li].

Figuring out the wetting behavior and interfacial structure of ionic liquid (IL) droplets on solid surfaces is imperative for the new IL-based application in the field of chemical engineering. In this work, the quantitative relations between the wetting properties and solid surface property are explored through molecular dynamics simulations. Interestingly, two different equilibrium configurations, nonspreading structure and partial spreading structure, are identified for ILs when the solid interface property changes from hydrophobic to hydrophilic. Considering the quantitative relation between the contact angle (CA) and the solid surface energy (εs), both EmimCl and EmimPF6show an abnormal wetting behavior compared with water, where the CA−εsrelation for ILs deviates the theoretical linear model when εsis beyond the critical surface energy εc. The reduced density distribution and orientation distribution show that ILs could form a denser solidified ionic layer near the solid surface, which will not happen to water. Moreover, the dynamical properties including the retention rate and vibrational displacement for ions and water molecules confirmed that the solidified ionic layer almost lost the fluid nature, while the adjacent water layer still possesses relatively high fluidity, especially when εs> εc. That is to say, the dense solidified ionic layer which lost its mobility can bring about such an abnormal wetting behavior of ILs. These factors can serve as key indicators in characterizing the mechanism of the structural transition of ILs wetting the solid surface and facilitate the rational design of the surface modification or strain engineering of the solid substrates.

The cycloaddition of CO2with epoxides catalyzed by ionic liquids (ILs) has been a widely ongoing studied hot topic over the years. Recent experimental research has shown that the protic ionic liquids (PILs) behave stronger hydrogen proton donating ability than aprotic ionic liquids (APILs), and can effectively catalyze the cycloaddition of CO2. Unfortunately, the mechanistic explanation remains primarily unraveled. Herein, a detailed simulation study on the cycloaddition reaction catalyzed by PIL ([HDBU][Mim]) in comparison with APIL ([MeDBU][Mim]) reaction catalysts was conducted, including the three-step route (ring-opening of PO (propylene oxide), insertion of CO2and ring-closure of propylene carbonate (PC)) and two-step route (simultaneously ring-opening of PO and addition of CO2, and then ring-closure of PC). Based on the activation energy barrier of the rate-determining step, PIL preferentially activates PO as the optimal route for the reaction with the energy barrier of 23.2 kcal mol-1, while that of APIL is 31.2 kcal mol-1. The role of [HDBU]+in the reaction was also explored and found that the direct formation of intermolecular hydrogen bond (H-bond) between [HDBU]+and the reactants (PO + CO2) was unfavorable for the reaction, while the cooperation with the anion [Mim]-to assist indirectly was more conducive. To fully consider the reaction microenvironment of ILs, ONIOM calculation was used to study the solvent effect. At last, the above conclusions were further verified by the analysis of intermediates with charge, non-covalent interaction (NCI), and atoms in molecules (AIM) methods. The computational findings show that ILs studied in this work have dual functions of catalyst and solvent, enabling a microscopic understanding of the ILs catalyst for CO2utilization as well as providing guidance for the rational design of more efficient ILs-based catalysts.

Heat transfer processes not only widely exist in practical industrial processes but are also very important and depend greatly on the thermal properties of the liquid medium. However, the numerous types and diverse structures of liquid media and insufficient data on thermal properties pose significant challenges in the application of thermal liquid media. In this work, we established a Fluid_Thermodatabase for molecular liquids and ionic liquids (ILs) containing 18 different physicochemical and electronic properties and, in total, 18,000 data points. Moreover, based on the database, the similarity of liquids was determined by clustering analysis methods, classifying the liquids into nine categories to analyze further the relationship between structure and thermal conductivity (TC). It was found that structures with single chains and double bonds significantly impact TC for molecular liquids, whereas for ILs, structures similar to 1-butyl-3-methylimidazolium tetrafluoroborate have a higher TC. We also analyzed the variation of TC with temperature for different liquids and constructed a predicted relationship between TC and temperature. Finally, the impact and connection of various physical properties on the TC are summarized and discussed. Such a database can provide valuable information for studying complex fluid media and deepen our understanding of the physical characteristics and behaviors of molecular liquids and ILs.

Evaporation power generation (EPG), hailed as a promising clean power generation technology, has garnered significant attention. Nonetheless, achieving consistent and replicable performance of EPG remains a major challenge, hampering its practical application potential. Herein, we present the design of a tri-layered poly-ionic membrane (TL-PIM) inspired by transpiration processes in plants, that can not only continuously output electricity with an average voltage of ~0.6V for over 8 consecutive days with a maximum power density of 1.6µWcm−2, but can also be reused for at least 70 cycles (> 350hours) with a stable voltage, demonstrating superior repeatability over most previous works. The excellent long-lasting and repeatable performance of EPG in the TL-PIM can be attributed to the stable nanochannels constructed by a hydrophilic polymer, 2D nanosheets, and poly-ionic liquids (PILs), where the bromide ions (Br-) in the PILs can shuttle back and forth selectively and efficiently during the power generation and discharge processes. More importantly, the TL-PIM can be integrated linearly to generate electricity within a wide range of temperatures and humidity, even outdoors, showcasing remarkable environmental adaptability. These findings on EPG indicate that the bio-inspired TL-PIM offers a promising venue for continuous and reproducible electricity generation by harnessing thermal energy from moisture, which holds significance for the sustainable utilization of EPG as a renewable energy source in the future.

The understanding and regulation of thermal transport across the solid–liquid interface, especially the electrical double layer (EDL) formed by ionic liquid (IL), is significant for the reasonable design of the efficient thermal dissipation capabilities in the field of chemical engineering. In the present work, by large-scale molecular dynamics simulation method, we reveal that rather than the strong solid–liquid interaction, the atomic structure of EDL dominates the entire interfacial thermal transport across the solid–IL interfaces. The simulation results show that as the surface charge increases, the interfacial thermal resistance (ITR) will decrease in two stages, first sharply and then slowly. The two-dimensional structure factors, the geometry state of cation, and the solid–liquid interfacial energy for different surface charges demonstrate that the evaluation of EDL agrees well with the trend of ITR. Furthermore, the vibrational spectrum and frequency-dependent heat flow also indicate that the high-ordered EDL will enhance the interfacial thermal transport in all frequencies, that is, the high-ordered EDL structure can induce the ultralow thermal resistance and enhance the heat dissipation process. These results also enlightened the future rational design and thermal management of the new IL-based nanoelectrical devices as well as coolants used in the advanced chemical engineering processes, such as supercapacitors, Li-ion batteries, and so forth.

Lithium battery with high energy density and enhanced safety is undoubtedly the ideal choice for consumer electronics and electric vehicles. Metal anode such as lithium has been considered as the most effective way to enhance the energy density as it provides ultra-high theoretical capacity and the lowest redox potential. However, due to the low coulombic efficiency as well as safety concerns originated from dendrite issue of lithium, its further commercial utilization is hindered. Dendrite growth is a common phenomenon in metal electrodeposition while the plating process of Li is more complicated than other metals for its high reactivity nature. As a matter of fact, the Li plating process is accompanied with the generation of solid electrolyte interphase (SEI) in which the electrolyte plays a vital role. In this paper, recent advances of electrolytes for Li protect application are reviewed, from liquid to gel polymer and solid state, on which we find that although tremendous progress has been accomplished, there are still great challenges before Li metal anode could be commercially used.

Carbon dioxide methanation is well known to achieve the catalytic conversion of the CO2molecule into value-added chemicals. At present, the important challenge is the development of efficient methanation catalysts at low reaction temperature. In this study, Ni–Al layered double hydroxides (LDHs) were used as catalyst precursors and modified by CeO2for CO2methanation. By the optimization of CeO2loading, the reaction activity was improved, especially at low temperature. Among the prepared catalysts, the NiAl-MO/CeO2-5 catalyst exhibited the highest catalytic activity with a CO2conversion of 91% at 250 °C. The addition of CeO2was beneficial to the formation of small particles with good dispersion and provided appropriate basic sites and oxygen vacancies, which were conducive to the catalytic performance. DFT calculation and in situDRIFTS results further verified that the catalyst with an appropriate amount of CeO2was favorable for CO2adsorption and conversion. The reaction mechanism results demonstrated that the high amount of formate intermediate species can accelerate the reaction and a certain amount of ceria in the catalyst could provide a suitable metal–support interaction, which was beneficial for CO2methanation. The LDH as a catalyst precursor integrated with CeO2shows a promising effect on CO2methanation at low temperature.

Biodegradable Polymers In article 2300068by Qiang Chen, Yulin Li, and co‐workers, a versatile disorder‐to‐order technology (VDOT) is proposed to fabricate a stereo‐composite self‐reinforced polymer fiber by mimicking the superstructure of nature bones at the nanoscale. The VDOT‐based polymer fiber shows an oriented shish‐kebab structure, excellent mechanical performance, and biodegradation stability, which overcome the mechanical inferiority of the current biomedical polymers and extend their applications.

Biodegradable polymer as traditional material has been widely used in the medical and tissue engineering fields, but there is a great limitation as to its inferior mechanical performance for repairing load‐bearing tissues. Thus, it is highly desirable to develop a novel technology to fabricate high‐performance biodegradable polymers. Herein, inspired by the bone's superstructure, a versatile disorder‐to‐order technology (VDOT) is proposed to manufacture a high‐strength and high‐elastic modulus stereo‐composite self‐reinforced polymer fiber. The mean tensile strength (336.1 MPa) and elastic modulus (4.1 GPa) of the self‐reinforced polylactic acid (PLA) fiber are 5.2 and 2.1 times their counterparts of the traditional PLA fiber prepared by the existing spinning method. Moreover, the polymer fibers have the best ability of strength retention during degradation. Interestingly, the fiber tensile strength is even higher than those of bone (200 MPa) and some medical metals (e.g., Al and Mg). Based on all‐polymeric raw materials, the VDOT endows bioinspired polymers with improved strength, elastic modulus, and degradation‐controlled mechanical maintenance, making it a versatile update technology for the massive industrial production of high‐performance biomedical polymers. Inspired by the design strategy of nature bones at the nanoscale, a versatile disorder‐to‐order technology (VDOT) is proposed to fabricate a high‐performance stereo‐composite self‐reinforced (SR) polymer fiber. The VDOT endows bioinspired polymers with improved strength, elastic modulus, and degradation‐controlled mechanical maintenance, and can be used for the massive industrial production of high‐performance biomedical polymers.

Because of the sluggish dynamic and complex electrostatic potential networks of ionic liquids, establishing a reasonable and efficient coarse-grained model with enough simulation time is very important for a large system. In this work, novel coarse-grained models of 1-n-alkyl-3-methylimidazolium chloride [Cnmim][Cl] (n= 4, 6, 8) have been developed from the united atom model of ionic liquids. There are two mapping strategies for the ionic liquids coarse graining, one is that the imidazolium cations ([Cnmim]+(4, 6, 8)) and Cl–anion are represented as single coarse-grained bead as an ionic model. The other is a pair of ionic liquids mapped to one bead as a molecular model. It was found that both of the coarse-grained models could give a good description of structures and thermodynamic properties for ionic liquids. Moreover, because of the reducing freedom of a coarse-grained model a correction of the results as a united atom force field was established for self-diffusion coefficients which could be reproduced effectively. Notably, the ionic model improves the calculation efficiency up to 9.5 times compared with united atom force field under the same simulation conditions because the electrostatic potentials in the ionic model are highly important for coarse-grained model for ionic liquids. In summary, the coarse-grained models could provide a theoretical basis for large-scale ionic liquids systems.

Understanding of energy transport across the solid–liquid interface is essential for the rational design of efficient heat dissipation capabilities. In this work, we show that the molecular orientation of liquid near the solid surface dominates the thermal transport across the imidazolium ionic liquids (IL)/graphene interface via molecular dynamics simulations. The molecular orientation is defined as the parallelism between the imidazole ring in IL and graphene and is controlled by wettability of graphene. Interfacial thermal resistance (ITR) will decrease linearly with the parallelism, which is suitable for IL with different tail chain length (2, 4, 6, and 8). From the linear relationship, a lower limit of ITR for the IL–graphene interface can be predicted, which is on the order of ∼6 m2K/GW and stands for the lower bound of ITR across the solid–liquid interface. Furthermore, it is indicated that the parallel imidazole ring in IL facilitates the thermal transport via shifting the dominating vibrational modes to a higher frequency (∼15 THz). These findings show that the molecular orientation can be an effective factor to control the interfacial thermal transport, which can shed light on the future rational designs of some key chemical engineering processes, such as IL-based coolants, batteries, nanoelectrical devices, and so on.