Converting the lignin into value-added chemicals and fuels represents a promising way to upgrade lignin. Here, we present an effective electrocatalytic approach that simultaneously modulates the depolymerization and hydrogenation pathways of lignin model compounds within a single reaction system. By fine-tuning the pH of the electrolyte, we achieve a remarkable shift in product selectivity, from acetophenone (with selectivity >99%) to 1-phenylethanol (with selectivity >99%), while effectively preventing over-hydrogenation. The robust metallic glass (MG) catalyst, endowed with an amorphous structure, demonstrates high stability, activity, and full recyclability across over 100 consecutive cycles in ionic liquid electrolytes. The relatively strong affinity of the MG catalyst for the substrate during the initial reaction stage, in conjunction with its weaker binding to the phenolic product, as the reaction progresses, creates a delicate balance that optimizes substrate adsorption and product desorption, which is pivotal in driving the cascade hydrogenation process of acetophenone. This work opens versatile pathways for lignin upgrading through integrated tandem reactions and expands the scope of catalyst design with amorphous structures.

Organic molecules containing azobenzene (azo) groups commonly undergo cis-trans isomerization upon light irradiation. It has been constructed azobenzene into the cation of ionic liquid (IL) for CO2 capture. A series of the derivatives based on the reported photo-responsive IL (trans-azo-IL) have been further designed by modifying the ortho-, meta-, and para-site of azo group with different electron-donating and electron-withdrawing groups (-NH2, -OH, -OCH3, -CH3, -CN, -NO2). By investigating the matching of the frontier molecular orbital energy levels between ILs and CO2, the trans-cis isomerization energy, the binding energy between the cation and anion, the hydrogen bond interaction, the UV-visible absorption properties, and diffusion behavior by multiscale simulations, it found that -OH substituted on ortho-site of azo could further improve the performance of CO2 capture compared to the original structure. The results provide a novel strategy for the screening and design of functional IL in CO2 capture in the future.

Balancing conductivity, adhesion, and environmental stability remains a central challenge for next-generation conductive adhesives. Here, we report a facile metal-doping strategy for poly(ionic liquid) (PIL) adhesives, embedding Li+, Na+, or Ag+ salts within an ionic-liquid-polymer network to simultaneously reinforce interfacial binding and optimize ion transport. Systematic synthesis, multiscale characterization, and molecular dynamics simulations reveal that metal coordination sites concentrate at the polymer-substrate interface, yielding record adhesion strength up to 9.15 MPa on stainless steel for PIL-[Ag]. Electrochemical impedance spectroscopy shows that Li+-doped PIL exhibits an ultralow charge-transfer resistance of 0.24 MΩ, 3 orders of magnitude lower than that of conventional PILs. These adhesives also offer tunable electromechanical properties, ∼88% optical transparency, and reliable low-temperature performance (-50 °C), making them ideal for flexible electronics, wearable sensors, and smart interface 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 CO 2 adsorption 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.

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.

In this study, we analyzed the species in a model electrolyte consisting of a lithium salt, lithium bis(trifluoromethane sulfone)imide (LiTFSI), and a widely used neutral solvent propylene carbonate (PC) with excess infrared (IR) spectroscopy, ab initio molecular dynamics simulations (AIMD), and quantum chemical calculations. Complexing species including the charged ones [Li+(PC)4, TFSI-, TFSI-(PC), TFSI-(PC)2, and Li(TFSI)2-] are identified in the electrolyte. Quantum chemical calculations show strong Li+···O(PC) interaction, which suggests that Li+ would transport in the mode of solvation-carriage. However, the interaction energy of each hydrogen bond in TFSI-(PC) is very weak, suggesting that TFSI- would transport in hopping mode. In addition, the concentration dependences of the relative population of the species were also derived, providing a scenario for the dissolving process of the salt in PC. These in-depth studies provide physical insights into the structural and interactive properties of the electrolyte of lithium-ion batteries.

Structural characterization of assemblies in solutions is essential for understanding the relationship between the structure and material properties. In this study, we introduce a novel approach to investigate amphiphilic self-assemblies in solutions using the phospholipid molecule 1-palmitoyl-2-hydroxy-sn-glycero-3-phosphocholine (Lyso PC) as a 31P NMR probe. The high natural abundance and gyromagnetic ratio of 31P make it one of the most sensitive nuclei in the low-frequency region, enabling efficient detection even in dilute solutions. Lyso PC can readily co-assemble with amphiphilic molecules and ions in aqueous solutions, forming various structures, such as hexagonal, lamellar, and micellar assemblies. The characteristic line shapes of these assemblies reflect the chemical environment around the probe and provide insights into the different phase states of the assemblies. This strategy offers a simple, cost-effective, and static method for obtaining structural information about various assemblies. Our work not only introduces a sensitive probe for characterizing assemblies in a solvent environment but also inspires new ideas for the development of similar spectroscopic probes.

One important quest for making high quality materials with amphiphiles is to understand how a disordered self-assembly changes to a stable crystalline state. Herein, we addressed the basic question by investigating the phase transition mechanism of imidazolium-based ionic liquid (IL) [C16mim]Br, using time-resolved small- and wide-angle X-ray scattering (SAXS-WAXS), differential scanning calorimetry, and Fourier transform infrared spectroscopy techniques. Totally, a hexagonal phase, two lamellar-gel phases, and three lamellar-crystalline phases were observed, showing the special polymorphism of the system. It was demonstrated that at low concentrations the two-dimensional gel phase (Lβ1) transforms into the most stable lamellar-crystal phase (Lc3) through two intermediate crystalline phases Lc1 and Lc2. At high concentrations, the Lβ1 phase changes to a condensed lamellar gel phase (Lβ2) before changing to Lc2 and eventually to Lc3. Comparative studies using [C16mim]Cl and [C16mim]NO3 unveiled that the interactions between the counterions and the headgroups of the IL, as well as the dehydration process, govern the nucleation process of Lc3 and thus the formation of the crystal. The in-depth investigation on the transition mechanism and the phase polymorphism in the present work advances our understanding of the crystallization of amphiphilic ionic liquids in dispersions and would promote future applications.

Lithium batteries have been widely used in all over the world for its high energy density, long-term cy-cle stability. While the resources of lithium metal and transition metal are limited, which restrict their applications in the grid energy storage. Dual ion sodium batteries (DISBs) possess higher energy density, especially owning high power density for its higher operating voltage (> 4.5 V). Nevertheless, the poor oxidation tolerance of carbonate electrolyte and the co-intercalation of solvents accompanied with anions are main obstacles to make the DISBs commercialization. Herein, a physical barrier (artificial SEI film) is pre-constructed in the Na||graphite batteries to solve these thorny problems. With the CSMG (covered SEI on modified graphite), batteries deliver higher capacity 40 mAh/g even under the current density of 300 mA/g and the capacity retention maintains very well after 100 cycles at a high operating voltage. Moreover, the function mechanism was revealed by in-situ XRD, demonstrating that the pre-constructed SEI can effectively suppress the irreversible phase transition and exfoliation of graphite, resulting from the co-intercalation of anions. Additionally, the work voltage windows of carbonate electrolyte are signif-icantly broadened by establishing electrode/electrolyte interphase. This method opens up an avenue for the practical application of DISBs on the grid energy storage and other fields.(c) 2023 Published by Elsevier B.V. on behalf of Chinese Chemical Society and Institute of Materia Medica, Chinese Academy of Medical Sciences.

Understanding the interactions between carbohydrate polymer molecules and biomolecules is of primary significance for its application. In this paper, the interaction between cellulose and biomolecules was studied using density functional theory method, in which cellobiose, nucleobases, and aromatic amino acids were employed as the structural models of cellulose, DNA, and protein, respectively. Quantitative molecular surface electrostatic potential (ESP) results well represented how cellulose perceived by organism during the recognition. The structural and energetic studies of cellulose with biomolecules complexes show that weak interactions, such as hydrogen bonding interaction, vdW interaction, and pi-H interaction, play an important role in stabilizing these complexes. Through systematic wavefunction analysis, including reduced density gradient (RDG) and natural bond orbital (NBO) methods, the nature of these weak interactions was revealed and further graphically visualized. In-depth understanding of the interaction between cellobiose with biological model molecules may shed lights on the application of carbohydrate polymer-based materials in biological fields.

Ionic liquids (ILs) exhibit fascinating properties due to special Z-bonds and have been widely used in electrochemical systems. The local Z-bond networks potentially cause a discrepancy in electrochemical properties. Understanding the correlations between the Z-bond energy (EZ-bond) and the electrochemical properties is helpful to identify appropriate ILs. It is difficult to estimate the correlations from single density functional theory calculations or molecular dynamic simulations. In this work, a machine learning model targeting the electronic density (ρBCP) of Z-bonds has been trained successfully, as expected for use in systems above the nanoscale size. The connection between the EZ-bond and the electrochemical potential window in ILs@TiO2, as well as that between the EZ-bond and the charge carrier mobility in ILs-PEDOT:Tos@SiO2, was separately investigated. This study highlights an efficient model for predicting ρBCP in nanoscale systems and anticipates exploring the connection between Z-bonds and the electrochemical properties of IL-based systems.

The fabrication of two-dimensional crystals (2DCs) has attracted very large interest because it creates materials with various surface structural features and special surface properties. Normally, this is limited to sheets networked together with strong covalent or coordination bonds. Against this understanding, we discovered macroscopic scale free-standing 2DCs in the aqueous dispersions of [Cnmim]X (X = Br, NO3; n = 14, 16, 18) using simultaneous synchrotron small- and wide-angle X-ray scattering techniques. On the other hand, the 2DCs are also a kind of novel hydrogel holding water content up to 98 wt %. This unusual phenomenon is attributed to the weak interactions between imidazole headgroups and counterions. The observation reported in this work is expected to contribute to theorists in their pursuit of the general principles governing the stability of 2D materials. It may also enlighten experimentalists in designing new free-standing 2DCs for various applications.

Ionic liquids (ILs), although being a class of promising green solvents, have received many reports on the toxicity to living organisms. In this work, aiming at elucidating the disruptive effect of ILs to cell membrane lipid rafts, we investigated the effect of three 1-octylimidazolium-based ILs on the properties of the liquid ordered phase (Lo, a commonly used lipid raft model) of egg sphingomyelin (SM)-cholesterol model membrane. We found that, in the absence of cholesterol, a very low IL:SM molar ratio of 0.01:1 could disrupt the integrity of the bilayer structure. In sharp contrast, the presence of cholesterol in lipid bilayers helps the Lo phase resist the damaging effect of the ILs. For the role of the IL headgroup, we found that the mono- and trisubstituted species show a stronger destructive effect on the structures of the model rafts than the commonly used disubstituted counterpart.

Evodiamine and rutaecarpine, derived from the traditional chinese medicine Euodia rutaecarpa (Juss.) Benth, have many similar pharmacological effects, but their pharmacological mechanisms are not exactly the same. In this study, liposomes were used as the model of biomembrane. DSC, synchrotron XRD and FTIR techniques have been employed to investigate and compare the interaction of evodiamine and rutaecarpine with DPPC liposomes. The results show that evodiamine and rutaecarpine remarkably affect the DPPC in a concentration-dependent manner. But the concentration dependence of the two drugs is obviously different. The effect of rutaecarpine on liposome membrane was stronger than that of evodiamine, which might be related to the different pharmacological mechanism of evodiamine and rutaecarpine. This study will play an important role in the further investigation of interaction of drugs with biomimetic membranes and further investigation of pharmacological mechanisms of drugs.

Existence and identification of ion pairing in aqueous electrolyte solutions are open questions to unveil the hydration structures of ions in water. In this work, we used a combination of infrared spectroscopy and quantum chemical calculations to investigate the ion pairing and hydrating properties of the aqueous solutions of lithium and sodium iodides by taking water molecules as probes. Spectral information of water molecules staying between the cations and anions in each case, as well as those contacting with the free ions of lithium and sodium, were extracted by using the strategy of equi-molar difference spectra. Peak positions of the solvent-shared ionpair (SIP) water molecules were found to be 3340 cm(-1) and 3580 cm(-1) for LiI and NaI, respectively. With increasing concentration of the salts, the SIPs of NaI appear earlier than the SIPs of LiI, in accordance with the law of matching water affinities. This work opens a window for the identification of ion pairs using FTIR and may shed light on the separation of the precious lithium from sodium and the investigation of the hydration properties of other inorganic salts. (C) 2020 Elsevier B.V. All rights reserved.

Understanding the self-assembly mechanisms of amphiphilic molecules in solutions and regulating their phase behaviors are of primary significance for their applications. To challenge the reported direct phase transitions from nonlamellar to ordered lamellar phases, the self-assembly and phase behavior of the 1-hexadecyl-3-methylimidazolium chloride aqueous dispersions were studied using a strategy of isothermal incubation after the temperature jump. A disordered lamellar phase (identified as the lamellar liquid-crystal (Lα) phase), serving as an intermediate, was found to bridge the transition from a spherical micellar (M) phase to a lamellar-gel (Lβ) phase. Meanwhile, the nonsynchronicity in the tail and headgroup regions of the ionic liquid surfactant during the transition process was also unveiled, with the former being prior to the latter. The in-depth understanding of the self-assembly mechanisms may help push forward the related applications in the future.

Ionic liquids (ILs) are potential green solvents with very broad application prospects. Their toxicity and other biological effects are largely related to their hydrophobic properties. In this work, the effects of two imidazolium-based ILs with either a butyl or a hexyl chain, [C(4)mim][OAc] or [C(6)mim][OAc], on the phase behaviours of a representative phospholipid, dipalmitoylphosphatidylcholine (DPPC), were examined using synchrotron small- and wide-angle X-ray scattering and differential scanning calorimetry techniques. A series of samples with a lipid : IL molar ratio ranging from 1 : 0 to 1 : 4/1 : 5 were prepared as aqueous dispersions in the form of multi-lamellar vesicles. The two ILs were found to have distinct effects on the phase behaviours of DPPC. For [C(4)mim][OAc], its effect is very limited. In contrast, for [C(6)mim][OAc], it could eliminate the pre-transition of DPPC, markedly affect the main phase transition of the lipid, and insert into the DPPC bilayer at gel state to form an interdigitated gel phase. The findings increased our understanding on the biological effects of imidazolium-based ILs and might shed light on the design of novel IL-based antimicrobials.

The sub-group element with low valence state and larger radius doping of a hybrid P2-layered Na0.5Li0.07Mn0.61Co0.16Ni0.16O2 were systematically investigated. The refined XRD results and operando XRD data revealed the improved Na-storage capability.

Baicalein is an important flavonoid compound extracted from the roots of Scutellaria baicalensis. The interaction between baicalein and DPPC liposomes has been studied by differential scanning calorimetry, synchrotron X-ray diffraction and Fourier transform infrared spectroscopy. The results showed the phase states of liposomes change under the disturbance of baicalein. When the molar percentage of baicalein (x) is not more than 5%, the baicalein molecules promote the hydration degree of the head groups. At x=5%, the liposomes undergo a change from L-beta' to L-beta phase. When x is between 5% and 10%, the liposomes are in P-beta' phase. When x is more than 10%, the baicalein molecules alter the hydration state of head groups. Meanwhile, the phase states shift from P-beta' to P-beta. This study is of great significance to further study the interaction between drugs and biomimetic membranes and to further investigate the phase transition mechanisms of DPPC liposome.

Deep-eutectic solvents (DESs) are a new class of green solvents. Here, we report the hydrogen bonding and structural properties of the archetypal DES ethaline, a mixture of choline chloride (ChCl) and ethylene glycol (EG) of a 1:2 molar ratio, and its pseudo-binary mixtures with acetonitrile. The investigations were carried out employing Fourier-transform infrared (FTIR) spectroscopy combined with quantum chemical calculations. Excess and two-dimensional (2D)-correlation spectroscopies were used to identify favorable species in the solutions and to explore the heterogeneity. The results show that the mixing process is the transformation from ethaline and CH3CN dimer to the complexes of ethaline-1CH3CN and ethaline-2CH3CN, together with the increased percentages of the EG dimer, EG trimer, and CH3CN monomer with respect to their total amounts in the mixtures. Theoretical calculations show that, for ChCl, the positive charge is located at the methyl groups and methylenes, rendering their ability to form hydrogen bonds. Adding CH3CN to ethaline can hardly break apart the doubly ionic hydrogen bonds between Ch+ and Cl-. The cosolvent molecules mainly surround the core structure of ethaline, forming noncovalent hydrogen bonds with hydroxyl groups of EG/Ch+ but not Cl-. These in-depth studies on the properties of ethaline and CH3CN/CD3CN mixed solvents may shed light on exploring their applications.