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.     

Helical Mechanoclinic Deformation of Main‐Chain Chiral Smectic Elastomers

The helical mechanoclinic deformation of a main‐chain chiral smectic elastomer, which is prepared by a crosslinking reaction under twist deformation, is investigated. The twist deformation induces a layer tilt angle that depends on the handedness of twist. The layer tilt angle in the right‐handedly twisted elastomer, of which the handedness is consistent with that of the helix in the SmC* phase of the non‐crosslinked backbone polymer, is estimated to be up to 16° at room temperature, although that in the left‐handedly twisted elastomer is less than several degrees. The experiments provide evidence of chiral coupling between tilt and twist for helical mechanoclinic deformation in the chiral smectic system.

     

Mode change in the self-motion of a benzoquinone disk coupled with a NADPH system

The self-motion of a benzoquinone (BQ) disk on NADPH was investigated as the coupling of an autonomous motor and an enzyme reaction. In the absence of the enzyme reaction, features of motion changed depending on the concentration of NADPH, that is, continuous motion→ intermittent oscillatory motion→ no motion. When the reverse reaction from NADP(+) to NADPH was introduced into the system with the addition of an enzyme reaction, continuous motion changed to intermittent oscillatory motion with small amplitude. The mechanism of this mode change is discussed in relation to the surface tension as a driving force and the time course of UV spectra as a window to the progress of the reaction. Characteristic features of the mode change were qualitatively reproduced by a numerical calculation.     

Photo-sensitive self-motion of a BQ disk

The photo-sensitive self-motion of a benzoquinone (BQ) disk was investigated on a hydroquinone (HQ) aqueous solution. The mode-switching of self-motion, i.e., continuous → intermittent → no motion, was observed with an increase in the concentration of HQ. Upon irradiation with UV light (～254 nm), the critical concentrations of HQ that were associated with the three modes of motion shifted to lower values, and the average speed of motion decreased. We discuss the mechanism of the photo-sensitive self-motion in relation to the photochemical reaction from BQ to HQ and the driving force of the disk.     

Selective permeation of CO2 and CH4 through kapton polyimide: Effects of penetrant competition and gas-phase nonideality

Sorption isotherms for pure CO₂ and pure CH₄ in Kapton H® polymide films at 60°C are reported for pressures up to 20 atm and are analyzed in terms of the dual-mode sorption model. An experimental scheme for the measurement of steady-state permeabilities of both pure and mixed gas feeds is described. Permeabilities of Kapton to the individual components at 60°C are presented for a mixture comprised of 32.2% CO₂ in CH₄ as functions of feed pressure up to 590 psi (absolute). The permeabilities for the individual penetrants in the mixed feed are lower than the respective purecomponent values at the corresponding partial pressures. Furthermore, the permeabilities of both penetrants drop as the feed pressure is increased at constant composition. The dual-mobility transport model used to analyze the data postulates that the observed pressure and composition dependence of the permeabilities is due to competition between penetrants for a limited microvoid sorption capacity in the glassy polymer. It is demonstrated that in addition to flux depressions due to dual-mode effects, nonideality of the gas phase must be accounted for to explain the substantial flux depressions observed for the CO₂/CH₄ mixtured used in this study.     

Adsorption and desorption behaviors of cationic liposome-DNA complexes upon lipofection in inside and outside biomembrane models using a dynamic quasi-elastic laser scattering method.

The dynamic behaviors of cationic liposome-DNA complexes in inside and outside biomembrane models upon lipofection were investigated using the time-resolved quasi-elastic laser scattering (QELS) method. Inside and outside biomembrane models with similar phospholipid compositions to those in living cells were formed at a tetradecane/phosphate buffered saline (TD/PBS) interface. Cationic liposome-DNA complexes were injected into the buffer subphase, and their adsorption/desorption behaviors at the biomembrane models were monitored through changes in the interfacial tension. We found that the adsorption rate of the complexes increased 2.6 times more in the outside model than in the inside one. The adsorption rate of DNA alone did not show a remarkable difference from one side to the other; however, the adsorption rate of the cationic liposome alone showed a similar tendency to that of the liposome-DNA complex. These results indicated that the difference in lipid composition induced a different dynamic behavior of exogenous biomolecules and that the cationic liposomes played an important role in the faster incorporation of DNA into cells upon lipofection.     

Self-assembly and subsequent accumulation of lipid nanotubes at oil/water interfaces.

We utilized oil/water interfaces as a new field to produce lipid nanotubes (LNTs), which are formed by the self-assembly of lipid molecules, and possess hollow nanometer-wide cylindrical structures. Compared to the self-assembling field in bulk water, oil/water interfaces produced shorter lipids nanotubes less than 10 microm long more efficiently. In addition, we found that the oil/water interface accumulates lipid nanotubes spontaneously. This methodology is favorable to fabricate LNTs as new nano-fluidic devices, or sensors that require accumulation and alignment in two dimensions.     

Photoinduced one-electron reduction of MV2+ in titania nanosheets using porphyrin in mesoporous silica thin films

Composite films of a meso-(tetramethylpyridinium)porphyrin (TMPyP) hybrid incorporated in mesoporous silica (MPS) and cast on a methyl viologen (MV2+)/titania nanosheet hybrid were synthesized and a light-induced charge separation between the two could be observed. These composite thin films were able to initiate a one-electron reduction of the MV2+ ions accompanied by the simultaneous decomposition of the TMPyP organic dye within the mesoporous silica channels.     

Supramolecular hydrogel formation based on inclusion complexation between poly(ethylene glycol)-modified chitosan and alpha-cyclodextrin

Supramolecular hydrogels have been prepared on the basis of polymer inclusion complex (PIC) formation between poly(ethylene glycol) (PEG)-modified chitosans and alpha-cyclodextrin (alpha-CD). A series of PEG-modified chitosans were synthesized by coupling reactions between chitosan and monocarboxylated PEG using water-soluble carbodiimide (EDC) as coupling agent. With simple mixing, the resultant supramolecular assembly of the polymers and alpha-CD molecules led to hydrogel formation in aqueous media. The supramolecular structure of the PIC hydrogels was confirmed by differential scanning calorimetry (DSC), X-ray diffraction, and (13)C cross-polarized/magic-angle spinning (CP/MAS) NMR characterization. The PEG side-chains on the chitosan backbones were found to form inclusion complexes (ICs) with alpha-CD molecules, resulting in the formation of channel-type crystalline micro-domains. The IC domains play an important role in holding together hydrated chitosan chains as physical junctions. The gelation property was affected by several factors including the PEG content in the polymers, the solution concentration, the mixing ratio of host and guest molecules, temperature, pH, etc. All the hydrogels in acidic conditions exhibited thermo-reversible gel-sol transitions under appropriate conditions of mixing ratio and PEG content in the mixing process. The transitions were induced by supramolecular association and dissociation. These supramolecular hydrogels were found to have phase-separated structures that consist of hydrophobic crystalline PIC domains, which were formed by the host-guest interaction between alpha-CD and PEG, and hydrated chitosan matrices below the pK(a).The formation of inclusion complexes between alpha-cyclodextrin and PEG-modified chitosan leads to the formation of hydrogels that can undergo thermo-reversible supramolecular dissociation.