Solution-Phase Magnetic Mechanistic Study of Ni-Seamed Pyrogallol[4]arene Nanocapsules Reveal Presence of Novel Cylindrical and Spherical Species.

The magnetic properties of nickel-seamed C-pyrogallol[4]arene (PgC Ni) hexamers and dimers are studied for the first time in solution. The combination of small-angle neutron scattering and superconducting quantum interference device magnetometer measurements of the solution species reveal their paramagnetic and weakly antiferromagnetic behaviour. Surprisingly, the magnetic results indicated the presence of an unprecedented 13 Å-radius species, larger than both the dimeric and hexameric nanocapsules with both octahedral and square-planar metal centers.

Mitigating background caused by extraneous scattering in small-angle neutron scattering instrument design.

Measurements, calculations and design ideas to mitigate background caused by extraneous scattering in small-angle neutron scattering (SANS) instruments are presented. Scattering includes processes such as incoherent scattering, inelastic scattering and Bragg diffraction. Three primary sources of this type of background are investigated: the beam stop located in front of the detector, the inside lining of the detector vessel and the environment surrounding the sample.

Solution structure of zinc-seamed -alkylpyrogallol[4]arene dimeric nanocapsules.

The structural stability and solution geometry of zinc-seamed--propylpyrogallol[4]arene dimers has been studied in solution using neutron scattering and 2D-DOSY NMR methods. In comparison with the structures of the analogous copper-/nickel-seamed dimeric entities, the spherical geometry of the PgCZn species ( = 9.4 Å; diffusion coefficient = 1.

Size effects of solvent molecules on the phase behavior and effective interaction of colloidal systems with the bridging attraction.

There has been much recent research interest towards understanding the phase behavior of colloidal systems interacting with a bridging attraction, where the small solvent particles and large solute colloidal particles can be reversibly associated with each other. These systems show interesting phase behavior compared to the more widely studied depletion attraction systems. Here, we use Baxter's two-component sticky hard sphere model with a Percus-Yevick closure to solve the Ornstein-Zernike equation and study the size effect on colloidal systems with bridging attractions.

Manipulating three-dimensional gel network entanglement by thin film shearing.

Vortex fluidic mediated shearing of supramolecular gels in thin films leads to complete disruption of fluorous bis-urea derived gels. Hydrocarbon analogues however, are only partially disrupted, which emphasizes the resistance of non-fluorous bis-urea gelators towards shear. The gel structures have been studied by combining the thin film shearing with small angle neutron scattering.

Fluorous 'ponytails' lead to strong gelators showing thermally induced structure evolution.

Appending perfluoroalkyl substituents to bis(urea) gelators results in significantly decreased inter-chain interactions with markedly thinner fibres and hence more cross-linked and more transparent gels with potential applications in the crystallisation of fluorinated pharmaceuticals. Gel structure has been probed by detailed SANS measurements which indicate a surprising structure evolution on thermal cycling, not seen for hydrocarbon analogues. The SANS data are complemented by the single crystal X-ray structure of one fluorinated gelator.

From the depletion attraction to the bridging attraction: the effect of solvent molecules on the effective colloidal interactions.

Depletion attraction induced by non-adsorbing polymers or small particles in colloidal solutions has been widely used as a model colloidal interaction to understand aggregation behavior and phase diagrams, such as glass transitions and gelation. However, much less attention has been paid to study the effective colloidal interaction when small particles/molecules can be reversibly attracted to large colloidal particles. At the strong attraction limit, small particles can introduce bridging attraction as it can simultaneously attach to neighbouring large colloidal particles.

Shear viscosity and structural scalings in model adhesive hard-sphere gels.

We present experiments and simulations that show a fundamental scaling for both the rheology and microstructure of flowing gels. Unique flow-SANS measurements demonstrate that the structure orients along both the neutral and compression axis. We quantify the anisotropy using a single parameter, α, that scales by a dimensionless number, M^{'}, that arises from a force balance on a particle.

Solution superstructures: truncated cubeoctahedron structures of pyrogallol[4]arene nanoassemblies.

Giant nanocapsules: the solution-phase structures of PgC1Ho and PgC3Ho have been investigated using in situ neutron scattering measurements. The SANS results show the presence of spherical nanoassemblies of radius 18.2 Å, which are larger than the previously reported metal-seamed PgC3 hexamers (radius = 10 Å).

Investigating structural alterations in pyrogallol[4]arene-pyrene nanotubular frameworks.

Small-angle neutron scattering (SANS) and diffusion NMR studies are performed to investigate the stability and geometry of hydrogen-bonded pyrene-guest-containing C-hexylpyrogallol[4]arene (PgC(6) -pyrene) nanotubular frameworks in solution. In the solid state, hydrogen-bonded pyrogallol[4]arene tubes are formed; however, the scattering data for PgC(6) -pyrene assemblies in acetone are best modeled as dimeric spheres of PgC(6) with no pyrene guest. The result of diffusion NMR study also indicates the rearrangement of tubular entity into spherical framework in acetone.

Solution-phase structures of gallium-containing pyrogallol[4]arene scaffolds.

The variations in architecture of gallium-seamed (PgCGa) and gallium-zinc-seamed (PgCGaZn) C-butylpyrogallol[4]arene nanoassemblies in solution (SANS/NMR) versus the solid state (XRD) have been investigated. Rearrangement from the solid-state spheroidal to the solution-phase toroidal shape differentiates the gallium-containing pyrogallol[4]arene nanoassemblies from all other PgCM nanocapsules studied thus far. Different structural arrangements of the metals and arenes of PgCGa versus PgCGaZn have been deduced from the different toroidal dimensions, C–H proton environments and guest encapsulation of the two toroids.

Investigation of encapsulation of insulin biotemplate within C-methylresorcin[4]arenes.

Solution structure of insulin templated C-methyl resorcin[4]arene nanocapsules has been investigated using neutron scattering. The insulin biotemplate has enhanced the limits of encapsulation and enabled formation of a larger spherical molecular host.

Solution structure of copper-seamed C-alkylpyrogallol[4]arene nanocapsules with varying chain lengths.

The stability of copper-seamed C-alkylpyrogallol[4]arene hexamers with varying chain lengths in solution has been studied using small-angle neutron scattering (SANS). The progression in diameter of spherical capsules with increasing alkyl chain lengths of copper-seamed hexamers in solution suggests both robustness as well as a close correlation between the solid phase and solution phase structures.

Exploring the ellipsoidal and core-shell geometries of copper-seamed C-alkylpyrogallol[4]arene nanocapsules in solution.

Small-angle neutron scattering (SANS) studies were used to probe the stability and geometry of copper-seamed C-alkylpyrogallol[4]arene (PgC(n)Cu; n = 11, 13, 17) hexamers in solution. Novel structural features are observed at chain lengths greater than 10 in both solid and solution phase. Scattering data for the PgC(11)Cu and PgC(13)Cu in chloroform fitted as core-shell spheres with a total spherical radius of about 22.

Formation of kinetically trapped nanoscopic unilamellar vesicles from metastable nanodiscs.

Zwitterionic long-chain lipids (e.g., dimyristoyl phosphatidylcholine, DMPC) spontaneously form onion-like, thermodynamically stable structures in aqueous solutions (commonly known as multilamellar vesicles, or MLVs).

Thermal fluctuation and elasticity of lipid vesicles interacting with pore-forming peptides.

The thermal fluctuation and elasticity of dioleoyl-phosphocholine large unilamellar vesicle interacting with pore-forming peptide, melittin, were investigated by neutron spin-echo measurements. The relaxation behavior of the membrane fluctuation with different peptide to lipid molar ratio P/L can be divided into three regions, resulting from characteristic changes of the effective bending modulus κ(˜) of the membrane which includes the effects of internal dissipation within the membrane. At low P/L, melittin is adsorbed parallel to the surface of membrane and κ(˜) decreases significantly due to perturbation of hydrocarbon chain packing.

Thermally switchable one- and two-dimensional arrays of single-walled carbon nanotubes in a polymeric system.

Fabrication of highly ordered arrays of single-walled carbon nanotubes (SWNTs) has been of great interest for a wide range of potential applications. Here, we report thermally switchable one- and two-dimensional arrays of individually isolated SWNTs formed by cooperative self-assembly of functionalized SWNTs and a block copolymer/water system. Small-angle X-ray scattering measurements reveal that when the block copolymer/water system is in an isotropic phase, two-dimensional hexagonal arrays of SWNTs are formed by depletion attraction, and when the block copolymer/water system is in a lamellar phase, one-dimensional lattices of SWNTs intercalated in the polar regions of the polymeric lamellar structure are formed by entropically driven segregation and two-dimensional depletion attraction.

Highly ordered self-assembly of 1D nanoparticles in phospholipids driven by curvature and electrostatic interaction.

Self-assembly of 1D nanoparticles such as carbon nanotubes or nanorods into highly ordered superstructures using various interactions has been of great interest as a route toward materials with new functionalities. However, the phase behavior of 1D nanoparticles interacting with surrounding materials, which is the key information to design self-assembled superstructures, has not been fully exploited yet. Here, we report for the first time a new phase diagram of negatively charged 1D nanoparticle and cationic liposome (CLs) complexes in water that exhibit three different highly ordered phases, intercalated lamellar, doubly intercalated lamellar, and centered rectangular phases, depending on particle curvature and electrostatic interactions.

Polymerized rodlike nanoparticles with controlled surface charge density.

Stable rodlike nanoparticles with highly controlled surface charge density have been developed by the free radical polymerization of the mixture of polymerizable cationic surfactant, cetyltrimethylammonium 4-vinylbenzoate (CTVB), and hydrotropic salt sodium 4-styrenesulfonate (NaSS) in aqueous solution. The surface charge of the polymerized CTVB/NaSS rodlike nanoparticles was controlled by varying the NaSS concentration during the polymerization process, and the charge variation was interpreted in terms of the overcharging effect in colloidal systems. The SANS measurements show that the diameter of the polymerized CTVB/NaSS rodlike nanoparticles is constant at 4 nm and the particle length ranges from 24 to 85 nm, depending on the NaSS concentration.

perpendicular organization of macromolecules: synthesis and alignment studies of a soluble poly(iptycene).

We describe herein a polymeric material that prefers to align perpendicular to a stretch-aligned polymer host in the solid state. Poly(iptycene) poly-1 was synthesized from monomer 1 under hyperbaric techniques via a Diels-Alder polymerization. Polarized excitation spectra of the anthracene end groups in this material in a stretch-aligned, solution-cast poly(vinyl chloride) (PVC) film showed that the poly(iptycene) prefers to align normal (counter aspect ratio) to the stretching direction of the PVC.

Metathesis depolymerization for removable surfactant templates.

Current methodologies for the production of meso- and nanoporous materials include the use of a surfactant to produce a self-assembled template around which the material is formed. However, post-production surfactant removal often requires centrifugation, calcination, and/or solvent washing which can damage the initially formed material architecture(s). Surfactants that can be disassembled into easily removable fragments following material preparation would minimize processing damage to the material structure, facilitating formation of templated hybrid architectures.