Nanoscale assembly in biological systems: from neuronal cytoskeletal proteins to curvature stabilizing lipids

The review will describe experiments inspired by the rich variety of bundles and networks of interacting microtubules (MT), neurofilaments, and filamentous-actin in neurons where the nature of the interactions, structures, and structure-function correlations remain poorly understood. We describe how three-dimensional (3D) MT bundles and 2D MT bundles may assemble, in cell free systems in the presence of counter-ions, revealing structures not predicted by polyelectrolyte theories. Interestingly, experiments reveal that the neuronal protein tau, an abundant MT-associated-protein in axons, modulates the MT diameter providing insight for the control of geometric parameters in bio- nanotechnology. In another set of experiments we describe lipid-protein-nanotubes, and lipid nano-tubes and rods, resulting from membrane shape evolution processes involving protein templates and curvature stabilizing lipids. Similar membrane shape changes, occurring in cells for the purpose of specific functions, are induced by interactions between membranes and proteins. The biological materials systems described have applications in bio-nanotechnology.     

Preparation and photoluminescence properties of γ-KCaPO4: Eu phosphors for near UV-based white LEDs

Novel whitish-blue phosphors based on a phosphate host matrix, γ-KCaPO₄: Eu²⁺, were prepared by a conventional solid-state reaction method using slightly phosphorus deficient conditions and their photoluminescence properties were investigated. The concentration quenching process, temperature dependence of the luminescence and decay curve were also investigated. The γ-KCaPO₄: Eu²⁺ phosphor was efficiently excited by UV-Visible light at wavelengths of 200-450 nm and exhibited a bright whitish-blue emission with a maximum peak wavelength of 473 nm. All of these characteristics suggest that the γ-KCaPO₄: Eu²⁺ phosphors combined with red phosphors could be applicable to near UV-based white LEDs, i.e., only two kinds of phosphor powders are needed for the formation of white light.     

Defining the nanostructured morphology of triblock copolymers using resonant soft X-ray scattering

The morphologies of a poly(1,4-isoprene)-block-polystyrene-block-poly(2-vinyl pyridine) (IS2VP) copolymer were investigated using resonant soft X-ray scattering (RSoXS) together with scanning force microscopy, small-angle X-ray scattering, and electron microscopy. Differences in the nanoscopic morphologies in the bulk and thin film samples were observed arising from the competition between segmental interactions between the blocks and the substrate and the surface energies of each block. Using soft X-rays at selected photon energies to isolate the scattering contribution from different polymer blocks, RSoXS unambiguously defined the complex morphology of the triblock copolymer. In the bulk sample, two nested, hexagonal arrays of P2VP and PI cylindrical microdomains residing in the PS matrix were observed. The cylindrical microdomains of one component were found to be located at the interstitial sites of the hexagonal array of the other component that has the larger d spacing. In solvent-annealed thin films with 40 nm in thickness, a hexagonal array of core-shell microdomains of P2VP cores with PS shells that reside in a PI matrix were observed.     

Development of bismuth tellurium selenide nanoparticles for thermoelectric applications via a chemical synthetic process

Bismuth tellurium selenide (Bi₂Te_ySe_3−y) nanoparticles for thermoelectric applications are successfully prepared via a water-based chemical reaction under atmospheric conditions. The nanostructured compound is prepared using a complexing agent (ethylenediaminetetraacetic acid) and a reducing agent (ascorbic acid) to stabilize the bismuth precursor (Bi(NO₃)₃) in water and to favor the reaction with reduced sources of tellurium and selenium. The resulting powder is smaller than ca. 100 nm and has a crystalline structure corresponding to the rhombohedral Bi₂Te_2.7Se_0.3. The nanocrystalline powder is sintered via a spark plasma sintering process to obtain a sintered body composed of nano-sized grains. Important transport properties of the sintered body are measured to calculate its most important characteristic, the thermoelectric performance. The results demonstrate a relationship between the nanostructure of the sintered body and its thermal conductivity.     

Electron-emission properties of carbon nanotube micro-tips coated by amorphous carbon nitride films

An approach to the preparation of a tip-type of field emitter that is made up of carbon nanotubes (CNTs) coated with amorphous carbon nitride (a-CN_x) films is presented for the purpose of enhancing its electron emission property. CNTs were directly grown on nano-sized conical-type tungsten tips via the inductively coupled plasma-chemical vapor deposition system, and a-CN_x films were coated on the CNTs using an radio frequency magnetron sputtering system. The morphologies and microstructures of the a-CN_x-coated CNTs were analyzed via field emission scanning electron microscopy, energy-dispersive x-ray spectroscopy, high-resolution transmission electron microscopy, and x-ray photoelectron spectroscopy. The electron emission properties of the a-CN_x/CNT hetero-structures were measured using a high-vacuum field emission measurement system. The best field emission properties, such as a very low turn-on voltage of 500 V and a maximum emission current of 176 μA were achieved for the CNT emitter coated with the 5 nm-thick a-CN_x film. In addition, this emitter showed a highly stable behavior in long-term (up to 25 h) electron emission.     

Novel SrCo1 − 2x(Fe,Nb)xO3 − δ (x = 0.05, 0.10) oxides targeting CO2 capture and O2 enrichment: Structural stability and oxygen sorption properties

The novel Fe/Nb co-doped SrCo_1 ? 2x(Fe,Nb)_xO_3 ? δ (x = 0.05, 0.10) perovskite oxides were synthesized by the solid-state method. Structural and chemical stability of the SrCo_1 ? 2x(Fe,Nb)_xO_3 ? δ (x = 0.05, 0.10) oxides were studied by differential scanning calorimetry (DSC), thermogravimetric analysis (TG) and X-ray diffraction (XRD). The results demonstrated that the structural and chemical stability of the Fe/Nb co-doped SrCo_1 ? 2x(Fe,Nb)_xO_3 ? δ (x = 0.05, 0.10) is improved significantly. The oxygen sorption properties of the SrCo_1 ? 2x(Fe,Nb)_xO_3 ? δ (x = 0.05, 0.10) oxides were investigated between 300–900 °C in air, and the high oxygen sorption capacity of 11.5 and 10.3 mL O₂ (STP)/g oxide, respectively, are obtained.     

Zirconium oxide nanotube surface prompts increased osteoblast functionality and mineralization

Electrochemical formation of tunable nanoscale oxide layers on biomedical metallic surfaces has recently drawn much attention in biomaterials research. In this study, we report on the cellular response to a unique vertically aligned, laterally spaced nanotube nanostructure made of zirconium oxide (ZrO₂) fabricated by anodization. The growth, morphology, and functionality of osteoblasts cultured on ZrO₂ nanotubes have been investigated. The initial adhesion and spreading was considerably improved on the nanotube surface as compared to a flat zirconium (Zr) surface without a nanostructure. The morphology of the adhered cells on the nanotube surface elicited a highly organized cytoskeleton with crisscross patterned actin, which was lacking on the flat Zr. Increased alkaline phosphatase activity levels and the formation of calcified extracellular matrix implied improved osteoblast functionality and mineralization on the nanotube substrate. This in vitro study suggests that the ZrO₂ nanotubes provided an enhanced osteoblast response and demonstrated their apparent role in providing a platform for bone growth.     

Measurement and modeling solubility of bioactive coumarin and its derivatives in supercritical carbon dioxide

To design a supercritical fluid extraction process for the separation of bioactive substances from natural products, a quantitative knowledge of phase equilibria between target biosolutes and solvent is necessary. How-ever, mostly no such information is available in literature to date. Thus in the present study, illustratively the solubility of bioactive coumarin and its various derivatives (i.e., hydroxy-, methyl-, and methoxy-derivatives) in supercritical CO₂ were measured at 308.15–328.15 K and 10–30 MPa. Also, the pure physical properties such as normal boiling point, critical constants, acentric factor, molar volume and standard vapor pressure for coumarin and its derivatives were estimated. By these estimated information, the measured solubilities were quantitatively correlated by an approximate lattice equation of state proposed recently by the present authors.     

Liquid-liquid phase separation in polysulfone/solvent/water systems

The cloud point curves for polysulfone (PSf)/solvent/water systems were determined by a titration method. A small amount of water was needed to induce liquid-liquid demixing and the temperature effect was small. From numerical calculations, it was found that the binary interaction parameters for the PSf/solvent/water system enlarges the homogeneous region in the phase diagram with a smaller nonsolvent-polymer interaction parameter χ₁₃, a greater nonsolvent-solvent interaction parameter χ₁₂, and a smaller solvent-polymer interaction parameter χ₂₃ and the effect of polymer molecular weight was negligible except in the range of low molecular weight. The phase diagrams, calculated with constant χ₁₂ that was chosen from the concentration-dependent interaction parameter g₁₂ value of the concentration range, were similar to the results obtained with g₁₂. The slope of the tie lines indicated that demixing of the ternary system occurred at relatively similar nonsolvent concentration in both phases. A value of 2.7 for the water-PSf interaction parameter was obtained by fitting the experimental cloud point curve with the calculated binodal lines. © 1997 John Wiley & Sons, Inc. J Appl Polym Sci 65: 2643–2653, 1997     

Fractal analysis of pressure fluctuations in a three phase bubble column reactor operating at low pressure

Pressure fluctuations in a three phase bubble column reactor operating at relatively low pressure (92 KPa) have been analyzed by adopting the spectral and fractal analyses to get the engineering informations for the on-line control and fault diagnosis of the reactors. The mean value, standard deviation, skewness and kurtosis of the pressure fluctuations have been obtained. The local fractal dimension has been determined from the Pox diagram obtained by means of the rescaled range analysis of the pressure fluctuations based on the fractional Brownian motion. The local fractal dimension of pressure fluctuations has increased and thus the pressure fluctuation signals have become less persistent and irregular, with increases in the gas flow rate reaction temperature, particle size and solid content in the slurry phase. The local fractal dimension has been well correlated in terms of the operating variables.