Tuning Low-Density Liquid Water with MgCl.

Perceiving a suitably tuned aqueous solution to unravel water's liquid-liquid critical point (LLCP) has become challenging. In this work, we investigated the structures of light and heavy water in the presence of MgCl using excess infrared spectroscopy and density functional theory calculations. The excess spectroscopy enabled us to differentiate the low-density liquid (LDL) water from the other liquid domains of pure water and reveal the new interaction modes between water and the ions.

In Situ Species Analysis of a Lithium-Ion Battery Electrolyte Containing LiTFSI and Propylene Carbonate.

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), TFSI, TFSI(PC), TFSI(PC), and Li(TFSI)] 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.

Transition Mechanism from the Metastable Two-Dimensional Gel to the Stable Three-Dimensional Crystal of Imidazolium-Based Ionic Liquids.

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) [Cmim]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.

Stochastic resonance analysis of a coupled high-speed maglev vehicle-bridge coupled system under bounded noise.

Coupled oscillations typically occur in maglev vehicle-bridge coupled systems excited by bounded noise caused by guideway irregularities. The paper employed Hamilton equations to derive the corresponding canonical transformation equations and determined the critical stable regions for two kinds of resonances using the largest Lyapunov exponents. The results show that the critical stable region between the excitation amplitude and the resonant frequency ratio is a valley shape when the system has external resonance only.

Free-Standing Two-Dimensional Crystals Formed from Self-Assembled Ionic Liquids.

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 [Cmim]X (X = Br, NO; = 14, 16, 18) using simultaneous synchrotron small- and wide-angle X-ray scattering techniques.

Abnormalities of the Halogen Bonds in the Complexes between YCTe (Y = H, F, CH) and XF (X = F, Cl, Br, I).

In this work, the hydrogen bonds and halogen bonds in the complexes between Y2CTe (Y = H, F, CH3) and XF (X = F, Cl, Br, I) have been studied by quantum chemical calculations. We found three interesting abnormalities regarding the interactions. Firstly, the strength of halogen bonds increases in the order of IF < BrF < ClF < F2.

Cholesterol Protects the Liquid-Ordered Phase of Raft Model Membranes from the Destructive Effect of Ionic Liquids.

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 (L, 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.

Generalized Excess Spectroscopy.

With a clear enhancement of the apparent resolution of experimentally determined spectra, excess spectroscopy has been developed as a powerful tool to study solution structures and molecular interactions. In the standard procedure of the method, excess spectra are calculated based on the ideal spectra constructed using two pure compounds. This limits the applications of the method when the pure compounds are unstable or their physical state is different from that of the mixtures.

The distinct effects of two imidazolium-based ionic liquids, [Cmim][OAc] and [Cmim][OAc], on the phase behaviours of DPPC.

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, [Cmim][OAc] or [Cmim][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.

Transition Mechanism from Nonlamellar to Well-Ordered Lamellar Phases: Is the Lamellar Liquid-Crystal Phase a Must?

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 (L) phase), serving as an intermediate, was found to bridge the transition from a spherical micellar (M) phase to a lamellar-gel (L) phase.

Fabrication of Asymmetric Phosphatidylserine-Containing Lipid Vesicles: A Study on the Effects of Size, Temperature, and Lipid Composition.

The asymmetric distribution of lipids in plasma membranes is closely related to the physiological functions of cells. To improve our previous approach in fabricating asymmetric vesicles, we defined a parameter, asymmetric degree, in this work and investigated the effects of vesicle size, incubation temperature, and lipid composition on the formation process of asymmetric phosphatidylserine (PS)-containing lipid vesicles. The results indicate that all of the three factors have marked but different effects on the time-dependent asymmetric degree of the vesicles as well as the flip and flop rate constants of the PS lipids.

Is the Fourier Transform Infrared Free-OH Band of -Butanol Only from Free OHs? Case Studies on the Binary Systems of the Alcohol with CCl and CHCl.

Attenuated total reflection-Fourier transform infrared spectroscopy and quantum chemical calculations were performed on -butyl alcohol (-BuOH) and its binary solutions with CCl and CHCl. The study was focused on the free-OH stretching bands. Two resolution-enhancing methods, excess spectroscopy and two-dimensional correlation spectroscopy, were employed to examine the structural heterogeneity and search for the detailed contributors to the free-OH bands.

Influence of Hydration on the Structure and Interactions of Ethaline Deep-Eutectic Solvent: A Spectroscopic and Computational Study.

Deep-eutectic solvents (DESs) are regarded as alternative green solvents to ionic liquids. In this work we report the structural properties and hydrogen bonding (H-bonding) interactions of an aqueous DES system. The used DES, ethaline (ETH), is composed of choline chloride and ethylene glycol (EG) in 1 : 2 molar ratio.

Structural Properties and Hydrogen-Bonding Interactions in Binary Mixtures Containing a Deep-Eutectic Solvent and Acetonitrile.

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.

Local Acid Strength of Solutions and Its Quantitative Evaluation Using Excess Infrared Nitrile Probes.

We propose the concept of local acidity in condensed-phase chemistry in this work. The feature is demonstrated in trifluoroethanol (TFE) by employing two Fourier-transform infrared spectroscopy (FTIR) nitrile probes, acetonitrile (CHCN) and benzonitrile (PhCN). Specifically, three positive excess peaks were found in the binary systems composed of TFE and a probe using excess spectroscopy.

Ammoniating Covalent Organic Framework (COF) for High-Performance and Selective Extraction of Toxic and Radioactive Uranium Ions.

An ideal porous adsorbent toward uranium with not only large adsorption capacity and high selectivity but also broad applicability even under rigorous conditions is highly desirable but still extremely scarce. In this work, a porous adsorbent, namely [NH][COF-SO ], prepared by ammoniating a SOH-decorated covalent organic framework (COF) enables remarkable performance for uranium extraction. Relative to the pristine SOH-decorated COF (COF-SOH) with uranium adsorption capacity of 360 mg g, the ammoniated counterpart of [NH][COF-SO ] affords ultrahigh uranium uptake up to 851 mg g, creating a 2.

Ultralow-Content Iron-Decorated Ni-MOF-74 Fabricated by a Metal-Organic Framework Surface Reaction for Efficient Electrocatalytic Water Oxidation.

Transition-metal-organic frameworks (MOFs) have been regarded as one of the most intriguing electrocatalysts because of its low cost and diversity in functional organic groups and metal centers. Different from the common strategies of tuning the ratio of metal centers in multivariate MOFs, here, ultralow-content FeO is decorated on the surface of monometallic Ni-MOF-74 based on the fast "phenol-iron (Fe)" surface reaction between Fe and the surface hydroxyl group in Ni-MOF-74. Benefiting from this flexible method, the Fe loading can be finely modulated and thus a series of Fe-decorated Ni-MOF-74 with different Fe contents are prepared.

Stable Iron Hydroxide Nanosheets@Cobalt-Metal-Organic-Framework Heterostructure for Efficient Electrocatalytic Oxygen Evolution.

Most studies are devoted to the use of metal-organic frameworks (MOFs) as templates to construct desirable electrocatalysts in situ by high-temperature pyrolysis. The emergence of heterostructures invokes new opportunities to use the full potential of pristine MOFs as efficient catalysts in the oxygen evolution reaction (OER). Here, a MOF surface-reaction strategy is developed to synthesize MOF-based heterostructures without pyrolysis.

Effect of Imidazolium-Based Ionic Liquids on the Structure and Phase Behavior of Palmitoyl-oleoyl-phosphatidylethanolamine.

Among various applications, ionic liquids (ILs) have been used as antimicrobial agents in laboratories, possibly through induction of the leakage of bacteria. A molecular-level understanding of the mechanism that describes how ILs enhance the permeation of membranes is still lacking. In this study, the effects of imidazolium-based ILs with different alky chain lengths on the structure and phase behavior of 1-palmitoyl-2-oleoyl-phosphatidylethanolamine (POPE), which is a representative bacteria-membrane-rich lipid, have been investigated.

Identifying Different Halogen-/Hydrogen-Bonding Interaction Modes in Binary Systems that Contain an Acetate Ionic Liquid and Various Halobenzenes.

Elucidation of the nature of noncovalent interactions between ionic liquids (ILs) and halogenated molecules is of particular importance for both fundamental research and drug development. Herein, the noncovalent interactions between 1-butyl-3-methyl-imidazolium acetate and three halobenzenes C F X (X=I, Br, H) were investigated. The iodine derivative shows the strongest interaction with the IL, followed by C F Br and C F H.

Controllable engineering of asymmetric phosphatidylserine-containing lipid vesicles using calcium cations.

A novel method to produce controllable asymmetric lipid vesicles using Ca is reported. The enrichment of negatively charged phosphatidylserine (PS) molecules in the inner leaflet is found not due to charge-charge attraction, but rather a modulation effect on the occupying size of the headgroups of PS molecules.

Plasma membrane activatable polymeric nanotheranostics with self-enhanced light-triggered photosensitizer cellular influx for photodynamic cancer therapy.

To address the issue of low cellular uptake of photosensitizers by cancer cells in photodynamic therapy (PDT), we designed a smart plasma membrane-activatable polymeric nanodrug by conjugating the photosensitizer protoporphyrin IX (PpIX) and polyethylene glycol (PEG) with glycol chitosan (GC). The as-prepared GC-PEG-PpIX can self-assemble into core-shell nanoparticles (NPs) in aqueous solution and the fluorescence of PpIX moieties in the inner core is highly quenched due to strong π-π stacking. Interestingly, when encountering plasma membranes, the GC-PEG-PpIX NPs can disassemble and stably attach to plasma membranes due to the membrane affinity of PpIX moieties, which effectively suppresses the self-quenching of PpIX, leading to significantly enhanced fluorescence and singlet oxygen (O) production upon laser irradiation.