Biocleavable polyrotaxane-plasmid DNA polyplex for enhanced gene delivery

A biocleavable polyrotaxane, having a necklace-like structure consisting of many cationic alpha-cyclodextrins (alpha-CDs) and a disulfide-introduced poly(ethylene glycol) (PEG), was synthesized and examined as a nonviral gene carrier. The polyrotaxane formed a stable polyplex having positively charged surface even at low charge ratio. This is likely to be due to structural factors of the polyrotaxane, such as the mobile motion of alpha-CDs in the necklace-like structure. Rapid endosomal escape was observed 90 min after transfection. The positively charged surface and the good buffering capacity are advantageous to show the proton sponge effect. The pDNA decondensation occurred through disulfide cleavage of the polyrotaxane and subsequent supramolecular dissociation of the noncovalent linkages between alpha-CDs and PEG. Transfection of the DMAE-SS-PRX polyplex is independent of the amount of free polycation. Those properties played a key role for delivery of pDNA clusters to the nucleus. Therefore, the polyplex nature and the supramolecular dissociation of the polyrotaxane contributed to the enhanced gene delivery.     

Synthesis and characterization of bromonium ylides and their unusual ligand transfer reactions with N-heterocycles

Stable aliphatic bromonium ylides (RfSO2)2C--Br+C6H4-p-CF3 (Rf = CF3, CF3(CF2)3) have been synthesized and structurally characterized for the first time. X-ray crystallographic analyses indicated a ylide structure with an sp2 hybridization of the ylide carbanions and with little double-bond character for the ylidic bond. The bromonium ylides selectively undergo transfer of the aryl group to nitrogen heterocycles, such as pyridines, yielding N-arylpyridinium salts. This is in a marked contrast to the reaction of the iodonium ylides, which produces pyridinium ylides through transylidations.     

Guanidinium ylide mediated aziridination: identification of a spiro imidazolidine-oxazolidine intermediate

We successfully isolated a spiro imidazolidine-oxazolidine intermediate in the reaction of guanidinium ylide mediated aziridination using alpha-bromocinnamaldehyde. X-ray crystallographic analysis unambiguously revealed that the stereogenic centers of the spiro intermediate were in a trans configuration. The role of the spiro compound as an intermediate in the aziridination reaction was confirmed by observation of its smooth chemical conversion into aziridine products.     

A miniaturization of the multi-degree-of-freedom ultrasonic actuator using a small cylinder fixed on a substrate

Multi-degree-of-freedom ultrasonic actuator has been studied for robot arms and multidimensional precision table and so on because of its simple structure, silent operation, and holding force. In this study, we aim to miniaturize multi-degree-of-freedom ultrasonic actuator for fabrication on a substrate. This actuator consists of a stainless steel cylinder and a PZT ring. The cylinder is fixed on a substrate and the PZT ring is glued to the substrate near the cylinder. The 1st longitudinal vibration and the 2nd bending vibration are simultaneously excited in the cylinder to make elliptical motion at the top of the cylinder and a ball rotor placed on the cylinder rotates because of the friction force. Length of the cylinder was decided so as to tune the resonance frequency of the 1st longitudinal vibration to the 2nd bending one. Actuator performances are evaluated experimentally using a 14 mm height and 7 mm diameter stainless steel cylinder with a 0.5 mm thickness PZT ring. The rotation about the cylinder axis is tested using the two orthogonal bending vibrations with 90 degrees phase difference. Also, the rotation about horizontal axes were investigated using the combination of the longitudinal vibration and one of two bending vibrations. We measured the rotation speed of a steel ball and obtained 15.8 rps using a 6 mm diameter ball rotor.     

Hydrogen generation by reaction of Si nanopowder with neutral water

Si and its oxide are nonpoisonous materials, and thus, it can be taken for medical effects. We have developed a method of generation of hydrogen by use of reactions of Si nanopowder with water in the neutral pH region. Si nanopowder is fabricated by the simple bead milling method. Si nanopowder reacts with water to generate hydrogen even in cases where pH is set at the neutral region between 7.0 and 8.6. The hydrogen generation rate strongly depends on pH and in the case of pH 8.0, ～55 ml/g hydrogen which corresponds to that contained in approximately 3 L saturated hydrogen-rich water is generated in 1 h. The reaction rate for hydrogen generation greatly increases with pH, indicating that the reacting species is hydroxide ions. The change of pH after the hydrogen generation reaction is negligibly low compared with that estimated assuming that hydroxide ions are consumed by the reaction. From these results, we conclude the following reaction mechanism: Si nanopowder reacts with hydroxide ions in the rate-determining reaction to form hydrogen molecules, SiO₂, and electrons in the conduction band. Then, generated electrons are accepted by water molecules, resulting in production of hydrogen molecules and hydroxide ions. The hydrogen generation rate strongly depends on the crystallite size of Si nanopowder, but not on the size of aggregates of Si nanopowder. The present study shows a possibility to use Si nanopowder for hydrogen generation in the body in order to eliminate hydroxyl radicals which cause various diseases.     

Focal length measurement of a varifocal liquid lens with capacitance detection

This paper reports on a detailed deformation model of varifocal liquid lenses fabricated by Parylene-on-liquid-deposition (POLD), which can be applied to measure and adjust the focal length of such lenses without using extra sensors or sensing mechanisms. The lens was fabricated by encapsulating a liquid between a transparent electrode and a polymer film that was covered with a metal electrode. When voltage is applied to the two electrodes, the lens deforms due to the electrostatic force, and its focal length and the capacitance between the two electrodes change simultaneously. This characteristic enables the focal length of the lens to be adjusted and detected by measuring the capacitance change. The focal length of the fabricated varifocal liquid lens changed from 153.6 to 82.6 mm by applying 150-V. The focal length change of the liquid lens was calculated from the change in its capacitance. Finally, to confirm the efficiency of this varifocal liquid lens, we fabricated a confocal distance sensor using the lens for laser scanning and demonstrated that this system can be used to measure distances of 94–140 mm with an average error of 0.83 mm and a standard deviation of 0.77 mm.     

Hybrid Mesoporous-Silica Materials Functionalized by Pt(II) Complexes: Correlation between the Spatial Distribution of the Active Center, Photoluminescence Emission, and Photocatalytic Activity

[Pt(tpy)Cl]Cl (tpy: terpyridine) was successfully anchored to a series of mesoporous-silica materials that were modified with (3-aminopropyl)triethoxysilane with the aim of developing new inorganic-organic hybrid photocatalysts. Herein, the relationship between the luminescence characteristics and photocatalytic activities of these materials is examined as a function of Pt loading to define the spatial distribution of the Pt complex in the mesoporous channel. At low Pt loading, the Pt complex is located as an isolated species and exhibits strong photoluminescence emission at room temperature owing to metal-to-ligand charge-transfer ((3) MLCT) transitions (at about 530?nm). Energy- and/or electron-transfer from (3) MLCT to O(2) generate potentially active oxygen species, which are capable of promoting the selective photooxidation of styrene derivatives. On the other hand, short Pt???Pt interactions are prominent at high loading and the metal-metal-to-ligand charge-transfer ((3) MMLCT) transition is at about 620?nm. Such Pt complexes, which are situated close to each other, efficiently catalyze H(2) -evolution reactions in aqueous media in the presence of a sacrificial electron donor (EDTA) under visible-light irradiation. This study also investigates the effect of nanoconfinement on anchored guest complexes by considering the differences between the pore dimensions and structures of mesoporous-silica materials.     

In situ time-resolved DXAFS study of Rh nanoparticle formation mechanism in ethylene glycol at elevated temperature

A combination of in situ time-resolved DXAFS and ICP-MS techniques reveals that the formation process of Rh nanoparticles (NPs) from rhodium trichloride trihydrate (RhCl(3)·3H(2)O) in ethylene glycol with polyvinylpyrrolidone (PVP) at elevated temperature is a first-order reaction, which indicates that uniform size Rh NPs appear consecutively and these Rh NPs do not aggregate with each other.