Liliana de Campo

Polycontinuous geometries for inverse lipid phases with more than two aqueous network domains.

Inverse bicontinuous cubic phases with two aqueous network domains separated by a smooth bilayer are firmly established as equilibrium phases in lipid/water systems. The purpose of this article is to highlight the generalisations of these bicontinuous geometries to polycontinuous geometries, which could be realised as lipid mesophases with three or more network-like aqueous domains separated by a branched bilayer. An analysis of structural homogeneity in terms of bilayer width variations reveals that ordered polycontinuous geometries are likely candidates for lipid mesophase structures, with similar chain packing characteristics to the inverse micellar phases (that once were believed not to exist due to high packing frustration). The average molecular shape required by global geometry to form these multi-network phases is quantified by the surfactant shape parameter, v/(al); we find that it adopts values close to those of the known lipid phases. We specifically analyse the 3etc(187 193) structure of hexagonal symmetry P6(3) /mcm with three aqueous domains, the 3dia(24 220) structure of cubic symmetry I43d composed of three distorted diamond networks, the cubic chiral 4srs(24 208) with cubic symmetry P4232 and the achiral 4srs(5 133) structure of symmetry P42/nbc, each consisting of four intergrown undistorted copies of the srs net (the same net as in the QII(G) gyroid phase). Structural homogeneity is analysed by a medial surface approach assuming that the headgroup interfaces are constant mean curvature surfaces. To facilitate future experimental identification, we provide simulated SAXS scattering patterns that, for the 4srs(24 208) and 3dia(24 220) structures, bear remarkable similarity to those of bicontinuous QII(G)-gyroid and QII(D)-diamond phases, with comparable lattice parameters and only a single peak that cannot be indexed to the well-established structures. While polycontinuous lipid phases have, to date, not been reported, the likelihood of their formation is further indicated by the reported observation of a solid tricontinuous mesoporous silicate structure, termed IBN-9, which formed in the presence of surfactants [Han et al., Nat. Chem., 2009, 1, 123].

A novel lyotropic liquid crystal formed by triphilic star-polyphiles: hydrophilic/oleophilic/fluorophilic rods arranged in a 12.6.4. tiling

Triphilic star-polyphiles are short-chain oligomeric molecules with a radial arrangement of hydrophilic, hydrocarbon and fluorocarbon chains linked to a common centre. They form a number of liquid crystalline structures when mixed with water. In this contribution we focus on a hexagonal liquid crystalline mesophase found in star-polyphiles as compared to the corresponding double-chain surfactant to determine whether the hydrocarbon and fluorocarbon chains are in fact demixed in these star-polyphile systems, or whether both hydrocarbon and fluorocarbon chains are miscible, leading to a single hydrophobic domain, making the star-polyphile effectively amphiphilic. We report SANS contrast variation data that are compatible only with the presence of three distinct immiscible domains within this hexagonal mesophase, confirming that these star-polyphile liquid crystals are indeed hydrophilic/oleophilic/fluorophilic 3-phase systems. Quantitative comparison with scattering simulations shows that the experimental data are in very good agreement with an underlying 2D columnar (12.6.4) tiling. As in a conventional amphiphilic hexagonal mesophase, the hexagonally packed water channels (dodecagonal prismatic domains) are embedded in a hydrophobic matrix, but that matrix is split into oleophilic hexagonal prismatic domains and fluorophilic quadrangular prismatic domains.

Hierarchical self-assembly of a striped gyroid formed by threaded chiral mesoscale networks

Significance Chirality and hierarchical ordering are two fundamental properties found in many of nature’s most complex self-assembled structures such as living cells. Simultaneous control over these properties in synthetic systems is vital to mimic or even surpass nature’s designs. Via numerical simulations, we describe a class of complex morphologies that afford radically new architectures for self-assembled shapes. Specifically, a mixture of two star block-copolymers are shown to form multiple interwoven 2D and 3D labyrinths—all chiral—and hierarchically ordered on two different length scales. Furthermore, we show that such intricate network morphologies forming at a confined, hyperbolic interface can be classified and modeled in terms of a much simpler isotropic model of packing based on tilings of the hyperbolic plane. Numerical simulations reveal a family of hierarchical and chiral multicontinuous network structures self-assembled from a melt blend of Y-shaped ABC and ABD three-miktoarm star terpolymers, constrained to have equal-sized A/B and C/D chains, respectively. The C and D majority domains within these patterns form a pair of chiral enantiomeric gyroid labyrinths (srs nets) over a broad range of compositions. The minority A and B components together define a hyperbolic film whose midsurface follows the gyroid minimal surface. A second level of assembly is found within the film, with the minority components also forming labyrinthine domains whose geometry and topology changes systematically as a function of composition. These smaller labyrinths are well described by a family of patterns that tile the hyperbolic plane by regular degree-three trees mapped onto the gyroid. The labyrinths within the gyroid film are densely packed and contain either graphitic hcb nets (chicken wire) or srs nets, forming convoluted intergrowths of multiple nets. Furthermore, each net is ideally a single chiral enantiomer, induced by the gyroid architecture. However, the numerical simulations result in defect-ridden achiral patterns, containing domains of either hand, due to the achiral terpolymeric starting molecules. These mesostructures are among the most topologically complex morphologies identified to date and represent an example of hierarchical ordering within a hyperbolic pattern, a unique mode of soft-matter self-assembly.

BILBY: Time-of-Flight Small Angle Scattering Instrument

Neutron News Volume 27 • Number 2 • 2016 9 The BILBY Time-of-Flight (ToF) Small Angle Neutron Scattering (SANS) instrument at the Bragg Institute at ANSTO is among a number of recent additions to the current suite of operating instruments. The fi ve-year project, beginning in October 2009, involved the development, design, manufacture, and installation of all components of the instrument. BILBY (Fig. 1) is the second pinhole SANS instrument utilising neutrons produced by the OPAL reactor, and was built to complement and extend the capabilities of the QUOKKA [1] SANS instrument. BILBY is a world class instrument capable of applying the technique of SANS to a broad range of research areas, including chemistry and industrial chemistry; physics; biochemistry; biology; polymer and colloid sciences; mechanical, chemical, polymer and materials engineering; environmental sciences; steel processing; geology and geosciences. The inspiration for BILBY is the D33 instrument located at the Institut Laue-Langevin [2]. Similar to D33, BILBY exploits neutron ToF to extend the measurable Qrange, over and above what is possible on a conventional reactor-based monochromatic SANS instrument. Time of fl ight is achieved using four choppers, which gives a wide range of choice in relation to the wavelength resolution (from ~3%‒30%, depending on the chopper setup and on the sample-detector distance). In March 2014, commissioning experiments were commenced on BILBY and currently we are readying for the commencement of our user program in March 2016. BILBY’s layout is shown on Figure 2.

A Bicontinuous Mesophase Geometry with Hexagonal Symmetry

We report that a specific realization of Schwarzs triply periodic hexagonal minimal surface is isotropic with respect to the Doi-Ohta interface tensor and simultaneously has minimal packing and stretching frustration similar to those of the commonly found cubic bicontinuous mesophases. This hexagonal surface, of symmetry P6(3)/mmc with a lattice ratio of c/a = 0.832, is therefore a likely candidate geometry for self-assembled lipid/surfactant or copolymer mesophases. Furthermore, both the peak position ratios in its powder diffraction pattern and the elastic moduli closely resemble those of the cubic bicontinuous phases. We therefore argue that a genuine possibility of experimental misidentification exists.

Chelating DTPA amphiphiles: ion-tunable self-assembly structures and gadolinium complexes

A series of chelating amphiphiles and their gadolinium (Gd(III)) metal complexes have been synthesized and studied with respect to their neat and lyotropic liquid crystalline phase behavior. These amphiphiles have the ability to form ion-tunable self-assembly nanostructures and their associated Gd(III) complexes have potential as magnetic resonance imaging (MRI) contrast enhancement agents. The amphiphiles are composed of diethylenetriaminepentaacetic acid (DTPA) chelates conjugated to one or two oleyl chain(s) (DTPA-MO and DTPA-BO), or isoprenoid-type chain(s) of phytanyl (DTPA-MP and DTPA-BP). The thermal phase behavior of the neat amphiphiles was examined by differential scanning calorimetry (DSC), thermogravimetric analysis (TGA) and cross polarizing optical microscopy (POM). Self-assembly of neat amphiphiles and their associated Gd complexes, as well as their lyotropic phase behavior in water and sodium acetate solutions of different ionic strengths, were examined by POM and small and wide angle X-ray scattering (SWAXS). All neat amphiphiles exhibited lamellar structures. The non-complexed amphiphiles showed a variety of lyotropic phases depending on the number and nature of the hydrophobic chain in addition to the ionic state of the hydration. Upon hydration with increased Na-acetate concentration and the subtle changes in the effective headgroup size, the interfacial curvature of the amphiphile increased, altering the lyotropic liquid crystalline structures towards higher order mesophases such as the gyroid (Ia3d) bicontinuous cubic phase. The chelation of Gd with the DTPA amphiphiles resulted in lamellar crystalline structures for all the neat amphiphiles. Upon hydration with water, the Gd-complexed mono-conjugates formed micellar or vesicular self-assemblies, whilst the bis-conjugates transformed only partially into lyotropic liquid crystalline mesophases.

Polymeric Ionic Liquid Nanoparticle Emulsions as a Corrosion Inhibitor in Anticorrosion Coatings

In this contribution, we report the facile preparation of cross-linked polymerizable ionic liquid (PIL)-based nanoparticles via thiol–ene photopolymerization in a miniemulsion. The synthesized PIL nanoparticles with a diameter of about 200 nm were fully characterized with regard to their chemical structures, morphologies, and properties using different techniques, such as Fourier transform infrared spectroscopy, thermogravimetric analysis, scanning electron microscopy, and transmission electron microscopy. To gain an in-depth understanding of the physical and morphological structures of the PIL nanoparticles in an emulsion, small-angle neutron scattering and ultra-small-angle neutron scattering were used. Neutron scattering studies revealed valuable information regarding the formation of cylindrical ionic micelles in the spherical nanoparticles, which is a unique property of this system. Furthermore, the PIL nanoparticle emulsion was utilized as an inhibitor in a self-assembled nanophase particle (SNAP) coating. The corrosion protection ability of the resultant coating was examined using potentiodynamic polarization and electrochemical impedance spectroscopy. The results show that the PIL nanoparticle emulsion in the SNAP coating acts as an inhibitor of corrosion and is promising for fabricating advanced coatings with improved barrier function and corrosion protection.

Investigating linear and nonlinear viscoelastic behaviour and microstructures of gelatin-multiwalled carbon nanotube composites

We have investigated the linear and nonlinear rheology of various gelatin-multiwalled carbon nanotube (gel-MWNT) composites, namely physically-crosslinked-gelatin gel-MWNT composites, chemically-crosslinked-gelatin gel-MWNT composites, and chemically–physically-crosslinked-gelatin gel-MWNT composites. Further, the internal structures of these gel-MWNT composites were characterized by ultra-small angle neutron scattering and scanning electron microscopy. The adsorption of gelatin onto the surface of MWNT is also investigated to understand gelatin-assisted dispersion of MWNT during ultrasonication. For all gelatin gels, addition of MWNT increases their complex modulus. The dependence of the storage modulus with frequency for gelatin-MWNT composites is similar to that of the corresponding neat gelatin matrix. However, by incorporating MWNT, the dependence of the loss modulus on frequency is reduced. The linear viscoelastic region is decreased approximately linearly with the increase of MWNT concentration. The pre-stress results demonstrate that the addition of MWNT does not change the strain-hardening behaviour of physically-crosslinked gelatin gel. However, the addition of MWNT can increase the strain-hardening behaviour of chemically-crosslinked gelatin gel, and chemically–physically crosslinked gelatin gel. Results from light microscopy, cryo-SEM, and USANS demonstrate the hierarchical structures of MWNT, including that tens-of-micron scale MWNT agglomerates are present. Furthermore, the adsorption curve of gelatin onto the surface of MWNT follows a two-stage pseudo-saturation behaviour.

Evaluation of Gd-DTPA-Monophytanyl and Phytantriol Nanoassemblies as Potential MRI Contrast Agents

Supramolecular self-assembling amphiphiles have been widely used in drug delivery and diagnostic imaging. In this report, we present the self-assembly of Gd (III) chelated DTPA-monophytanyl (Gd-DTPA-MP) amphiphiles incorporated within phytantriol (PT), an inverse bicontinuous cubic phase forming matrix at various compositions. The dispersed colloidal nanoassemblies were evaluated as potential MRI contrast agents at various magnetic field strengths. The homogeneous incorporation of Gd-DTPA-MP in PT was confirmed by polarized optical microscopy (POM) and synchrotron small-angle X-ray scattering (SAXS) of the bulk phases of the mixtures. The liquid crystalline nanostructures, morphology, and the size distribution of the nanoassemblies were studied by SAXS, cryogenic transmission electron microscopy (cryo-TEM), and dynamic light scattering (DLS). The dispersions with up to 2 mol % of Gd-DTPA-MP in PT retained inverse cubosomal nanoassemblies, whereas the rest of the dispersions transformed to liposomal nanoassemblies. In vitro relaxivity studies were performed on all the dispersions at 0.54, 9.40, and 11.74 T and compared to Magnevist, a commercially available contrast agent. All the dispersions showed much higher relaxivities compared to Magnevist at both low and high magnetic field strengths. Image contrast of the nanoassemblies was also found to be much better than Magnevist at the same Gd concentration at 11.74 T. Moreover, the Gd-DTPA-MP/PT dispersions showed improved relaxivities over the pure Gd-DTPA-MP dispersion at high magnetic fields. These stable colloidal nanoassemblies have high potential to be used as combined delivery matrices for diagnostics and therapeutics.

Design and performance of the variable-wavelength Bonse–Hart ultra-small-angle neutron scattering diffractometer KOOKABURRA at ANSTO

The double-crystal ultra-small-angle neutron scattering (USANS) diffractometer KOOKABURRA at ANSTO was made available for user experiments in 2014. KOOKABURRA allows the characterization of microstructures covering length scales in the range of 0.1–10 µm. Use of the first- and second-order reflections coming off a doubly curved highly oriented mosaic pyrolytic graphite premonochromator at a fixed Bragg angle, in conjunction with two interchangeable pairs of Si(111) and Si(311) quintuple-reflection channel-cut crystals, permits operation of the instrument at two individual wavelengths, 4.74 and 2.37 A. This unique feature among reactor-based USANS instruments allows optimal accommodation of a broad range of samples, both weakly and strongly scattering, in one sample setup. The versatility and capabilities of KOOKABURRA have already resulted in a number of research papers, clearly demonstrating that this instrument has a major impact in the field of large-scale structure determination.