Diblock-copolymer-mediated self-assembly of protein-stabilized iron oxide nanoparticle clusters for magnetic resonance imaging.

Superparamagnetic iron oxide nanoparticles (SPIONs) can be used as efficient transverse relaxivity (T2 ) contrast agents in magnetic resonance imaging (MRI). Organizing small (D<10 nm) SPIONs into large assemblies can considerably enhance their relaxivity. However, this assembly process is difficult to control and can easily result in unwanted aggregation and precipitation, which might further lead to lower contrast agent performance. Herein, we present highly stable protein-polymer double-stabilized SPIONs for improving contrast in MRI. We used a cationic-neutral double hydrophilic poly(N-methyl-2-vinyl pyridinium iodide-block-poly(ethylene oxide) diblock copolymer (P2QVP-b-PEO) to mediate the self-assembly of protein-cage-encapsulated iron oxide (γ-Fe2 O3 ) nanoparticles (magnetoferritin) into stable PEO-coated clusters. This approach relies on electrostatic interactions between the cationic N-methyl-2-vinylpyridinium iodide block and magnetoferritin protein cage surface (pI≈4.5) to form a dense core, whereas the neutral ethylene oxide block provides a stabilizing biocompatible shell. Formation of the complexes was studied in aqueous solvent medium with dynamic light scattering (DLS) and cryogenic transmission electron microcopy (cryo-TEM). DLS results indicated that the hydrodynamic diameter (Dh ) of the clusters is approximately 200 nm, and cryo-TEM showed that the clusters have an anisotropic stringlike morphology. MRI studies showed that in the clusters the longitudinal relaxivity (r1 ) is decreased and the transverse relaxivity (r2 ) is increased relative to free magnetoferritin (MF), thus indicating that clusters can provide considerable contrast enhancement.

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.

Controlling the dimensionality of charge transport in organic thin-film transistors.

Electrolyte-gated organic thin-film transistors (OTFTs) can offer a feasible platform for future flexible, large-area and low-cost electronic applications. These transistors can be divided into two groups on the basis of their operation mechanism: (i) field-effect transistors that switch fast but carry much less current than (ii) the electrochemical transistors which, on the contrary, switch slowly. An attractive approach would be to combine the benefits of the field-effect and the electrochemical transistors into one transistor that would both switch fast and carry high current densities. Here we report the development of a polyelectrolyte-gated OTFT based on conjugated polyelectrolytes, and we demonstrate that the OTFTs can be controllably operated either in the field-effect or the electrochemical regime. Moreover, we show that the extent of electrochemical doping can be restricted to a few monolayers of the conjugated polyelectrolyte film, which allows both high current densities and fast switching speeds at the same time. We propose an operation mechanism based on self-doping of the conjugated polyelectrolyte backbone by its ionic side groups.

Superhydrophobic and superoleophobic nanocellulose aerogel membranes as bioinspired cargo carriers on water and oil.

We demonstrate that superhydrophobic and superoleophobic nanocellulose aerogels, consisting of fibrillar networks and aggregates with structures at different length scales, support considerable load on a water surface and also on oils as inspired by floatation of insects on water due to their superhydrophobic legs. The aerogel is capable of supporting a weight nearly 3 orders of magnitude larger than the weight of the aerogel itself. The load support is achieved by surface tension acting at different length scales: at the macroscopic scale along the perimeter of the carrier, and at the microscopic scale along the cellulose nanofibers by preventing soaking of the aerogel thus ensuring buoyancy. Furthermore, we demonstrate high-adhesive pinning of water and oil droplets, gas permeability, light reflection at the plastron in water and oil, and viscous drag reduction of the fluorinated aerogel in contact with oil. We foresee applications including buoyant, gas permeable, dirt-repellent coatings for miniature sensors and other devices floating on generic liquid surfaces.

Poly(ethylene imine) and tetraethylenepentamine as protecting agents for metallic copper nanoparticles.

The aim of this research was to explore the use of amine-containing polymeric and low-molar-mass organic protecting agents in the preparation of copper nanoparticles. Particles were synthesized using poly(ethylene imine) (PEI) or tetraethylenepentamine (TEPA) as protecting agents. The resulting particles were studied with UV-vis spectrometry, thermogravimetry, scanning electron microscopy, and transmission electron microscopy, wide-angle X-ray scattering with heating, X-ray photoelectron spectroscopy, and Auger electron spectroscopy. The average crystal sizes for the particles were at room temperature 8.5 and 19.4 nm for PEI and TEPA, respectively, and some surface oxidation was observed. The particles were sintered on paper, and the resistance and resistivity were measured. For Cu/PEI samples, the protecting agent was removed upon sintering at relatively low temperatures (between 150 and 200 degrees C). At this temperature range, particles exhibited a rapid increase in the crystal size. Sintered particles exhibited high conductivity, indicating that these kinds of materials might find use in paper-based printing.

Evidence of PPII-like helical conformation and glass transition in a self-assembled solid-state polypeptide-surfactant complex: poly(L-histidine)/docylbenzenesulfonic acid.

We present lamellar self-assembly of cationic poly(L-histidine) (PLH) stoichiometrically complexed with an anionic surfactant, dodecyl benzenesulfonic acid (DBSA), which allows a stabilized conformation reminiscent of polyproline type II (PPII) left-handed helices. Such a conformation has no intrapeptide hydrogen bonds, and it has previously been found to be one source of flexibility, e.g., in collagen and elastin, as well as an intermediate in silk processing. PLH(DBSA)1.0 complexes were characterized by Fourier transform infrared spectroscopy (FTIR), circular dichroism (CD), small-angle X-ray scattering (SAXS), transmission electron microscopy (TEM), and differential scanning calorimetry (DSC). The PPII-like conformation in PLH(DBSA)1.0 is revealed by characteristic CD and FTIR spectra, where the latter indicates absence of intrachain peptide hydrogen bonds. In addition, a glass transition was directly verified by DSC at ca. 135 degrees C for PLH(DBSA)1.0 and indirectly by SAXS and TEM in comparison to pure PLH at 165 degrees C, thus indicating plasticization. Glass transitions have not been observed before in polypeptide-surfactant complexes. The present results show that surfactant binding can be a simple scheme to provide steric crowding to stabilize PPII conformation to tune the polypeptide properties, plasticization and flexibility.

Organic memory using [6,6]-phenyl-C(61) butyric acid methyl ester: morphology, thickness and concentration dependence studies.

We report a simple memory device in which the fullerene-derivative [6,6]-phenyl-C(61) butyric acid methyl ester (PCBM) mixed with inert polystyrene (PS) matrix is sandwiched between two aluminum (Al) electrodes. Transmission electron microscopy (TEM) images of PCBM:PS films showed well controlled morphology without forming any aggregates at low weight percentages (<10 wt%) of PCBM in PS. Energy dispersive x-ray spectroscopy (EDX) analysis of the device cross-sections indicated that the thermal evaporation of the Al electrodes did not lead to the inclusion of Al metal nanoparticles into the active PCBM:PS film. Above a threshold voltage of <3 V, independent of thickness, a consistent negative differential resistance (NDR) is observed in devices in the thickness range from 200 to 350 nm made from solutions with 4-10 wt% of PCBM in PS. We found that the threshold voltage (V(th)) for switching from the high-impedance state to the low-impedance state, the voltage at maximum current density (V(max)) and the voltage at minimum current density (V(min)) in the NDR regime are constant within this thickness range. The current density ratio at V(max) and V(min) is more than or equal to 10, increasing with thickness. Furthermore, the current density is exponentially dependent on the longest tunneling jump between two PCBM molecules, suggesting a tunneling mechanism between individual PCBM molecules. This is further supported with temperature independent NDR down to 240 K.

A rheo-optical apparatus for real time kinetic studies on shear-induced alignment of self-assembled soft matter with small sample volumes.

In soft materials, self-assembled nanoscale structures can allow new functionalities but a general problem is to align such local structures aiming at monodomain overall order. In order to achieve shear alignment in a controlled manner, a novel type of rheo-optical apparatus has here been developed that allows small sample volumes and in situ monitoring of the alignment process during the shear. Both the amplitude and orientation angles of low level linear birefringence and dichroism are measured while the sample is subjected to large amplitude oscillatory shear flow. The apparatus is based on a commercial rheometer where we have constructed a flow cell that consists of two quartz teeth. The lower tooth can be set in oscillatory motion whereas the upper one is connected to the force transducers of the rheometer. A custom made cylindrical oven allows the operation of the flow cell at elevated temperatures up to 200 degrees C. Only a small sample volume is needed (from 9 to 25 mm(3)), which makes the apparatus suitable especially for studying new materials which are usually obtainable only in small quantities. Using this apparatus the flow alignment kinetics of a lamellar polystyrene-b-polyisoprene diblock copolymer is studied during shear under two different conditions which lead to parallel and perpendicular alignment of the lamellae. The open device geometry allows even combined optical/x-ray in situ characterization of the alignment process by combining small-angle x-ray scattering using concepts shown by Polushkin et al. [Macromolecules 36, 1421 (2003)].