Bulk Nanostructure of Mixtures of Choline Arginate, Choline Lysinate, and Water.

Neutron diffraction with empirical potential structure refinement was used to investigate the bulk liquid nanostructure of mixtures of choline arginate (Ch[Arg]), choline lysinate (Ch[Lys]), and water at mole ratios of 1Ch[Arg]:1Ch[Lys]:6H2O (balanced), 1Ch[Arg]:1Ch[Lys]:20H2O (balanced dilute), 3Ch[Arg]:1Ch[Lys]:12H2O (Arg- rich), and 1Ch[Arg]:3Ch[Lys]:12H2O (Lys- rich). The Arg- and Lys- anions tend not to associate due to electrostatic repulsion between charge groups and weak anion-anion attractions. This means that the local ion structures around the anions in these mixtures resemble the parent single-component systems. The bulk liquid nanostructure varies with the Arg-:Lys- ratio. In the Lys--rich mixture (1Ch[Arg]:3Ch[Lys]:12H2O), Lys- side chains cluster into a continuous apolar domain separated from a charged domain of polar groups. In the balanced mixture (1Ch[Arg]:1Ch[Lys]:6H2O), Lys- side chains form discrete apolar aggregates within a continuous polar domain of Arg-, Ch+, and water, and in the Arg--rich mixture (3Ch[Arg]:1Ch[Lys]:12H2O), the distribution of Lys- and Arg- is nearly homogeneous. Finally, in the balance dilute system (1Ch[Arg]:1Ch[Lys]:20H2O), a percolating water domain forms.

Nanostructure and Dynamics of Aprotic Ionic Liquids at Graphite Electrodes as a Function of Potential.

Atomic force microscope (AFM) videos reveal the near-surface nanostructure and dynamics of the ionic liquids (ILs) 1-butyl-3-methylimidazolium dicyanamide (BMIM DCA) and 1-hexyl-3-methylimidazolium dicyanamide (HMIM DCA) above highly oriented pyrolytic graphite (HOPG) electrodes as a function of surface potential. Molecular dynamics (MD) simulations reveal the molecular-level composition of the nanostructures. In combination, AFM and MD show that the near-surface aggregates form via solvophobic association of the cation alkyl chains at the electrode interface. The diffusion coefficients of interfacial nanostructures are ≈0.01 nm2 s-1 and vary with the cation alkyl chain length and the surface potential. For each IL, the nanostructure diffusion coefficients are similar at open-circuit potential (OCP) and OCP + 1V, but BMIM DCA moves about twice as fast as HMIM DCA. At negative potentials, the diffusion coefficient decreases for BMIM DCA and increases for HMIM DCA. When the surface potential is switched from negative to positive, a sudden change in the direction of the nanostructure motion is observed for both BMIM DCA and HMIM DCA. No transient dynamics are noted following other potential jumps. This study provides a new fundamental understanding regarding the dynamics of electrochemically stable ILs at electrodes vital for the rational development of IL-based electrochemical devices.

Inelastic neutron scattering and spectroscopy methods to characterize dynamics in colloidal and soft matter systems.

Colloidal systems and soft materials are well suited to neutron scattering, and the community has readily adopted elastic scattering techniques to investigate their structure. Due to their unique properties, neutrons may also be used to characterize the dynamics of soft materials over a wide range of length and time scales in situ. Both static structures and an understanding of how molecules move about their equilibrium positions is essential if we are to deliver on the promise of rationally designing soft materials. In this review we introduce the basics of neutron spectroscopy and explore the ways in which inelastic neutron scattering can be used to study colloidal and soft materials. Illustrative examples are chosen that highlight the phenomena suitable for investigation using this suite of techniques.

H-bond network, interfacial tension and chain melting temperature govern phospholipid self-assembly in ionic liquids.

HYPOTHESIS: The self-assembly structures and phase behaviour of phospholipids in protic ionic liquids (ILs) depend on intermolecular forces that can be controlled through changes in the size, polarity, and H-bond capacity of the solvent. EXPERIMENTS: The structure and temperature stability of the self-assembled phases formed by four phospholipids in three ILs was determined by a combination of small- and wide-angle X-ray scattering (SAXS and WAXS) and small-angle neutron scattering (SANS). The phospholipids have identical phosphocholine head groups but different alkyl tail lengths and saturations (DOPC, POPC, DPPC and DSPC), while the ILs' amphiphilicity, H-bond network density and polarity are varied between propylammonium nitrate (PAN) to ethylammonium nitrate (EAN) to ethanolammonium nitrate (EtAN). FINDINGS: The observed structures and phase behaviour of the lipids becomes more surfactant-like with decreasing average solvent polarity, H-bond network density and surface tension. In PAN, all the investigated phospholipids behave like surfactants in water. In EAN they exhibit anomalous phase sequences and unexpected transitions as a function of temperature, while EtAN supports structures that share characteristics with water and EAN. Structures formed are also sensitive to proximity to the lipid chain melting temperature.

Effect of Potential on the Nanostructure Dynamics of Ethylammonium Nitrate at a Graphite Electrode.

Video-rate atomic force microscopy (AFM) is used to study the near-surface nanostructure dynamics of the ionic liquid ethylammonium nitrate (EAN) at a highly oriented pyrolytic graphite (HOPG) electrode as a function of potential in real-time for the first time. The effects of varying the surface potential and adding 10 wt% water on the nanostructure diffusion coefficient are probed. For both EAN and the 90 wt% EAN-water mixture, disk-like features ≈9 nm in diameter and 1 nm in height form above the Stern layer at all potentials. The nanostructure diffusion coefficient increases with potential (from OCP -0.5 V to OCP +0.5 V) and with added water. Nanostructure dynamics depends on both the magnitude and direction of the potential change. Upon switching the potential from OCP -0.5 V to OCP +0.5 V, a substantial increase in the diffusion coefficients is observed, likely due to the absence of solvophobic interactions between the nitrate (NO3 - ) anions and the ethylammonium (EA+ ) cations in the near-surface region. When the potential is reversed, EA+ is attracted to the Stern layer to replace NO3 - , but its movement is hindered by solvophobic attractions. The outcomes will aid applications, including electrochemical devices, catalysts, and lubricants.

Ions Adsorbed at Amorphous Solid/Solution Interfaces Form Wigner Crystal-like Structures.

When a surface is immersed in a solution, it usually acquires a charge, which attracts counterions and repels co-ions to form an electrical double layer. The ions directly adsorbed to the surface are referred to as the Stern layer. The structure of the Stern layer normal to the interface was described decades ago, but the lateral organization within the Stern layer has received scant attention. This is because instrumental limitations have prevented visualization of the ion arrangements except for atypical, model, crystalline surfaces. Here, we use high-resolution amplitude modulated atomic force microscopy (AFM) to visualize in situ the lateral structure of Stern layer ions adsorbed to polycrystalline gold, and amorphous silica and gallium nitride (GaN). For all three substrates, when the density of ions in the layer exceeds a system-dependent threshold, correlation effects induce the formation of close packed structures akin to Wigner crystals. Depending on the surface and the ions, the Wigner crystal-like structure can be hexagonally close packed, cubic, or worm-like. The influence of the electrolyte concentration, species, and valence, as well as the surface type and charge, on the Stern layer structures is described. When the system parameters are changed to reduce the Stern layer ion surface excess below the threshold value, Wigner crystal-like structures do not form and the Stern layer is unstructured. For gold surfaces, molecular dynamics (MD) simulations reveal that when sufficient potential is applied to the surface, ion clusters form with dimensions similar to the Wigner crystal-like structures in the AFM images. The lateral Stern layer structures presented, and in particular the Wigner crystal-like structures, will influence diverse applications in chemistry, energy storage, environmental science, nanotechnology, biology, and medicine.

Bulk nanostructure of a deep eutectic solvent with an amphiphilic hydrogen bond donor.

Neutron diffraction with empirical potential structure refinement (EPSR) show the deep eutectic solvent (DES) 1 : 4 choline chloride : butyric acid is amphiphilically nanostructured. Nanostructure results from solvophobic interactions between the alkyl chains of the butyric acid hydrogen bond donor (HBD) and is retained with addition of 10 wt% water. EPSR fits to the diffraction data is used to produce a three-dimensional model of the liquid which is interrogated to reveal the interactions leading to the solvophobic effect, and therefore nanostructure, in this DES at atomic resolution. The model shows electrostatic and hydrogen bond interactions cause the cation, anion and HBD acid group to cluster into a polar domain, from which the acid alkyl chains are solvophobically excluded into theapolar domain. The polar and apolar domains percolate through the liquid in a bicontinuous sponge-like structure. The effect of adding 10 wt% water is probed, revealing that water molecules are sequestered around the cation and anion within the polar domain, while the neat bulk structure is retained. Alkyl chain packing in the apolar domain becomes slightly better-defined indicating water marginally strengthens solvophobic segregation. These findings reveal bulk self-assembled nanostructure can be produced in DESs via an amphiphilic HBD.

Nanostructure of Locally Concentrated Ionic Liquids in the Bulk and at Graphite and Gold Electrodes.

The physical properties of ionic liquids (ILs) have led to intense research interest, but for many applications, high viscosity is problematic. Mixing the IL with a diluent that lowers viscosity offers a solution if the favorable IL physical properties are not compromised. Here we show that mixing an IL or IL electrolyte (ILE, an IL with dissolved metal ions) with a nonsolvating fluorous diluent produces a low viscosity mixture in which the local ion arrangements, and therefore key physical properties, are retained or enhanced. The locally concentrated ionic liquids (LCILs) examined are 1-hexyl-3-methylimidazolium bis(trifluoromethylsulfonyl)imide (HMIM TFSI), 1-hexyl-3-methylimidazolium tris(pentafluoroethyl)trifluorophosphate (HMIM FAP), or 1-butyl-3-methylimidazolium tris(pentafluoroethyl)trifluorophosphate (BMIM FAP) mixed with 1,1,2,2-tetrafluoroethyl 2,2,2-trifluoroethyl ether (TFTFE) at 2:1, 1:1, and 1:2 (w/w) IL:TFTFE, as well as the locally concentrated ILEs (LCILEs) formed from 2:1 (w/w) HMIM TFSI-TFTFE with 0.25, 0.5, and 0.75 m lithium bis(trifluoromethylsulfonyl)imide (LiTFSI). Rheology and conductivity measurements reveal that the added TFTFE significantly reduces viscosity and increases ionic conductivity, and cyclic voltammetry (CV) reveals minimal reductions in electrochemical windows on gold and carbon electrodes. This is explained by the small- and wide-angle X-ray scattering (S/WAXS) and atomic force microscopy (AFM) data, which show that the local ion nanostructures are largely retained in LCILs and LCILEs in bulk and at gold and graphite electrodes for all potentials investigated.

Phase behaviour and aggregate structures of the surface-active ionic liquid [BMIm][AOT] in water.

HYPOTHESIS: The surface-active ionic liquid, 1-butyl-3-methylimidazolium 1,4-bis-2-ethylhexylsulfosuccinate ([BMIm][AOT]), has a sponge-like bulk nanostructure consisting of percolating polar and apolar domains formed by the ion charge groups and alkyl chains, respectively. We hypothesise that added water will swell the polar domains and change the liquid nanostructure. EXPERIMENTS: Small angle X-ray scattering (SAXS), small angle neutron scattering (SANS) and polarizing optical microscopy (POM) were used to investigate the nanostructure of [BMIm][AOT] as a function of water content. Differential scanning calorimetry (DSC) was employed to probe the thermal transitions of [BMIm][AOT]-water mixtures and the mobility of water molecules. FINDINGS: SAXS, SANS and POM show that at lower water contents, [BMIm][AOT]-water mixtures have a sponge-like nanostructure similar to the pure SAIL, at medium water contents a lamellar phase forms, and at high water contents vesicles form. DSC results reveal that water molecules are supercooled in the lamellar phase. For the first time, results reveal a series of transitions from inverse sponge, to lamellar then to vesicles, for [BMIm][AOT] upon dilution with water.

Unusual phosphatidylcholine lipid phase behavior in the ionic liquid ethylammonium nitrate.

HYPOTHESIS: The forces that govern lipid self-assembly ionic liquids are similar to water, but their different balance can result in unexpected behaviour. EXPERIMENTS: The self-assembly behaviour and phase equilibria of two phospholipids, 1,2-distearoyl-sn-glycero-3-phosphocholine (DSPC) and 1-palmitoyl-2-oleoyl-sn-glycero-3-phosphocholine (POPC), in the most common protic ionic liquid, ethylammonium nitrate (EAN) have been investigated as function of composition and temperature by small- and wide-angle X-ray scattering (SAXS/WAXS) and small-angle neutron scattering (SANS). FINDINGS: Both lipids form unusual self-assembly structures and show complex and unexpected phase behaviour unlike that seen in water; DSPC undergoes a gel Lß to crystalline Lc phase transition on warming, while POPC forms worm-like micelles L1 upon dilution. This surprising phase behaviour is attributed to the large size of the EAN ions that solvate the lipid headgroup compared to water changing amphiphile packing. Weaker H-bonding between EAN and lipid headgroups also contributes. These results provide new insight for the design of lipid based nanostructured materials in ionic liquids with atypical properties.

How Does Nanostructure in Ionic Liquids and Hybrid Solvents Affect Surfactant Self-Assembly?

Ionic liquids (ILs) have recently emerged as novel classes of solvents that support surfactant self-assembly into micelles, liquid crystals, and microemulsions. Their low volatility and wide liquid stability ranges make them attractive for many diverse applications, especially in extreme environments. However, the number of possible ion combinations makes systematic investigations both challenging and rare; this is further amplified when mixtures are considered, whether with water or other H-bonding components such as those found in deep eutectics. In this Perspective we examine what factors determine amphiphilicity, solvophobicity and solvophilicity, in ILs and related exotic environments, in what ways these differ from water, and how the underlying nanostructure of the liquid itself affects the formation and structure of micelles and other self-assembled materials.

Molecular Resolution Nanostructure and Dynamics of the Deep Eutectic Solvent-Graphite Interface as a Function of Potential.

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 is switched 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.

Extremely slow dynamics of ionic liquid self-assembled nanostructures near a solid surface.

HYPOTHESIS: 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. EXPERIMENTS: 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. FINDINGS: 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.

Effect of ion structure on the nanostructure and electrochemistry of surface active ionic liquids.

HYPOTHESIS: 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. EXPERIMENTS: 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. FINDINGS: 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 windows >4 V, which are not affected by the alkyl chain structure and cation charge groups.

Intracellular Communication between Synthetic Macromolecules.

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.

Lipid Membrane Flexibility in Protic Ionic Liquids.

Here, we determine by neutron spin echo spectrometry (NSE) how the flexibility of egg lecithin vesicles depends on solvent composition in two protic ionic liquids (PILs) and their aqueous mixtures. In combination with small-angle neutron scattering (SANS), dynamic light scattering (DLS), and fluorescent probe microscopy, we show that the bending modulus is up to an order of magnitude lower than in water but with no change in bilayer thickness or nonpolar chain composition. This effect is attributed to the dynamic association and exchange of the IL cation between the membrane and bulk liquid, which has the same origin as the underlying amphiphilic nanostructure of the IL solvent itself. This provides a new mechanism by which to tune and control lipid membrane behavior.

Polycation radius of gyration in a polymeric ionic liquid (PIL): the PIL melt is not a theta solvent.

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 q scattering that can be mitigated using mixtures of hydrogen- and deuterium-rich materials, allowing determination of the polycation conformation and radius of gyration (Rg). In the pure PIL, the polycation adopts a random coil conformation with Rg = 52 ± 0.5 Å. In contrast to conventional polymer melts, the pure PIL is not a theta solvent for the polycation. The TFSI- anions, which comprise 48% v/v of the PIL, are strongly attracted to the polycation and act like small solvent molecules which leads to chain swelling analogous to an entangled, semi-dilute, or concentrated polymer solution in a good solvent.

Self-assembled nanostructure induced in deep eutectic solvents via an amphiphilic hydrogen bond donor.

HYPOTHESIS: Popular deep eutectic solvents (DESs) typically lack amphiphilic molecules and ions and therefore do not have the useful self-assembled nanostructures prevalent in many ionic liquids. We hypothesise that nanostructure in DESs can be induced via an amphiphilic hydrogen bond donor (HBD), and that nanostructure becomes better defined with HBD chain length. EXPERIMENTS: The structure of DESs formed from choline chloride mixed with either butyric acid (ChCl/BuOOH) or hexanoic acid (ChCl/HeOOH) in a 1:4 M ratio were studied using atomic force microscopy (AFM) imaging, force curves, and friction measurements combined with bulk rheology. FINDINGS: DESs formed with both the C4 and C6 acids are nanostructured. As the length of the acid group is increased from C4 to C6, AFM images reveal the nanostructure becomes larger and better defined due to the longer acid chain, and AFM force curves show the interfacial nanostructure extends further from the surface. Self-assembled nanostructure in these systems is a consequence of choline cations, chloride anions, and acid alcohol groups clustering together due to electrostatic attractions and hydrogen bonding to form polar domains. Acid alkyl chains are solvophobically excluded from the polar domains and aggregate into apolar domains.

Interfacial nanostructure and friction of a polymeric ionic liquid-ionic liquid mixture as a function of potential at Au(111) electrode interface.

HYPOTHESIS: The polymeric cations of polymeric ionic liquids (PILs) can adsorb from the bulk of a conventional ionic liquid (IL) to the Au(111) 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(111) 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.

Nanostructure, electrochemistry and potential-dependent lubricity of the catanionic surface-active ionic liquid [P6,6,6,14] [AOT].

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.