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.

Aqueous choline amino acid deep eutectic solvents.

We have investigated the structure and phase behavior of biocompatible, aqueous deep eutectic solvents by combining choline acetate, hydrogen aspartate, and aspartate amino acid salts with water as the sole molecular hydrogen bond donor. Using contrast-variation neutron diffraction, interpreted via computational modeling, we show how the interplay between anion structure and water content affects the hydrogen bond network structure in the liquid, which, in turn, influences the eutectic composition and temperature. These mixtures expand the current range choline amino acid ionic liquids under investigation for biomass processing applications to include higher melting point salts and also explain how the ionic liquids retain their desirable properties in aqueous solution.

Hydration of sulfobetaine dizwitterions as a function of alkyl spacer length.

The solvation and structure of bolaform dizwitterions containing two sulfobetaine moieties in concentrated aqueous solution were determined using neutron diffraction with isotopic substitution (NDIS) combined with modelling of the measured structure factors using Empirical Potential Structure Refinement (EPSR). Strongly directional local hydration was observed in the polar regimes of the dizwitterions with 48-52 water molecules shared between dizwitterion molecules in a first shell water network around each zwitterion pair. Overall, the double zwitterions were highly hydrated, providing experimental evidence in support of the potential formation of protein-resistant hydration layers at zwitterion-water interfaces.

Applying neutron diffraction with isotopic substitution to the structure and proton-transport pathways in protic imidazolium bis{(trifluoromethyl)sulfonyl}imide ionic liquids.

Neutron diffraction with isotopic substitution has been applied to examine the potential for complex-ion formation in protic imidazolium bis{(trifluoromethyl)sulfonyl}imide ionic liquids. Strong cation-anion hydrogen-bonding in the 1 : 1 base : acid ionic liquid results in a high population of anions adopting a cis-conformation and, on adding excess imidazole (2 : 1 base : acid stoichiometry), cation-base and base-base correlations were identified, however, persistent hydrogen-bond associations were not observed.

Nuclear dynamics and phase polymorphism in solid formic acid.

We apply a unique sequence of structural and dynamical neutron-scattering techniques, augmented with density-functional electronic-structure calculations, to establish the degree of polymorphism in an archetypal hydrogen-bonded system - crystalline formic acid. Using this combination of experimental and theoretical techniques, the hypothesis by Zelsmann on the coexistence of the ß1 and ß2 phases above 220 K is tested. Contrary to the postulated scenario of proton-transfer-driven phase coexistence, the emerging picture is one of a quantitatively different structural change over this temperature range, whereby the loosening of crystal packing promotes temperature-induced shearing of the hydrogen-bonded chains. The presented work, therefore, solves a fifty-year-old puzzle and provides a suitable framework for the use neutron-Compton-scattering techniques in the exploration of phase polymorphism in condensed matter.

Ionic liquid nanostructure enables alcohol self assembly.

Weakly structured solutions are formed from mixtures of one or more amphiphiles and a polar solvent (usually water), and often contain additional organic components. They contain solvophobic aggregates or association structures with incomplete segregation of components, which leads to a poorly defined interfacial region and significant contact between the solvent and aggregated hydrocarbon groups. The length scales, polydispersity, complexity and ill-defined structures in weakly structured solutions makes them difficult to probe experimentally, and obscures understanding of their formation and stability. In this work we probe the nanostructure of homogenous binary mixtures of the ionic liquid (IL) propylammonium nitrate (PAN) and octanol as a function of composition using neutron diffraction and atomistic empirical potential structure refinement (EPSR) fits. These experiments reveal why octanol forms weakly structured aggregates in PAN but not in water, the mechanism by which PAN stabilises the octanol assemblies, and how the aggregate morphologies evolve with octanol concentration. This new understanding provides insight into the general stabilisation mechanisms and structural features of weakly structured mixtures, and reveals new pathways for identifying molecular or ionic liquids that are likely to facilitate aggregation of non-traditional amphiphiles.

How the surface structure determines the properties of CuH.

CuH is a material that appears in a wide diversity of circumstances ranging from catalysis to electrochemistry to organic synthesis. There are both aqueous and nonaqueous synthetic routes to CuH, each of which apparently leads to a different product. We developed synthetic methodologies that enable multigram quantities of CuH to be produced by both routes and characterized each product by a combination of spectroscopic, diffraction and computational methods. The results show that, while all methods for the synthesis of CuH result in the same bulk product, the synthetic path taken engenders differing surface properties. The different behaviors of CuH obtained by aqueous and nonaqueous routes can be ascribed to a combination of very different particle size and dissimilar surface termination, namely, bonded hydroxyls for the aqueous routes and a coordinated donor for the nonaqueous routes. This work provides a particularly clear example of how the nature of an adsorbed layer on a nanoparticle surface determines the properties.

Conformation and interactions of dopamine hydrochloride in solution.

The aqueous solution of dopamine hydrochloride has been investigated using neutron and X-ray total scattering data together with Monte-Carlo based modelling using Empirical Potential Structure Refinement. The conformation of the protonated dopamine molecule is presented and the results compared to the conformations found in crystal structures, dopamine-complexed protein crystal structures and predicted from theoretical calculations and pharmacophoric models. It is found that protonated dopamine adopts a range of conformations in solution, highlighting the low rotational energy barrier between different conformations, with the preferred conformation being trans-perpendicular. The interactions between each of the species present (protonated dopamine molecules, water molecules, and chloride anions) have been determined and are discussed with reference to interactions observed in similar systems both in the liquid and crystalline state, and predicted from theoretical calculations. The expected strong hydrogen bonds between the strong hydrogen bond donors and acceptors are observed, together with evidence of weaker CH hydrogen bonds and π interactions also playing a significant role in determining the arrangement of adjacent molecules.

Characterization of the hydrides in Stryker's reagent: [HCu{P(C6H5)3}]6.

A structural, spectroscopic, and computational investigation of Stryker's reagent, [HCu{P(C6H5)3}]6, and its isotopomers has provided new insights into the complex. Neutron diffraction shows that the hydrides are best described as edge bridging rather than face bridging. The combination of infrared and inelastic neutron scattering spectroscopies has allowed the location of most of the modes associated with the hydrides and their assignments. The structural and spectroscopic conclusions are supported by the ab initio studies of the complex.

Nanostructure of an ionic liquid-glycerol mixture.

The nanostructure of a 50 : 50 vol% mixture of glycerol and ethylammonium formate (EAF), a protic ionic liquid (IL), has been investigated using neutron diffraction and empirical potential structure refinement (EPSR) fits. EPSR fits reveal that the mixture is nanostructured. Electrostatic interactions between IL charge groups leads to the formation of ionic regions. These solvophobically repel cation alkyl groups which cluster together to form apolar domains. The polar glycerol molecules are preferentially incorporated into the charged domains, and form hydrogen bonds with EAF groups rather than with other glycerol molecules. However, radial distribution functions reveal that glycerol molecules pack around each other in a fashion similar to that found in pure glycerol. This suggests that a glycerol channel runs through the ionic domain of EAF. The absence of significant glycerol-glycerol hydrogen bonding indicates that glycerol molecules are able to span the polar domain, bridging EAF charge groups. Glycerol can adopt six distinct conformations. The distribution of conformers in the EAF mixture is very different to that found in the pure liquid because hydrogen bonds form with EAF rather than with other glycerol molecules, which imparts different packing constraints.

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.

The nature of hydrogen bonding in protic ionic liquids.

The size, direction, strength, and distribution of hydrogen bonds in several protic ionic liquids (PILs) has been elucidated using neutron diffraction and computer simulation. There is significant variation in PIL hydrogen bond interactions ranging from short and linear to long and bi-/trifurcated. The nature of the PIL's hydrogen bonds reflects its macroscopic properties.

Pronounced sponge-like nanostructure in propylammonium nitrate.

The bulk structure of the ionic liquid propylammonium nitrate (PAN) has been determined using neutron diffraction. Empirical potential structure refinement (EPSR) fits to the data show that PAN self-assembles into a quasi-periodic bicontinuous nanostructure reminiscent of an amphiphile L(3)-sponge phase. Atomic detail on the ion arrangements around the propylammonium cation and nitrate anion yields evidence of hydrogen bonding between ammonium and nitrate groups and of strong alkyl chain aggregation and interdigitation. The resultant amphiphilic PAN nanostructure is more pronounced than that previously determined for ethylammonium nitrate (EAN) or ethanolammonium nitrate (EtAN).

Amphiphilicity determines nanostructure in protic ionic liquids.

The bulk structure of the two oldest ionic liquids (ILs), ethylammonium nitrate (EAN) and ethanolammonium nitrate (EtAN), is elucidated using neutron diffraction. The spectra were modelled using empirical potential structure refinement (EPSR). The results demonstrate that EAN exhibits a long-range structure of solvophobic origin, similar to a bicontinuous microemulsion or disordered L(3)-sponge phase, but with a domain size of only 1 nm. The alcohol (-OH) moiety in EtAN interferes with solvophobic association between cation alkyl chains resulting in small clusters of ions, rather than an extended network.

Neutron Scattering Techniques for Studying Metal Complexes in Aqueous Solution.

Neutron scattering combined with ab initio calculations provides a powerful tool for studying metal complexes in different solvents and, particularly, in water. The majority of traditional characterization techniques in catalysis provide only limited information on homogeneous catalytic processes. Neutron scattering, on the other hand, thanks to its sensitivity to hydrogen atoms, and therefore water molecules, can be used to build detailed models of reaction paths and to observe, at a molecular level, the influence of solvent molecules on a catalytic process. In this Mini-Review we describe several examples on how neutron scattering combined with ab initio calculations can be used to examine the nature of the interaction of water molecules with catalytically active metal complexes in solution.

Neutron total scattering investigation on the dissolution mechanism of trehalose in NaOH/urea aqueous solution.

Trehalose is chosen as a model molecule to investigate the dissolution mechanism of cellulose in NaOH/urea aqueous solution. The combination of neutron total scattering and empirical potential structure refinement yields the most probable all-atom positions in the complex fluid and reveals the cooperative dynamic effects of NaOH, urea, and water molecules in the dissolution process. NaOH directly interacts with glucose rings by breaking the inter- and intra-molecular hydrogen bonding. Na+, thus, accumulates around electronegative oxygen atoms in the hydration shell of trehalose. Its local concentration is thereby 2-9 times higher than that in the bulk fluid. Urea molecules are too large to interpenetrate into trehalose and too complex to form hydrogen bonds with trehalose. They can only participate in the formation of the hydration shell around trehalose via Na+ bridging. As the main component in the complex fluid, water molecules have a disturbed tetrahedral structure in the presence of NaOH and urea. The structure of the mixed solvent does not change when it is cooled to -12 °C. This indicates that the dissolution may be a dynamic process, i.e., a competition between hydration shell formation and inter-molecule hydrogen bonding determines its dissolution. We, therefore, predict that alkali with smaller ions, such as LiOH, has better solubility for cellulose.

Liquid Structure of Single and Mixed Cation Alkylammonium Bromide Urea Deep Eutectic 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).

Hydration of Carboxyl Groups: A Route toward Molecular Recognition?

On Earth, water plays an active role in cellular life, over several scales of distance and time. At a nanoscale, water drives macromolecular conformation through hydrophobic forces and at short times acts as a proton donor/acceptor providing charge carriers for signal transmission. At longer times and larger distances, water controls osmosis, transport, and protein mobility. Neutron diffraction experiments augmented by computer simulation, show that the three-dimensional shape of the hydration shell of carboxyl and carboxylate groups belonging to different molecules is characteristic of each molecule. Different hydration shells identify and distinguish specific sites with the same chemical structure. This experimental evidence suggests an active role of water also in controlling, modulating, and mediating chemical reactions involving carboxyl and carboxylate groups.

Role of Water in Sucrose, Lactose, and Sucralose Taste: The Sweeter, The Wetter?

Natural sugars combine energy supply and, except a few cases, a pleasant taste. On the other hand, exaggerated consumption may impact population health. This has busted the research for the synthesis of increasingly cheaper artificial sweeteners, with low energy content and intense taste. Here, we suggest that studies of the hydration properties of three disaccharides, namely, the natural sucrose and lactose and the artificial sucralose, may explain the difference by orders of magnitude among their sweetness. This is done by analyzing via Monte Carlo simulations the neutron diffraction differential cross sections of aqueous solutions of the three sugars and their isotopes. Our results show that the strength of the sugar-water hydrogen bond interaction is one of the factors influencing sweetness, another being the number of water molecules within the first neighboring shell of the sugar whether bonded or not.

Structural Design of Ionic Liquids for Optimizing Aromatic Dissolution.

Certain protic ionic liquids (PILs) are potentially low-cost, high-efficiency solvents for the extraction and processing of aromatic compounds. To understand the key design features of PILs that determine solubility selectivity at the atomic level, neutron diffraction was used to compare the bulk structure of two PILs with and without an aromatic solute, guaiacol (2-methoxyphenol). Guaiacol is a common lignin residue in biomass processing, and a model compound for anisole- or phenol-based food additives and drug precursors. Although the presence of amphiphilic nanostructure is important to facilitate the dissolution of solute nonpolar moieties, the local geometry and competitive interactions between the polar groups of the cation, anion, and solute are found to also strongly influence solvation. Based on these factors, a framework is presented for the design of PIL structure to minimize competition and to enhance driving forces for the dissolution of small aromatic species.