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Surface active ionic liquids (SAILs) combine useful characteristics of both ionic liquids (ILs) and surfactants, hence are promising candidates for a wide range of applications.

The tribological properties of the epoxy were significantly improved due to the tribological synergy of biomimetic F-CDs and sulfonated h-BN.

The ion structure of surface active ionic liquids (SAILs), i.e. ion charge group and alkyl chain structure, controls their bulk and interfacial nanostructure and the electrochemical properties near an electrode.The structures in the bulk and at the interface were investigated by small and wide-angle X-ray scattering (SAXS) and atomic force microscopy (AFM), respectively. An investigation was performed using cyclic voltammetry.All SAILs show pronounced sponge-like bulk nanostructure. For the first time, the bulk nanostructures of SAILs are found to change from anion bilayer structures to cation-anion interdigitated structures as the ion structures change from short alkyl chain cations and linear alkyl chain anions to long alkyl chain cations and branched alkyl chain anions. The bulk nanostructure packs more compactly at a higher temperature, likely due to the conformational change and enhanced interdigitations of alkyl chains. The thicknesses of SAIL interfacial layers align with the repeat distances of the bulk nanostructure, similar to conventional ILs with long cation alkyl chains. All SAILs have wide electrochemical windows4 V, which are not affected by the alkyl chain structure and cation charge groups.

The dynamics of the self-assembled liquid nanostructure of the ionic liquids (ILs) near a mica surface can be determined from video-rate atomic force microscopy (AFM) data.Video-rate AFM has been used to record the nanostructure dynamics of two most widely studied ILs, 1-butyl-3-methylimidazolium bis(trifluoromethylsulfonyl)imide (BMIM TFSI) and ethylammonium nitrate (EAN), as well as EAN-water mixtures, above a model anode, mica. Diffusion coefficients were extracted from the AFM videos using dynamic differential microscopy and direct tracking.Video rate AFM is able to record the movement of the IL nanostructure. This is the first time that any liquid has been directly visualized at a scale of 10 nm × 10 nm in real-time. Diffusion coefficients determined from AFM videos reveal IL nanostructures near surfaces diffuse orders of magnitude more slowly than individual ions in the bulk. Thus, rather than free-flowing liquid, the near-surface nanostructure is better conceptualized as self-assembled aggregates of IL ions diffusing slowly over the cation-rich Stern layer, akin to adsorbed surfactant micelles in aqueous systems. This new and surprising insight affects wide-ranging processes involving the interfacial dynamics of concentrated electrolytes.

Hypothesis A catanionic surface-active ionic liquid (SAIL) trihexyltetradecylphosphonium 1,4-bis(2-ethylhexoxy)-1,4-dioxobutane-2-sulfonate ([P6,6,6,14] [AOT]) is nanostructured in the bulk and at the interface. The interfacial nanostructure and lubricity may be changed by applying a potential. Experiments The bulk structure and viscosity have been investigated using small angle X-ray scattering (SAXS) and rheometry. The interfacial structure and lubricity as a function of potential have been investigated using atomic force microscopy (AFM). The electrochemistry has been investigated using cyclic voltammetry. Findings [P6,6,6,14] [AOT] shows sponge-like bulk nanostructure with distinct interdigitation of cation–anion alkyl chains. Shear-thinning occurs at 293 K and below, but becomes less obvious on heating up to 313 K. Voltammetric analysis reveals that the electrochemical window of [P6,6,6,14] [AOT] on a gold micro disk electrode exceeds the potential range of the AFM experiments and that negligible redox activity occurs in this range. The interfacial layered structure of [P6,6,6,14] [AOT] is weaker than conventional ILs and SAILs, whereas lubricity is better, confirming the inverse correlation between the near-surface structure and lubricity. The adhesive forces of [P6,6,6,14] [AOT] are lower at −1.0 V than at open circuit potential and +1.0 V, likely due to reduced electrostatic interactions caused by shielding of charge centres via long alkyl chains.

Interest in deep eutectic solvents (DESs), particularly for electrochemical applications, has boomed in the past decade because they are more versatile than conventional electrolyte solutions and are low cost, renewable, and non-toxic. The molecular scale lateral nanostructures as a function of potential at the solid–liquid interface—critical design parameters for the use of DESs as electrochemical solvents—are yet to be revealed. In this work, in situ amplitude modulated atomic force microscopy complemented by molecular dynamics simulations is used to probe the Stern and near-surface layers of the archetypal and by far most studied DES, 1:2 choline chloride:urea (reline), at the highly orientated pyrolytic graphite surface as a function of potential, to reveal highly ordered lateral nanostructures with unprecedented molecular resolution. This detail allows identification of choline, chloride, and urea in the Stern layer on graphite, and in some cases their orientations. Images obtained after the potential isswitched from negative to positive show the dynamics of the Stern layer response, revealing that several minutes are required to reach equilibrium. These results provide valuable insight into the nanostructure and dynamics of DESs at the solid–liquid interface, with implications for the rational design of DESs for interfacial applications.

ChAAILs are often used in mixtures to lower cost and improve handling, but the effects of water and other molecular additives are poorly understood. This review describes structure at different dilution stages and design strategies for task-specific ChAAIL-based mixtures.

Hypothesis: The properties of the oxidized surface for common materials, such as silicon and titanium, are known to be markedly different from the reduced surface. We hypothesize that surface-oxidized aluminum gallium nitride ((oxidized-AlGaN)/GaN) surface charge behavior is different to unoxidized AlGaN (with ultrathin native oxide only), which can be validated via surfactant adsorption. Understanding these differences will explain why (oxidized-AlGaN)/GaN-based sensors are better performing than AlGaN ones, which has been previously demonstrated but not understood. Experiments: The surface of an AlGaN/GaN structure was oxidized with hot piranha solution and oxygen plasma. AFM force measurements and imaging were performed to probe the charge properties of the surface in aqueous solutions of varying pH containing only an acid or base, or with an added ionic surfactant: cationic cetyltrimethylammonium bromide (CTAB) or anionic sodium dodecylsulfate (SDS). Findings: The (oxidized-AlGaN)/GaN surface is positively charged at pH 4 and pH 5.5, although pH 5.5 should be close to the isoelectric point of the surface. The surface is negatively charged at pH 10 and pH 12, and sufficiently charged to attract cooperative adsorption of CTAB aggregates at pH 12. At pH 2, the evidence is inconclusive, but the surface is most likely positively charged. Compared to unoxidized AlGaN, the (oxidized-AlGaN)/GaN surface shows a wider range of surface charge magnitude over pH values between 2 and 12. This suggests that the (oxidized-AlGaN)/GaN surface has a higher surface hydroxyl group density than unoxidized AlGaN, which explains the higher sensitivity for pH sensors based on (oxidized-AlGaN)/GaN structures.

Mesoporous glass 58S (60SiO2, 36CaO, 4P2O5 mol.%) has excellent bioactivity, biocompatibility, and forms strong bonds with bone making it attractive for implants. Mesoporous bioactive glass 58S powder is typically consolidated through sintering in order to produce an implant with sufficient strength to withstand the in vivo loads. However, heating the glass often leads to crystallinity, which is undesirable because it can reduce bioactivity. Hence, there is a trade-off between minimising crystallinity and maximising glass strength. Even at relatively low temperatures, it has been suggested that segregation of calcium and phosphate from silica within the glass can lead to crystallization. In this work, we confirm the occurrence of low temperature segregation in bioactive glass 58S using electron microscopy with elemental mapping. We probe how segregation affects the material properties of post-sintered glasses via comparison to a glass where phase separation is prevented via addition citric acid to the parent sol.

Due to their excellent biocompatibility, outstanding mechanical properties, high strength-to-weight ratio, and good corrosion resistance, titanium (Ti) alloys are extensively used as implant materials in artificial joints. However, Ti alloys suffer from poor wear resistance, resulting in a considerably short lifetime. In this study, we demonstrate that the chemical self-assembly of novel two-dimensional (2D) diamond nanosheet coatings on Ti alloys combined with natural silk fibroin used as a novel lubricating fluid synergistically results in excellent friction and wear performance. Linear-reciprocating sliding tests verify that the coefficient of friction and the wear rate of the diamond nanosheet coating under silk fibroin lubrication are reduced by 54 and 98%, respectively, compared to those of the uncoated Ti alloy under water lubrication. The lubricating mechanism of the newly designed system was revealed by a detailed analysis of the involved microstructural and chemical changes. The outstanding tribological behavior was attributed to the establishment of artificial joint lubrication induced by the cross binding between the diamond nanosheets and silk fibroin. Additionally, excellent biocompatibility of the lubricating system was verified by cell viability, which altogether paves the way for the application of diamond coatings in artificial Ti joint implants.

The lubricities of four quaternary phosphonium ionic liquids-trihexyltetradecylphosphonium bis( 2,4,4-trimethylpentyl) phosphinate ([P-6,P-6,P-6,P-14][(C-1(8))(2)PO2]), trihexyltetradecylphosphoniu ...

Cholinium argininate ([Ch][Arg]) and water mixtures are biocompatible solvents which are efficient for the dissolution of various kinds of biomass, but the molecular origins of their efficacy are u...

Hypothesis The net surface charge of AlGaN/GaN structures, where AlGaN is in contact with the solution, is controlled by the pH-dependent protonation and deprotonation of the surface hydroxyl groups and possibly the electron-deficient surface electronic states. We hypothesize that atomic force microscopy (AFM) force measurements of ionic surfactant adsorption can reveal how the AlGaN surface properties vary with pH. Experiments AFM force curves and images were used to probe the AlGaN/solution interface in water as a function of pH, and with added cationic surfactant cetyltrimethylammonium bromide (CTAB) or anionic surfactant sodium dodecylsulfate (SDS). Findings The AlGaN/solution interface is negatively charged at pH 12, has an isoelectric point near pH 5.5, and is positively charged at pH values less than 5.5. Surfactant adsorption data suggests AlGaN surface is somewhat hydrophobic at acidic pH. Compared to gallium nitride (GaN), at pH 2, AlGaN has a lower charge density and hydrophobicity, but at other values of pH, the surface properties of AlGaN and GaN are similar.

Non-viral delivery is an important strategy for selective and efficient gene therapy, immunization, and RNA interference, which overcomes problems of genotoxicity and inherent immunogenicity associated with viral vectors. Liposomes and polymers are compelling candidates as carriers for intracellular, non-viral delivery, but maximal efficiencies of around 1% have been reported for the most advanced non-viral carriers. Here, we develop a library of dendronized bottlebrush polymers with controlled defects, displaying a level of precision surpassed only by biological molecules like DNA, RNA, and proteins. We test concurrent and competitive delivery of DNA and show for the first time that, while intracellular communication is thought to be an exclusively biomolecular phenomenon, such communication between synthetic macromolecular complexes can also take place. Our findings challenge the assumption that delivery agents behave as bystanders that enable transfection by passive intracellular release of genetic cargo and improve upon coarse strategies in intracellular carrier design lacking control over polymer sequence, architecture, and composition, leading to a hit-or-miss outcome. Understanding the communication that takes place between macromolecules will help improve the design of non-viral delivery agents and facilitate translation of genome engineering, vaccines, and nucleic acid-based therapies.

We present a series of synthetic polymer hydrogels which break the traditional correlation between pore size and mechanical properties. The hydrogels are prepared from a dendronised polymer architecture based on a methacrylate copolymer to which poly(amido amine) dendrons are attached. Our approach will be useful in tailoring hydrogels for tissue engineering, controlled drug release, and flexible electronics.

The structure of the ionic liquid choline lysinate ([Ch][Lys]) and its water mixtures, including a dissolved model lignin residue, guaiacol, is revealed at atomic and nanoscale resolution using neutron diffraction. The performance of [Ch][Lys] for biomass pretreatment depends on both its detailed H-bonding capacity and bicontinuous polar/apolar nanostructure, which is stabilised by lysinate adopting an H-bonded cyclic conformer that enhances its amphiphilicity. These features are heightened by the addition of water, which forms nanoscale pockets but also extends the H-bonding network within the IL polar domains while largely preserving its bicontinuous nanostructure, rendering the ionic liquid–water mixture an effective solvent for organic molecules bearing various functional groups. A model representative lignin compound, guaiacol, is found to H-bond through its phenol group to both the anion and water, destabilising the lysinate cyclic conformer and altering the liquid nanostructure.

Mixing of cationic and anionic surfactants in water can result in pseudo-double-tailed catanionic surfactant ion pairs that form lamellar phases or vesicles that are unstable toward electrolyte addition. Here we show that despite the very high ionic strengths, catanionic surfactants counterintuitively form a wider variety of self-assembled aggregates in pure ionic liquids (ILs, pure salts in a liquid phase) than in water, including micelles, vesicles, and lyotropic phases. Self-assembled structures only form when the IL is sufficiently polar to drive self-assembly through electrostatic interactions and/or H-bond networks, but the catanionic effect is manifested only when the IL does not itself exhibit pronounced amphiphilic nanostructure. This enables the type of catanionic aggregate formed to be designed by changing the hydrogen bonds between the ions through variation of the structures of the cation and anion. These results reveal an entirely new way of controlling catanionic surfactant self-assembly under nonaqueous and high-salt conditions.

Atomic force microscopy has been used to measure the lubricity of a series of ionic liquids (ILs) at mica surfaces in the boundary friction regime. A previously unreported cation bilayer structure is detected at the IL-mica interface due to the formation of H-bonds between the hydroxy-functionalized cations [(c-c) H-bonds], which enhances the ordering of the ions in the boundary layer and improves the lubrication. The strength of the cation bilayer structure is controlled by altering the strength of (c-c) H-bonding via changes in the hydroxyalkyl chain length, the cation charge polarizability, and the coordination strength of the anions. This reveals a new means of controlling IL boundary nanostructure via H-bonding between ions of the same charge, which can impact diverse applications, including surface catalysis, particle stability, electrochemistry, etc.

The emergence of ionic liquids and deep eutectics as neoteric solvents that support surfactant self-assembly creates a vast new playing field for creating new forms of soft matter with distinctive properties. Solvophobic self-assembly in ionic liquids and deep eutectics has unique and novel features arising from strong interactions between constituents, high ionic strengths, and the molecular structures of the components, which can induce amphiphilic nanostructure in these nonaqueous solvents. This nanostructure is often reminiscent of microemulsions and sponge phases. Here we review recent new understanding of solvent nanostructure and its effect on self-assembly of surfactants and lipids.

The conformation of the polycation in the prototypical polymeric ionic liquid (PIL) poly(3-methyl-1-aminopropylimidazolylacrylamide) bis(trifluoromethylsulfonyl)imide (poly(3MAPIm)TFSI) was probed using small-angle neutron scattering (SANS) and ultra-small-angle neutron scattering (USANS) at 25 °C and 80 °C. Poly(3MAPIm)TFSI contains microvoids which lead to intense low

A catanionic surface-active ionic liquid (SAIL) trihexyltetradecylphosphonium 1,4-bis(2-ethylhexoxy)-1,4-dioxobutane-2-sulfonate ([PThe bulk structure and viscosity have been investigated using small angle X-ray scattering (SAXS) and rheometry. The interfacial structure and lubricity as a function of potential have been investigated using atomic force microscopy (AFM). The electrochemistry has been investigated using cyclic voltammetry.[P

Defects at discontinuities of the perovskite lattice limit the performance of the perovskite solar cell (PSC). Lead iodide (PbI2) and pyridine have been shown to passivate these defects. We treat methylammonium lead iodide (MAPbI3) films with pyridine solutions to investigate the effects of the two passivators. By comparing confocal fluorescence microscopy (CFM) images at 405 nm excitation and then at 559 nm excitation we demonstrate the pyridine treatment passivates and forms PbI2 crystallites which cause additional passivation.

The liquid structures of six choline carboxylate/amino acid ionic liquids (bio-ILs) and their mixtures with water and various n-alkanols have been investigated by small-angle X-ray scattering (SAXS). The ILs exhibit long-range amphiphilic nanostructure comprised of polar and apolar domains that can be controlled by choice of anion, and which is tolerant to water dilution. Mixtures with n-alkanols can lead to marked changes in domain size and ordering. Utilising the Teubner-Strey model, we find amphiphilicity factors in many of these mixtures are comparable to those observed in conventional microemulsions, and that cooperative assembly in bio-IL/alkanol mixtures can enhance amphiphilicity, with potential to improve performance in a range of applications.

Hypothesis The surface charge of gallium nitride (GaN) in contact with solution is controlled by pH via surface protonation and deprotonation, similar to silica. Ionic surfactants adsorb on surfaces via electrostatic and hydrophobic interactions and can be utilized to reflect the surface charge of GaN. Experiments The surface charge properties of Ga-polar GaN in solution were probed as a function of pH using atomic force microscopy (AFM). AFM soft-contact images and force curves were used to study the pH-dependent adsorption of the cationic surfactant cetyltrimethylammonium bromide (CTAB) and anionic surfactant sodium dodecylsulfate (SDS) on GaN surfaces. To further confirm the AFM results, GaN/AlGaN/GaN heterostructure-based ion sensing devices were used to measure the surfactant adsorption over the same pH range. Findings SDS aggregates adsorb on GaN below pH 2.75 while CTAB aggregates adsorb above pH 10. This shows that the GaN surface carries substantial net positive charge at low pH, and negative charge at high pH. There is no clear SDS or CTAB adsorption on the GaN surface between pH 3 and 9.75, which indicates the surface is weakly charged. GaN/AlGaN/GaN heterostructure-based devices confirm these results, and demonstrate the utility of these devices for measuring surfactant adsorption.

The quartz crystal microbalance (QCM) has been used to study how the interfacial layer of an ionic liquid dissolved in a polar oil at low weight percentages responds to changes in applied potential. The changes in surface composition at the QCM gold surface depend on both the magnitude and sign of the applied potential. The time-resolved response indicates that the relaxation kinetics are limited by the diffusion of ions in the interfacial region and not in the bulk, since there is no concentration dependence. The measured mass changes cannot be explained only in terms of simple ion exchange; the relative molecular volumes of the ions and the density changes in response to ion exclusion must be considered. The relaxation behavior of the potential between the electrodes upon disconnecting the applied potential is more complex than that observed for pure ionic liquids, but a measure of the surface charge can be extracted from the exponential decay when the rapid initial potential drop is accounted for. The adsorbed film at the gold surface consists predominantly of ionic liquid despite the low concentration, which is unsurprising given the surtactant-like structures of (some of) the ionic liquid ions. Changes in response to potential correspond to changes in the relative numbers of cations and anions, rather than a change in the oil composition. No evidence for an electric field induced change in viscosity is observed. This work shows conclusively that electric potentials can be used to control the surface composition, even in an oil-based system, and paves the way for other ion solvent studies.

The effective pre-treatment methods are required for the destruction of the complex biomass structure to economically produce high grade fuels and valuable platform chemicals. Ionic liquids have high potential for energy efficient biomass pre-treatment due to their low vapour pressure, emission profile, recyclability and tuneable properties; some ionic liquids can even be prepared from renewable biomass feedstocks. However, a number of issues currently impede the large scale uptake of ionic liquids including their cost of production, detailed understanding the macro, micro and molecular level deconstruction mechanisms which inhibits process optimisation and modelling, and the need for techno-economic astable sessment on large scale trials. So far, laboratory to bench scale IL pre-treatments of various lignocellulosic biomasses were studied by changing various process parameters where the aims were to investigate the biomass dissolution mechanism and understand the pre-treatment performance of ILs. This review outlines current research gaps and potential applications for ionic liquids in the destruction of biomass into its components followed by separation of lignin, hemicellulose and cellulose rich fractions.

Hypothesis Micelle formation, particularly the formation of compact, globular micelles in the high ionic strength environment of an ionic liquid, seems to be at odds with the principle of opposing forces and the concept of the surfactant packing parameter. Here we examine how interactions between polar head-groups, with solvent ions, and chain packing affect self-assembly structure in ionic liquids. Experiments The self-assembly of pure cationic and anionic surfactants, their catanionic mixtures, and the effect of the cosurfactant tetradecanol in the ionic liquid ethylammonium nitrate (EAN) is investigated by small-angle neutron scattering (SANS). Findings The critical micelle concentrations of cationic surfactants are much higher and micelles much smaller in EAN than in water, whereas anionic micelles are less dramatically affected. Catanionic surfactant mixtures form small micelles in EAN at all compositions, unlike their counterparts in water which form vesicle dispersions or precipitates near 1:1 mol ratios. This contrasts with the behavior of cationic surfactants when mixed with double-chained analogs or alkanol cosurfactants, which induce micelle growth and shape transitions to rod-like and bilayer aggregates through chain packing effects similar to aqueous systems. This enables the aggregate morphology in the ionic liquid to be controlled through the composition of the surfactant mixtures.

Asphaltenes, which comprise polycyclic aromatic hydrocarbon cores with attached short aliphatic side chains, are the most polar fraction of crude oils. Asphaltenes are prone to precipitation, which requires expensive cleaning procedures using solvents like toluene or xylene. The toxicity and high vapour pressures of toluene and xylene means there is an urgent need for new liquids that are able to dissolve or suspend asphaltenes but are less environmentally problematic. This study reports treatment results of asphaltenes with 16 different ionic liquids covering three different types of cation charge groups, namely, cholinium, imidazolium and phosphonium with a wide variety of anions. The two oil-miscible ionic liquids, trihexyl(tetradecyl)phosphonium bis(2,4,4-trimethylphentyl)phosphinate and trihexyl(tetradecyl)phosphonium bis(2-ethylhexyl)phosphate, solubilised or suspended a significant fraction of raw asphaltenes. Elemental analysis, TGA and FTIR revealed that asphaltenes recovered from these ionic liquids had increased aliphatic and oxygen content compared to the raw material, and decomposed at lower temperatures during TGA test. The relative hydrophobicity of the ionic liquid is the major factor controlling the asphaltene mass in the ionic liquid, followed by the strength of interactions between ionic liquid and asphaltene alkyl groups. These findings provide a platform for the development of new ionic liquid based cleaners for asphaltene deposits.

Hypothesis The polymeric cations of polymeric ionic liquids (PILs) can adsorb from the bulk of a conventional ionic liquid (IL) to the Au(1 1 1) electrode interface and form a boundary layer. The interfacial properties of the PIL boundary layer may be tuned by potential. Experiments Atomic force microscopy has been used to investigate the changes of surface morphology, normal and lateral forces of a 5 wt% PIL/IL mixture as a function of potential. Findings Polymeric cations adsorb strongly to Au(1 1 1) and form a polymeric cation-enriched boundary layer at −1.0 V. This boundary layer binds less strongly to the surface at open circuit potential (OCP) and weakly at + 1.0 V. The polymeric cation chains are compressed at −1.0 V and OCP owing to electrical attractions with the electrode surface, but fully stretched at + 1.0 V due to electrical repulsions. The lateral forces of the 5 wt% PIL/IL mixture at −1.0 V and OCP are higher than at + 1.0 V as the polymeric cation-enriched boundary layer is rougher and has stronger interactions with the AFM probe; at + 1.0 V, the lateral force is low and comparable to pure conventional IL due to displacement of polymeric cations with conventional anions in the boundary layer.

Hypothesis Hybrid solvents based on cholinium amino acid ionic liquids ([Ch][AA] ILs) mixed with water are environmentally benign solvents with low toxicity. [Ch][AA] ILs are used in biomass pretreatment processes to dissolve targeted (macro)molecules such as lignin from lingnocellulose. Understanding how [Ch][AA] ILs dissolve polymers is therefore of great interest for the rational design of ILs towards industrial application. Variation of the IL anion and the water concentration are hypothesised to change the solvent properties of [Ch][AA] hybrid solvents. Therefore, we probe the solvent quality of [Ch][AA] aqueous solutions with different anions (glycinate, prolinate and argininate) and water concentration for the simple model solute poly(ethylene glycol) (PEG). Experiments Partial phase diagrams were produced to probe the salting-out effect of [Ch][AA] ILs towards PEG (Mw = 38 kDa). Small-angle neutron scattering experiments of deuterated PEG in hydrogenous [Ch][AA] aqueous solutions were performed to determine the polymer radius of gyration at infinite dilution (Rg,0) via Zimm-plots. Polymer concentration dependent apparent Rg values were obtained fitting an excluded volume polymer model onto the scattering data. Blends of hydrogenous and deuterated PEG under zero average contrast conditions were analysed to probe Rg at high polymer concentrations. Findings Hydrogen bond capacity of the anion is key to the salting-out effect of [Ch][AA] ILs on PEG. Rg,0 depends on anion species and water concentration. At IL:water = 1:30 (mole:mole) and 37 °C, cholinium argininate and cholinium glycinate are close to theta solvents while cholinium prolinate and dilute cholinium argininate (IL:water = 1:100) are between theta and good solvents.

The liquid structures of three alkyl ammonium bromide and urea DESs, ethylammonium bromide:urea (1:1), butylammonium bromide:urea (1:1), and ethylammonium bromide/butylammonium bromide:urea (0.5:0.5:1), have been studied using small-angle neutron diffraction with H/D substituted sample contrasts. The diffraction data was fit using empirical potential structure refinement (EPSR). An amphiphilic nanostructure was found in all DESs due to cation alkyl chains being solvophobically excluded from charged domains, and due to clustering together. The polar domain was continuous in all three DESs, whereas the apolar domain was continuous for the butylammonium DES and in the mixed DES, but not the ethylammonium DES. This is attributed to solvophobic interactions being weaker for the short ethyl chain. Surprisingly, the urea also forms large clusters in all three DESs. In ethylammonium bromide:urea (1:1), urea-urea orientations are mainly perpendicular, but in butylammonium bromide:urea (1:1) and the mixed system in-plane and perpendicular arrangements are found. The liquid nanostructures found in this work, especially for the ethylammonium DES, are different from those found previously for the corresponding DESs formed using glycerol, revealing that the DES amphiphilic nanostructure is sensitive to the nature of the HBD (hydrogen bond donor).

The protic ionic liquid diethylmethylammonium methanesulfonate ([DEMA][OMs]) was analyzed in depth by differential scanning calorimetry (DSC), nuclear magnetic resonance (NMR) spectroscopy, Fourier transform infrared (FT-IR) spectroscopy, Raman spectroscopy and broadband dielectric spectroscopy (BDS) under anhydrous conditions. Karl Fischer titration, NMR and FT-IR spectra confirmed the high purity of [DEMA][OMs]. The melting point (37.7 °C) and the freezing point (14.0 °C) obtained by DSC agree well with the values determined by BDS (40.0 °C and 14.0 °C). The dc conductivity (σdc) above the melting/freezing point obeys Vogel-Fulcher-Tammann (VFT) equation well and thus the proton conduction in [DEMA][OMs] is assumed to be dominated by the vehicle mechanism. In contrast, the σdc below the melting/freezing point can be fitted by the Arrhenius equation separately and therefore the proton conduction is most likely governed by the proton-hopping mechanism. The non-negligible influence of previously reported low water contents on the physicochemical properties of [DEMA][OMs] is found, indicating the importance of reducing water content as much as possible for the study of “intrinsic” properties of protic ionic liquids. ispartof: Journal Of Chemical Physics vol:152 issue:23 ispartof: location:United States status: Published online

Defects at discontinuities of the perovskite lattice limit the performance of the perovskite solar cell (PSC). Lead iodide (PbI

Pinewoods are the dominant species in Australian softwood plantations and an important source of renewable lignocellulosic biomass. This work examines interactions between cholinium amino acid (Ch[AA]) ionic liquid (IL) – Water mixtures and pinewood. The Ch[AA] ILs employed were cholinium arginate (Ch[Arg]), cholinium glycinate (Ch[Gly]), and cholinium aspartate (Ch[Asp]), with water contents between 32 and 42 wt%. Pinewood and Ch[AA] ILs were mixed at 90 °C for all samples, and also 120 °C for Ch[Arg], as it dissolved the most biomass at 90 °C. Thermogravimetric analysis (TGA), scanning electron microscopy (SEM), x-ray diffraction (XRD), and compositional (CHNS) analysis were performed on the raw and treated biomass samples to reveal the changes in physical and chemical properties. While Ch[Arg] solubilised the greatest mass of biomass during treatment, the most pronounced changes in decomposition properties was obtained using Ch[Gly]. The TGA analysis revealed the maximum in the derivative weight loss data shifted to lower temperatures by 29 °C.

Hypothesis The solvation characteristics of poly(ethylene oxide) (PEO) in nanostructured protic ionic liquids (PILs) are driven by polymer-solvent interactions in the polar domains of the PIL. This work hypothesises that the nanostructure of a PIL can be altered via halide addition, directly affecting the solvation of PEO. Experiments Small angle neutron scattering (SANS) is used to explore the conformation of 38 kDa PEO dissolved in the PIL propylammonium nitrate (PAN), a mol fraction of 10% propylammonium chloride (PACl) in PAN, and a mole fraction of 10% propylammonium bromide (PABr) in PAN. Findings Each of these solutions are shown to behave as a good solvent for PEO, as determined by their Flory exponents and Zimm plot analysis. The quality of solvation is reduced by the addition of the halide salt, with the order of solvation as follows: PAN > Br− addition > Cl− addition. Our experimental observations are consistent with the recently reported solvation structure of PEO in these solutions (Stefanovic et al., 2018). The increased charge density from NO3− to Br− to Cl− results in greater net ionic interaction between the ionic charge centres. As PEO interacts with PAN primarily through the ammonium hydrogens of the cation, this increased ionic interaction effectively displaces the PEO, resulting in poorer solvation.

The interfacial nanostructure of the three most widely-studied Deep Eutectic Solvents (DESs), choline chloride:urea (ChCl:Urea), choline chloride:ethylene glycol (ChCl:EG), and choline chloride:glycerol (ChCl:Gly) at a Pt(111) electrode has been studied as a function of applied potential and water content up to 50 wt%. Contact mode atomic force microscope (AFM) force–distance curves reveal that for all three DESs, addition of water increases the interfacial nanostructure up to ∼40 wt%, after which it decreases. This differs starkly from ionic liquids, where addition of small amounts of water rapidly decreases the interfacial nanostructure. For the pure DESs, only one interfacial layer is measured at OCP at 0.5 nm, which increases to 3 to 6 layers extending ∼5 nm from the surface at 40 or 50 wt% water. Application of a potential of ±0.25 V to the Pt electrode for the pure DESs increases the number of near surface layers to 3. However, when water is present the applied potential attenuates the steps in the force curve, which are replaced by a short-range exponential decay. This change was most pronounced for ChCl:EG with 30 wt% or 50 wt% water, so this system was probed using cyclic voltammetry, which confirms the interfacial nanostructure is akin to a salt solution.

Nannochloropsis sp. has been a very attractive microalgae species because of its high omega-3 fatty acid content. However, it is also one of the species with the strongest cell wall. Currently, energy-intensive mechanical techniques and harmful and flammable organic solvents are used for extracting lipids from Nannochloropsis sp. biomass. Thus, in this study, cholinium [Ch] amino acid-based ionic liquids (ILs) were investigated for their capability to extract lipids from Nannochloropsis sp. Among all the ILs tested, cholinium arginate ([Ch][Arg]) extracted the highest amount leaving only 1.4 ± 0.2% lipid in the remaining biomass. The extraction was still efficient at room temperature leaving only 7.9 ± 0.3% lipid. Thus, [Ch][Arg] is an efficient green solvent for Nannochloropsis lipid extraction.