Effect of temperature, water content and free fatty acid on reverse micelle formation of phospholipids in vegetable oil.

The self-assembly of phospholipids in oil, specifically lecithin in rapeseed oil, was investigated by combining experimental and computational methods The influence of temperature, water, and free fatty acids on the onset of lecithin aggregation in the rapeseed oil was determined using the 7,7,8,8 -tetracyanoquinodimethane dye (TCNQ) solubilization method and the size and shape of the self-assembled lecithin structures were investigated by small-angle X-ray scattering and cryogenic transmission electron microscopy. In the absence of excess water in the system (0.03wt-% water in oil), stable cylindrical lecithin reverse micelles were observed above the critical micelle concentration (CMC). Comparing the aggregation response in room temperature and at 70°C revealed that CMC decreased with increasing temperature. Furthermore, already a modest amount of added water (0.3wt-% water in oil) was sufficient to induce the formation of lamellar lecithin structures, that phase separated from the oil. In low water content, oleic acid suppressed the formation of lecithin reverse micelles whereas in the presence of more water, the oleic acid stabilized the reverse micelles. Consequently, more water was needed to induce phase separation in the presence of oleic acid. Molecular dynamics simulations indicated that the stabilizing effect of oleic acid resulted from oleic acid enhancing phospholipid solubilization in the oil by forming a solvating shell around the phosphate head group. The findings showed that the response of the mixed surfactant system is a delicate interplay of the different components and variables. The significance of the observations is that multiple parameters need to be controlled for desired system response, for example towards vegetable oil purification or phospholipid based microemulsions.

Electrostatic assembly of binary nanoparticle superlattices using protein cages.

Binary nanoparticle superlattices are periodic nanostructures with lattice constants much shorter than the wavelength of light and could be used to prepare multifunctional metamaterials. Such superlattices are typically made from synthetic nanoparticles, and although biohybrid structures have been developed, incorporating biological building blocks into binary nanoparticle superlattices remains challenging. Protein-based nanocages provide a complex yet monodisperse and geometrically well-defined hollow cage that can be used to encapsulate different materials. Such protein cages have been used to program the self-assembly of encapsulated materials to form free-standing crystals and superlattices at interfaces or in solution. Here, we show that electrostatically patchy protein cages--cowpea chlorotic mottle virus and ferritin cages--can be used to direct the self-assembly of three-dimensional binary superlattices. The negatively charged cages can encapsulate RNA or superparamagnetic iron oxide nanoparticles, and the superlattices are formed through tunable electrostatic interactions with positively charged gold nanoparticles. Gold nanoparticles and viruses form an AB(8)(fcc) crystal structure that is not isostructural with any known atomic or molecular crystal structure and has previously been observed only with large colloidal polymer particles. Gold nanoparticles and empty or nanoparticle-loaded ferritin cages form an interpenetrating simple cubic AB structure (isostructural with CsCl). We also show that these magnetic assemblies provide contrast enhancement in magnetic resonance imaging.

Hierarchical self-assembly and optical disassembly for controlled switching of magnetoferritin nanoparticle magnetism.

Protein cages such as ferritin and viral capsids are interesting building blocks for nanotechnology due to their monodisperse structure and ability to encapsulate various functional moieties. Here we show that recombinant ferritin protein cages encapsulating Fe(3)O(4)-γ-Fe(2)O(3) iron oxide (magnetoferritin) nanoparticles and photodegradable Newkome-type dendrons self-assemble into micrometer-sized complexes with a face-centered-cubic (fcc) superstructure and a lattice constant of 13.1 nm. The magnetic properties of the magnetoferritin particles are affected directly by the hierarchical organization. Magnetoferritin nanoparticles dispersed in water exhibit typical magnetism of single domain noninteracting nanoparticles; however, the same nanoparticles organized into fcc superstructures show clearly the effects of the altered magnetostatic (e.g., dipole-dipole) interactions by exhibiting, for example, different hysteresis of the field-dependent magnetization. The magnetoferritin-dendron assemblies can be efficiently disassembled by a short optical stimulus resulting in release of free magnetoferritin particles. After the triggered release the nanomagnetic properties of the pristine magnetoferritin nanoparticles are regained.

Nanoporous network channels from self-assembled triblock copolymer supramolecules.

Supramolecular complexes of a poly(tert-butoxystyrene)-block-polystyrene-block-poly(4-vinylpyridine) triblock copolymers and less than stoichiometric amounts of pentadecylphenol (PDP) are shown to self-assemble into a core-shell gyroid morphology with the core channels formed by the hydrogen-bonded P4VP(PDP)complexes. After structure formation, PDP was removed using a simple washing procedure, resulting in well-ordered nanoporous films that were used as templates for nickel plating.

Inorganic hollow nanotube aerogels by atomic layer deposition onto native nanocellulose templates.

Hollow nano-objects have raised interest in applications such as sensing, encapsulation, and drug-release. Here we report on a new class of porous materials, namely inorganic nanotube aerogels that, unlike other aerogels, have a framework consisting of inorganic hollow nanotubes. First we show a preparation method for titanium dioxide, zinc oxide, and aluminum oxide nanotube aerogels based on atomic layer deposition (ALD) on biological nanofibrillar aerogel templates, that is, nanofibrillated cellulose (NFC), also called microfibrillated cellulose (MFC) or nanocellulose. The aerogel templates are prepared from nanocellulose hydrogels either by freeze-drying in liquid nitrogen or liquid propane or by supercritical drying, and they consist of a highly porous percolating network of cellulose nanofibrils. They can be prepared as films on substrates or as freestanding objects. We show that, in contrast to freeze-drying, supercritical drying produces nanocellulose aerogels without major interfibrillar aggregation even in thick films. Uniform oxide layers are readily deposited by ALD onto the fibrils leading to organic-inorganic core-shell nanofibers. We further demonstrate that calcination at 450 °C removes the organic core leading to purely inorganic self-supporting aerogels consisting of hollow nanotubular networks. They can also be dispersed by grinding, for example, in ethanol to create a slurry of inorganic hollow nanotubes, which in turn can be deposited to form a porous film. Finally we demonstrate the use of a titanium dioxide nanotube network as a resistive humidity sensor with a fast response.

Tailoring of the hierarchical structure within electrospun fibers due to supramolecular comb-coil block copolymers: polystyrene-block-poly(4-vinyl pyridine) plasticized by hydrogen bonded pentadecylphenol.

Previously we demonstrated hierarchical self-assembly and mesoporosity in electrospun fibers using selected polystyrene--poly(4-vinylpyridine) (PS--P4VP) diblock copolymers with hydrogen-bonded 3--pentadecylphenol (PDP), which rendered distorted spherical P4VP(PDP) domains within the PS matrix, internal lamellar order within the P4VP(PDP) domains, and allowed distorted spherical pores by removing PDP (. 2005, , 1048). Here we study whether the internal structure of electrospun fibers can be systematically tailored by varying the compositions of PS--P4VP(PDP). We expect these complexes to be feasible choices to combine electrospinning and self-assembly, as relatively high molecular weight block copolymers are useful for electrospinning, and enhanced structure formation due to plasticization by the amphiphilic PDP was expected. Not surprisingly, the self-assembled structures of the as-prepared fibers were less perfect than those in the corresponding well-annealed bulk materials. Compositions that show spherical self-assembly of P4VP(PDP) within the PS matrix in bulk lead to distinct and elongated worm-like P4VP(PDP) domains within the PS matrix in electrospun fibers. More symmetric compositions, which showed lamellar self-assembly in bulk, lead to structures where both PS and P4VP(PDP) domains were worm-like and elongated in a relatively symmetric manner. Finally, compositions which in bulk showed self-assembly of PS spheres within the P4VP(PDP) matrix, lead to separate distorted PS domains in the P4VP(PDP) matrix. Additionally, SAXS measurements suggest a lamellar structure within the P4VP(PDP) domains. As electrospinning is a facile method to prepare mesoscale fibers, and it is known that the amphiphiles can be removed from the hierarchical assemblies, the present method offers the potential to tune the internal porosity of the fibers for release and absorption purposes.