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.

Stiffness-Dependent Intracellular Location of Cylindrical Polymer Brushes.

Cylindrical polymer brushes (CPBs) are macromolecules with nanoparticle proportions. Their modular synthesis enables tailoring of their chemical composition as well as the dialing-up of overall dimensions and physicochemical properties. In this study, two rod-like poly[(ethylene glycol) methyl ether methacrylate] (PEGMA)-based CPBs with varying stiffness but otherwise comparable features and functionality, are synthesized. Differences in particle stiffness are assessed using small angle neutron scattering (SANS). It is observed that the fate of the two CPBs within cells is distinctly different. Stiffer CPBs seem to gravitate toward the mitochondria, whereas CPBs with reduced stiffness are present in different intracellular vesicles.

Effect of halides on the solvation of poly(ethylene oxide) in the ionic liquid propylammonium nitrate.

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.

Hydrophobic Monomer Type and Hydrophilic Monomer Ionization Modulate the Lyotropic Phase Stability of Diblock Co-oligomer Amphiphiles.

The phase behavior and self-assembly structures of a series of amphiphilic diblock co-oligomers comprising an ionizable hydrophilic block (5 to 10 units of acrylic acid) and a hydrophobic block (5 to 20 units of n-butyl acrylate, t-butyl acrylate, or ethyl acrylate), synthesized by RAFT polymerization, have been examined by polarizing optical microscopy and small-angle X-ray scattering (SAXS). Self-assembled structure and lyotropic phase stability in these systems is highly responsive to the degree of ionization of the acrylic acid hydrophilic block (i.e., pH), concentration, and nature of the hydrophobic block. Increasing headgroup ionization switched the amphiphiles from behaving like soluble to insoluble surfactants. Liquid isotropic (micellar), hexagonal, lamellar, and discrete cubic phases were found under different solution conditions. The surfactant packing parameter was adapted to understand the self-assembly structures in these diblock co-oligomers. The hydrophobic chain structure and length were shown to strongly affect the relative stabilities of these phases, allowing the self-assembled structure to be varied at will.

Study of (Cyclic Peptide)-Polymer Conjugate Assemblies by Small-Angle Neutron Scattering.

We present a fundamental study into the self-assembly of (cyclic peptide)-polymer conjugates as a versatile supramolecular motif to engineer nanotubes with defined structure and dimensions, as characterised in solution using small-angle neutron scattering (SANS). This work demonstrates the ability of the grafted polymer to stabilise and/or promote the formation of unaggregated nanotubes by the direct comparison to the unconjugated cyclic peptide precursor. This ideal case permitted a further study into the growth mechanism of self-assembling cyclic peptides, allowing an estimation of the cooperativity. Furthermore, we show the dependency of the nanostructure on the polymer and peptide chemical functionality in solvent mixtures that vary in the ability to compete with the intermolecular associations between cyclic peptides and ability to solvate the polymer shell.

Structural effect of glyme-Li(+) salt solvate ionic liquids on the conformation of poly(ethylene oxide).

The conformation of 36 kDa polyethylene oxide (PEO) dissolved in three glyme-Li(+) solvate ionic liquids (SILs) has been investigated by small angle neutron scattering (SANS) and rheology as a function of concentration and compared to a previously studied SIL. The solvent quality of a SIL for PEO can be tuned by changing the glyme length and anion type. Thermogravimetric analysis (TGA) reveals that PEO is dissolved in the SILs through Li(+)-PEO coordinate bonds. All SILs (lithium triglyme bis(trifluoromethanesulfonyl)imide ([Li(G3)]TFSI), lithium tetraglyme bis(pentafluoroethanesulfonyl)imide ([Li(G4)]BETI), lithium tetraglyme perchlorate ([Li(G4)]ClO4) and the recently published [Li(G4)]TFSI) are found to be moderately good solvents for PEO but solvent quality decreases in the order [Li(G4)]TFSI ∼ [Li(G4)]BETI > [Li(G4)]ClO4 > [Li(G3)]TFSI due to decreased availability of Li(+) for PEO coordination. For the same glyme length, the solvent qualities of SILs with TFSI(-) and BETI(-) anions ([Li(G4)]TFSI and [Li(G4)]BETI) are very similar because they weakly coordinate with Li(+), which facilitates Li(+)-PEO interactions. [Li(G4)]ClO4 presents a poorer solvent environment for PEO than [Li(G4)]BETI because ClO4(-) binds more strongly to Li(+) and thereby hinders interactions with PEO. [Li(G3)]TFSI is the poorest PEO solvent of these SILs because G3 binds more strongly to Li(+) than G4. Rheological and radius of gyration (Rg) data as a function of PEO concentration show that the PEO overlap concentrations, c* and c**, are similar in the three SILs.

Structural and aggregate analyses of (Li salt + glyme) mixtures: the complex nature of solvate ionic liquids.

The structure and interactions of different (Li salt + glyme) mixtures, namely equimolar mixtures of lithium bis(trifluoromethylsulfonyl)imide, nitrate or trifluoroacetate salts combined with either triglyme or tetraglyme molecules, are probed using Molecular Dynamics simulations. structure factor functions, calculated from the MD trajectories, confirmed the presence of different amounts of lithium-glyme solvates in the aforementioned systems. The MD results are corroborated by S(q) functions derived from diffraction and scattering data (HEXRD and SAXS/WAXS). The competition between the glyme molecules and the salt anions for the coordination to the lithium cations is quantified by comprehensive aggregate analyses. Lithium-glyme solvates are dominant in the lithium bis(trifluoromethylsulfonyl)imide systems and much less so in systems based on the other two salts. The aggregation studies also emphasize the existence of complex coordination patterns between the different species (cations, anions, glyme molecules) present in the studied fluid media. The analysis of such complex behavior is extended to the conformational landscape of the anions and glyme molecules and to the dynamics (solvate diffusion) of the bis(trifluoromethylsulfonyl)imide plus triglyme system.

Conformation of poly(ethylene oxide) dissolved in the solvate ionic liquid [Li(G4)]TFSI.

The conformation of 38 kDa PEO in a solvate ionic liquid (SIL), lithium tetraglyme bis(trifluoromethane-sulfonyl)amide ([Li(G4)]TFSI) from dilute to concentrated solution regimes has been determined by small angle neutron scattering and rheology. SANS analysis reveals that [Li(G4)]TFSI is better than a theta solvent (theta-good) for PEO. The variation of the radius of gyration (Rg) and viscosity as a function of polymer concentration allow the overlap concentrations, c* and c**, to be identified at 13 mg mL(-1) and 50 mg mL(-1), respectively, which are similar to values reported previously for conventional ionic liquids. Unlike water and conventional ionic liquids, [Li(G4)]TFSI cannot form hydrogen bonds with PEO. Thermal gravimetric analysis indicates that the solvation of PEO by [Li(G4)]TFSI is a consequence of PEO forming coordinate bonds with the lithium by displacing the anion, but without displacing the glyme molecule.

Micelle structure in a photoresponsive surfactant with and without solubilized ethylbenzene from small-angle neutron scattering.

Photoresponsive micellar systems of 4-butylazobenzene-4'- (oxyethyl)trimethylammonium bromide (AZTMA) were examined with and without ethylbenzene using small-angle neutron scattering (SANS). Analysis of SANS profiles showed that an aqueous solution containing 5, 10, and 50 mM AZTMA forms prolate spheroids with a long radius (Ra) of 38 Å and a short radius (Rb) of 21 Å. In the 5 mM AZTMA solution, the concentration of micelles decreased upon UV light irradiation, while their size and shape remained almost unchanged. Subsequent visible light irradiation reversed the decrease and increased the number of micelles. In contrast, 10 and 50 mM AZTMA solutions showed that the number and long radius of the micelles decreased with UV light irradiation, while subsequent exposure to visible light irradiation restored them. For AZTMA micellar solutions equilibrated with excess ethylbenzene, the solubilized amount of ethylbenzene increased upon UV light irradiation due to enhanced swelling of the micelles with cis-AZTMA. This photoinduced uptake of the solubilizate has potential applicability for the collection and removal of hazardous oily substances.

Interfacial and bulk nanostructure of liquid polymer nanocomposites.

Liquid polymer nanocomposites (l-PNCs) have been prepared using silica nanoparticles with diameters of 15 nm (l-PNC-15) and 24 nm (l-PNC-24), and Jeffamine M-2070, an amine-terminated ethylene oxide/propylene oxide (PEO/PPO, ratio 31/10) copolymer. Jeffamine M-2070 was used as the host liquid in which the particles were suspended and was also grafted onto the particle surface to prevent aggregation. The grafting density of Jeffamine M-2070 on the particle surfaces was ∼0.75 chains nm(-2). When the total polymer content (surface layer + host) was greater than ∼30 wt %, the PNC was a liquid, while at lower polymer volume fractions the PNC was solid. In this work, the bulk and surface structures of l-PNCs with ∼70 wt % polymer and 30% silica are characterized and compared. Small-angle neutron scattering (SANS) was used to probe the bulk structure of the l-PNCs and revealed that the particles are well-dispersed with minor clustering in l-PNC-15 and substantial clustering in l-PNC-24. This is attributed to stronger van der Waals attractions between particles due to the larger particle size in l-PNC-24. Corresponding effects were revealed using tapping mode atomic force microscopy (TM-AFM) at the l-PNC-air interface; clustering was minimal on the surface of l-PNC-15 but significant for l-PNC-24 droplets. In regions of the l-PNC where the particles were well-dispersed, the spacing between particles is consistent with their volume fractions. This is the first time that the distribution of polymer and particles within l-PNCs has been imaged in situ.

Structure and composition of mixed micelles of polymerized and monomeric surfactants.

Micelle structure and composition has been determined by small-angle neutron scattering for mixed micellar solutions of in situ polymerized ω-methacryloyloxyundecyl-trimethylammonium bromide (MUTAB) in equilibrium with its monomeric form at various concentrations, as well as in mixtures with a fluorinated cationic surfactant, heptadecafluorodecylpyridinium chloride (HFDePC), and the non-ionic surfactant, C12E7. Whereas polymerized MUTAB is immiscible with HFDePC and forms two populations of distinct spheroidal micelles, it mixes with C12E7 in all proportions and forms a single average micelle structure depending on composition. These results allow us to explain the origin of the previously reported formation of mixed worm-like micelles of polymerized and monomeric MUTAB that coexist with globular monomeric MUTAB micelles as a consequence of the unfavourable electrostatic interactions that accompany the uncoiling of polymerized MUTAB chains in unimer micelles when swollen by monomeric cationic surfactants.

Amphiphilic self-assembly of alkanols in protic ionic liquids.

Strong cohesive forces in protic ionic liquids (PILs) can induce a liquid nanostructure consisting of segregated polar and apolar domains. Small-angle X-ray scattering has shown that these forces can also induce medium chain length n-alkanols to self-assemble into micelle- and microemulsion-like structures in ethylammonium (EA(+)) and propylammonium (PA(+)) PILs, in contrast to their immiscibility with both water and ethanolammonium (EtA(+)) PILs. These binary mixtures are structured on two distinct length scales: one associated with the self-assembled n-alkanol aggregates and the other with the underlying liquid nanostructure. This suggests that EA(+) and PA(+) enable n-alkanol aggregation by acting as cosurfactants, which EtA(+) cannot do because its terminating hydroxyl renders the cation nonamphiphilic. The primary determining factor for miscibility and self-assembly is the ratio of alkyl chain lengths of the alkanol and PIL cation, modulated by the anion type. These results show how ILs can support the self-assembly of nontraditional amphiphiles and enable the creation of new forms of soft matter.

Temperature- and pH-responsive micelles with collapsible poly(N-isopropylacrylamide) headgroups.

We have studied the micelle formation and phase behavior of a series of temperature- and pH-responsive surfactants prepared by controlled radical (RAFT) polymerization. These C12NIPAMm surfactants consist of a dodecyl tail, a poly(N-isopropylacrylamide) (polyNIPAM) headgroup with average degrees of polymerization of between 7 and 96, and an ionizable carboxylate group. In the un-ionized state, these surfactants phase separate on warming toward a lower critical solution temperature (LCST), which decreases as the length of the NIPAM group is decreased. This is in agreement with the behavior of conventional nonionic poly(ethylene oxide)-based surfactants but is very different from that of polyNIPAM oligomer solutions. Small angle neutron scattering (SANS) shows that these surfactants self-assemble into micelles consisting of a nearly spherical hydrophobic core surrounded by a "hairy" polyNIPAM shell far below their LCST. Upon warming, the micelles undergo a sphere-to-rod transition induced by the collapse of the polyNIPAM shell, causing a reduction in the headgroup area. In the un-ionized state the demixing follows at the LCST, but a single charge on the free polymer end completely suppresses phase separation, allowing micelles to undergo a shape change but remain dissolved.

Effect of protic ionic liquid and surfactant structure on partitioning of polyoxyethylene non-ionic surfactants.

The partitioning constants and Gibbs free energies of transfer of poly(oxyethylene) n-alkyl ethers between dodecane and the protic ionic liquids (ILs) ethylammonium nitrate (EAN) and propylammonium nitrate (PAN) are determined. EAN and PAN have a sponge-like nanostructure that consists of interpenetrating charged and apolar domains. This study reveals that the ILs solvate the hydrophobic and hydrophilic parts of the amphiphiles differently. The ethoxy groups are dissolved in the polar region of both ILs by means of hydrogen bonds. The environment is remarkably water-like and, as in water, the solubility of the ethoxy groups in EAN decreases on warming, which underscores the critical role of the IL hydrogen-bond network for solubility. In contrast, amphiphile alkyl chains are not preferentially solvated by the charged or uncharged regions of the ILs. Rather, they experience an average IL composition and, as a result, partitioning from dodecane into the IL increases as the cation alkyl chain is lengthened from ethyl to propyl, because the IL apolar volume fraction increases. Together, these results show that surfactant dissolution in ILs is related to structural compatibility between the head or tail group and the IL nanostructure. Thus, these partitioning studies reveal parameters for the effective molecular design of surfactants in ILs.

Structure of polymerizable surfactant micelles: insights from neutron scattering.

Although polymerization of reactive surfactants (surfmers) in micelles and other self-assembled phases has been studied for at least 30 years, the last decade or so has seen substantial advances in understanding both the structure and dynamics of these systems. In this review we highlight the new insights yielded primarily by small-angle neutron scattering (SANS) using high-flux sources, the perspective this provides for realizing topochemical polymerization in micellar systems, and the prospects and new developments for further exploiting SANS in this field. We present some new neutron contrast variation results exemplifying these elements.

Micellization of monomeric and poly-ω-methacryloyloxyundecyltrimethylammonium surfactants.

We have used small-angle neutron scattering to study how micelle morphology of the tail-polymerizable surfactants MUTAB and MUTAC (ω-methacryloyloxyundecyltrimethylammonium bromide and chloride) is affected by classic self-assembly modifiers such as temperature changes, salt addition, and counterion exchange, as a function of their conversion from monomer into polymer amphiphile in aqueous solution. Contrary to common assumptions about polymerized surfactants, these systems remain in dynamic equilibrium under all conditions examined and at all conversions (except for a small amount of high-molecular-weight precipitation by MUTAC). Counterintuitively, the polymerized methacrylate backbone has little influence on aggregate morphology, except for the formation of rod-like mixed micelles of polymerized and unpolymerized surfactant at intermediate conversions. The addition of salt produces a transition to rod-like micelles at all conversions except in the unpolymerized surfactant, which has some characteristics of an asymmetric bolaform surfactant and retains its spheroidal geometry under almost all conditions.

Swelling and collapse of an adsorbed pH-responsive film-forming microgel measured by optical reflectometry and QCM.

The swelling and deswelling of a pH-responsive electrosterically stabilized poly[2-(diethylamino)ethyl methacrylate] microgel adsorbed to silica surfaces have been quantified using the techniques of optical reflectometry (OR) and quartz crystal microbalance (QCM). It is shown that by utilizing and comparing OR measurements performed on wafers with differing oxide layer thicknesses the adsorbed amount and film thickness of the adsorbed microgel in both the swollen and deswollen forms can be determined. Also, the kinetics of the transition can be followed, revealing that collapse is a slower process than swelling, and direct support is provided for the formation of a dense outer layer or skin during collapse that slows the deswelling process. It is shown that the adsorption of this low glass transition temperature film-forming microgel latex is robust to changes in pH after an initial swelling event which is responsible for desorption of a large and variable fraction of the initially adsorbed polymer. Subsequent deswelling and swelling of the adsorbed film indicates that adsorption to a surface greatly hinders the volumetric swelling capacity of the microgel film. In its swollen state the film is only 3-4 times thicker than the collapsed film, whereas for particles in bulk the volume increases by a factor of 20 upon protonation of the tertiary amine residues. QCM results show that even in the collapsed form the film contains a considerable amount of water. Further, the viscoelasticity of the deswollen film is similar to that of the swollen film, suggesting that the degree of cross-linking is the primary determinant of viscoelasticity.

Polymerizable cationic micelles form cylinders at intermediate conversions.

The structural evolution of micelles of the polymerizable surfactant omega-methacryloyloxyundecyltrimethylammonium bromide (MUTAB) during UV-initiated polymerization in aqueous micellar solution has been followed by small-angle neutron scattering. Although the micelles are short spheroids both before and after polymerization, a significant, distinct population of rodlike micelles develops during the reaction, which accounts for as much as 40 vol % of the micellized surfactant and coexists with the spheroids and dissolved monomer. These coexisting micelle populations are shown to remain in dynamic equilibrium throughout the reaction and can be understood by treating it as a ternary mixture of surfactant, amphiphilic polyelectrolyte, and water.

Film-forming microgels for pH-triggered capture and release.

The pH-responsive behavior for a series of lightly cross-linked, sterically stabilized poly(tertiary amine methacrylate)-based latexes adsorbed onto mica and silica was investigated using in situ tapping mode AFM at room temperature. The adsorbed layer structure was primarily determined by the glass transition temperature, T(g), of the latex: poly[2-(diethylamino)ethyl methacrylate]-based particles coalesced to form relatively featureless uniform thin films, whereas the higher T(g) poly[2-(diisopropylamino)ethyl methacrylate] latexes retained their original particulate character. Adsorption was enhanced by using a cationic poly[2-(dimethylamino)ethyl methacrylate] steric stabilizer, rather than a nonionic poly(ethylene glycol)-based stabilizer, since the former led to stronger electrostatic binding to the oppositely charged substrate. Both types of adsorbed latexes acquired cationic microgel character and swelled appreciably at low pH, even those that had coalesced to form films. Fluorescence spectroscopy was used to study the capture of a model hydrophobic probe, pyrene, by these adsorbed latex layers followed by its subsequent release by lowering the solution pH. The repeated capture and release of pyrene through several pH cycles was also demonstrated. Since these poly(tertiary amine methacrylate) latexes are readily prepared by aqueous emulsion polymerization and adsorption occurs spontaneously from aqueous solution, this may constitute an attractive route for the surface modification of silica, mica and other oxides.

In situ observations of adsorbed microgel particles.

The formation and morphological changes of a pH-responsive microgel layer on silica and mica were studied by tapping mode atomic force microscopy. First, lightly cross-linked, sterically-stabilised poly(2-vinylpyridine) (P2VP) particles were adsorbed in their non-solvated latex form at pH 4.8 to produce a structurally-disordered monolayer that covers the entire substrate. Addition of acid to this particulate film induces a latex-to-microgel transition at pH 3.0, causes particle swelling (and also some desorption) and produces a uniform, swollen film with localised hexagonal packing. Returning to pH 4.8 causes partial microgel deswelling to form individual oblate spheroidal P2VP latex particles, which retain the localised order previously induced by swelling. The swelling and collapse of this P2VP film was reversible during subsequent pH cycles, with no further desorption observed. The adsorbed amount of P2VP microgel/latex was quantified at each pH by determining the surface density and dimensions of the adsorbed particles. These measurements allow the microgel surface excess to be calculated for the first time. The initial adsorbed amount is less than that predicted by the standard Random Sequential Adsorption model (RSA) for hard particle adsorption, and is explained by the unexpected deformation of these high Tg particles due to their strong electrostatic attraction to the solid-liquid interface.