Supramolecular nanodevices: from design validation to theranostic nanomedicine

The increasing importance of nanotechnology in the biomedical field and the recent progress of nanomedicines into clinical testing have spurred the development of even more sophisticated nanoscale drug carriers. Current nanocarriers can successfully target cells, release their cargo in response to stimuli, and selectively deliver drugs. More sophisticated nanoscale carriers should evolve into fully integrated vehicles with more complex capabilities. First, they should be able to sense targets inside the body and adapt their functions based on these targets. Such devices will also have processing capabilities, modulating their properties and functions in response to internal or external stimuli. Finally, they will direct their function to the aimed site through both subcellular targeting and delivery of loaded drugs. These nanoscale, multifunctional drug carriers are defined here as nanodevices. Through the integration of various imaging elements into their design, the nanodevices can be made visible, which is an essential feature for the validation. The visualization of nanodevices also facilitates their use in the clinic: clinicians can observe the effectiveness of the devices and gain insights into both the disease progression and the therapeutic response. Nanodevices with this dual diagnostic and therapeutic function are called theranostic nanodevices. In this Account, we describe various challenges to be overcome in the development of smart nanodevices based on supramolecular assemblies of engineered block copolymers. In particular, we focus on polymeric micelles. Polymeric micelles have recently received considerable attention as a promising vehicle for drug delivery, and researchers are currently investigating several micellar formulations in preclinical and clinical studies. By engineering the constituent block copolymers to produce polymeric micelles that integrate multiple smart functionalities, we and other researchers are developing nanodevices with favorable clinical properties.     

Quality inspection in polymer processing by a thermophysical handy tester

This paper presents the applicability of a thermophysical handy tester for quality inspection and diagnostic technique such as in situ measurement of polymeric resin products. Influence of crystallinity known as a rating factor of quality, or filler concentration upon thermal conductivity is determined for the case of unsaturated polyester resin products by using the tester. Consequently, good correlations between the thermal conductivity and the crystallinity or the filler concentration are certified. The variation or the distribution of thermal conductivity of products molded under various conditions can be detected nondestructively using the tester. As an example, the thermal conductivity distribution around the forming gate is demonstrated, indicating the density‐uniformity of the resin product. © 2006 Wiley Periodicals, Inc. Heat Trans Asian Res, 35(6): 421–433, 2006; Published online in Wiley InterScience ( www.interscience.wiley.com ). DOI 10.1002/htj.20124     

Characteristics of atmospheric pressure plasma jet generated by compact and inexpensive high voltage modulator

An atmospheric pressure plasma jet has been successfully generated using a compact high voltage modulator driven by 12 V alkaline batteries. A jet nozzle was composed of a quartz tube with two cylindrical electrodes. The grounded electrode was rolled on the tube and the powered one was inserted in the tube for discharging at lower voltage. V-Q Lissajous analysis of the plasma jet indicated that energy and power consumed for the plasma generation were linear along the distance between the electrodes. Length of the plasma plume from the tip of the tube was 11 mm for the gap length of 5 mm and the input voltage DC of 12 V. At the input voltage, the energy and power consumed for the plasma generation were 4.1 μJ and 0.12 W, respectively. Optical emission spectroscopy analysis of the plasma showed that the plasma contained hydroxyl radicals and exited nitrogen molecules which are chemically active species. The plasma jet can be applied to plasma cleaning for material surface though was generated with the alkaline batteries.     

Precise slit-width control of niobium apertures for superconducting LEDs

We introduce a novel three-step procedure for precise niobium (Nb)-etching on the nanometer-scale, including the design of high contrast resist patterning and sacrifice layer formation under high radio frequency (RF) power. We present the results of precise slit fabrication using this technique and discuss its application for the production of superconducting devices, such as superconductor-semiconductor-superconductor (S-Sm-S) Josephson junctions. For the reactive ion etching (RIE) of Nb, we selected CF(4) as etchant gas and a positive tone resist to form the etching mask. We found that the combination of resist usage and RIE process allows for etching of thicker Nb layers when utilizing the opposite dependence of the etching rate (ER) on the CF(4) pressure in the case of Nb as compared to the resist. Precise slit-width control of 80 and 200 nm thick Nb apertures was performed with three kinds of ER control, for the resist, the Nb, and the underlying layer. S-Sm-S Josephson junctions were fabricated with lengths as small as 80 nm, which can be considered clean and short and thus exhibit critical currents as high as 50 μA. Moreover, possible further applications, such as for apertures of superconducting light emitting diodes (SC LEDs), are addressed.     

Comparison between silicon thin films with and without incorporating crystalline silicon nanoparticles into the film

We have deposited Si thin films using a multi-hollow discharge plasma CVD method to compare properties of the films with and without incorporating crystalline Si nanoparticles into the films. After the deposition of the films, we have evaluated crystallization of the films by irradiating laser. We have found that a laser power at which crystalline Si nanoparticles embedded a-Si:H films start to be crystallized is lower than that for a-Si:H films without the nanoparticles. The incorporation of the nanoparticles has no effect on the defect density of the films. These results suggest incorporation of crystalline Si nanoparticles into the films play a role of crystallization of Si films during the deposition.     

Evaluation of charge transfer characteristics of metal-free phthalocyanine thin films by displacement current measurement

We have investigated phthalocyanine thin films using displacement current measurement. Two types of samples were prepared by vacuum evaporation method. One is the sample with a passivation film. The other is the sample without a passivation film. The passivation films were prepared by casting toluene solution containing 3 wt.% of polystyrene. The results obtained by measuring the samples elucidate the relation between carrier behavior and ambience. It is clarified that there are many traps in the sample without the passivation film. On the other hand, in the sample with the passivation film, traps are not observed. Therefore, it is concluded that the passivation film provides the constraint of oxygen doping as well as the preservation of carrier transfer system.     

Surfactant effects on hydrate formation in an unstirred gas/liquid system: An experimental study using methane and sodium alkyl sulfates

This paper reports an experimental study on the effects of surfactant additives on the formation of a clathrate hydrate in a quiescent methane/liquid-water system, which was initially composed of a 300-cm³ aqueous phase and an ∼640-cm³ methane-gas phase, then successively provided with methane such that the system pressure was held constant. The surfactants used in the present study were three sodium alkyl sulfates appreciably different in the alkyl chain length—they were sodium dodecyl sulfate (abbreviated as SDS), sodium tetradecyl sulfate (abbreviated as STS) and sodium hexadecyl sulfate (abbreviated as SHS). For each surfactant added to water up to, at most, 1.82-3.75 times the solubility, we performed visual observations of hydrate formation simultaneously with the measurements of methane uptake due to the hydrate formation. The qualitative hydrate-formation behavior thus observed was almost the same irrespective of the species as well as the initial concentration of the surfactant used; i.e., thick, highly porous hydrate layers were formed and grew on the horizontal gas/liquid interface and also on the test-chamber wall above the level of the gas/liquid interface. In each experimental operation, hydrate formation continued for a limited time (from ∼6 to ) and then practically ceased, leaving only a small proportion (typically 15% or less) of the aqueous solution unconverted into hydrate crystals. The variations in the time-averaged rate of hydrate formation (as measured by the rate of methane uptake) and the final water-to-hydrate conversion ratio with the initial concentration of each surfactant were investigated. Moreover, we examined the promotion of hydrate formation with the aid of a water-cooled cold plate, a steel-made flat-plate-type heat sink, vertically dipped into the aqueous phase across the gas/liquid interface.     

Application of chitosan solutions gelled by melB tyrosinase to water‐resistant adhesives

An investigation was undertaken on the application of dilute chitosan solutions gelled by melB tyrosinase‐catalyzed reaction with 3,4‐dihydroxyphenethylamine (dopamine). The tyrosinase‐catalyzed reaction with dopamine conferred water‐resistant adhesive properties to the semi‐dilute chitosan solutions. The viscosity of the chitosan solutions highly increased by the tyrosinase‐catalyzed quinone conversion and the subsequent nonenzymatic reactions of o‐quinones with amino groups of the chitosan chains. The viscosity of chitosan solutions highly increased in shorter reaction times by addition of melB tyrosinase. Therefore, in this study, the gelation of a chitosan solution was carried out without poly(ethylene glycol) (PEG), which was added for the gelation of chitosan solutions using mushroom tyrosinase. The highly viscous, gel‐like modified chitosan materials were allowed to spread onto the surfaces of the glass slides, which were tightly lapped together and were held under water. Tensile shear adhesive strength of over 400 kPa was observed for the modified chitosan samples. An increase in either amino group concentration of the chitosan solutions or molecular mass of the chitosan samples used effectively led to an increase in adhesive strength of the glass slides. Adhesive strength obtained by chitosan materials gelled enzymatically was higher than that obtained by a chitosan gel prepared with glutaraldehyde as a chemical crosslinking agent. In addition, the use of melB tyrosinase led to a sharp increase in adhesive strength in shorter reaction times without other additives such as PEG. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci, 2008