The phase behavior, including glass, devitrification, solid crystal melting, and liquid boiling transitions, and physicochemical properties, including density, refractive index, viscosity, conductivity, and air-liquid surface tension, of a series of 25 protic ionic liquids and protic fused salts are presented along with structure-property comparisons. The protic fused salts were mostly liquid at room temperature, and many exhibited a glass transition occurring at low temperatures between -114 and -44 degrees C, and high fragility, with many having low viscosities, down to as low as 17 mPa.s at 25 degrees C, and ionic conductivities up to 43.8 S/cm at 25 degrees C. These protic solvents are easily prepared through the stoichiometric combination of a primary amine and Brønsted acid. They have poor ionic behavior when compared to the far more studied aprotic ionic liquids. However, some of the other physicochemical properties possessed by these solvents are highly promising and it is anticipated that these, or analogous protic solvents, will find applications beyond those already identified for aprotic ionic liquids. This series of protic fused salts was employed to determine the effect of structural changes on the physicochemical properties, including the effect of hydroxyl groups, increasing alkyl chain lengths, branching, and the differences between inorganic and organic anions. It was found that simple structural modifications provide a mechanism to manipulate, over a wide range, the temperature at which phase transitions occur and to specifically tailor physicochemical properties for potential end-use applications.

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The structures of the four metal dioxides GeO2, SnO2, RuO2 and IrO2 (germanium, tin, ruthenium and iridium dioxides, respectively) have been redetermined by Rietveld refinement from neutron diffraction powder data. The four dioxides all adopt the rutile-type structure, space group P42/mnm (no. 136), with a = 4.4066 (1), 4.7374 (1), 4.4968 (2) and 4.5051 (3), c = 2.8619 (1), 3.1864 (1), 3.1049 (1) and 3.1586 (2) Å, and x = 0.3060 (1), 0.3056 (1), 0.3053 (1) and 0.3077 (3), respectively. These results are compared with those for other metal dioxides that adopt the rutile structure and trends in structural and thermal vibrations for a series of 11 metal dioxides which adopt the rutile-type structure are described.

Future nanoscale soft matter design will be guided to a large extent by the teachings of amphiphile (lipid or surfactant) self-assembly. Ordered nanostructured lyotropic liquid crystalline mesophases may form in select mixtures of amphiphile and solvent. To reproducibly engineer the low energy amphiphile self-assembly of materials for the future, we must first learn the design principles. In this critical review we discuss the evolution of these design rules and in particular discuss recent key findings regarding (i) what drives amphiphile self-assembly, (ii) what governs the self-assembly structures that are formed, and (iii) how can amphiphile self-assembly materials be used to enhance product formulations, including drug delivery vehicles, medical imaging contrast agents, and integral membrane protein crystallisation media. We focus upon the generation of 'dilutable' lyotropic liquid crystal phases with two- and three-dimensional geometries from amphiphilic small molecules (225 references).

A large number of protic ionic liquids (PILs) have been found to mediate solvent-hydrocarbon interactions and promote amphiphile self-assembly. Hexagonal, cubic, and lamellar lyotropic liquid crystalline phases were observed in PIL-hexadecyltrimethylammonium bromide systems. The driving force for the formation of the self-assembled aggregate structures has been attributed to an entropic contribution to the free energy of association, analogous to the hydrophobic effect in water. The specific aggregate structures formed depend upon the cationic and anionic components of the PIL and their interactions with the amphiphiles.

Nonlamellar lyotropic liquid crystalline (LLC) lipid nanomaterials have emerged as a promising class of advanced materials for the next generation of nanomedicine, comprising mainly of amphiphilic lipids and functional additives self-assembling into two- and three-dimensional, inverse hexagonal, and cubic nanostructures. In particular, the lyotropic liquid crystalline lipid nanoparticles (LCNPs) have received great interest as nanocarriers for a variety of hydrophobic and hydrophilic small molecule drugs, peptides, proteins, siRNAs, DNAs, and imaging agents. Within this space, there has been a tremendous amount of effort over the last two decades elucidating the self-assembly behavior and structure–function relationship of natural and synthetic lipid-based drug delivery vehicles in vitro, yet successful clinical translation remains sparse due to the lack of understanding of these materials in biological bodies. This review provides an overview of (1) the benefits and advantages of using LCNPs as drug delivery nanocarriers, (2) design principles for making LCNPs with desirable functionalities for drug delivery applications, (3) current understanding of the LLC material–biology interface illustrated by more than 50 in vivo, preclinical studies, and (4) current patenting and translation activities in a pharmaceutical context. Together with our perspectives and expert opinions, we anticipate that this review will guide future studies in developing LCNP-based drug delivery nanocarriers with the objective of translating them into a key player among nanoparticle platforms comprising the next generation of nanomedicine for disease therapy and diagnosis.

A range of protic ionic liquids (PILs) have been identified as being capable of supporting the self-assembly of the nonionic surfactants myverol 18-99 K (predominantly monoolein) and phytantriol. PIL-surfactant penetration scans have provided a high throughput technique to determine which lyotropic liquid crystalline phases were formed in the 40 PIL-surfactant systems investigated. Lamellar, inverse hexagonal, and bicontinuous cubic phases that are stable in excess PIL have been observed in surfactant-PIL systems. The studied PILs possess a wide range of solvent properties, including surface tension and viscosity. The nature of the formed amphiphile self-assembly phases is discussed in terms of the PIL structure and solvent properties.

Review: 225 refs.