Nanocatalosomes as Plasmonic Bilayer Shells with Interlayer Catalytic Nanospaces for Solar‐Light‐Induced Reactions

Interest and challenges remain in designing and synthesizing catalysts with nature‐like complexity at few‐nm scale to harness unprecedented functionalities by using sustainable solar light. We introduce “nanocatalosomes”—a bio‐inspired bilayer‐vesicular design of nanoreactor with metallic bilayer shell‐in‐shell structure, having numerous controllable confined cavities within few‐nm interlayer space, customizable with different noble metals. The intershell‐confined plasmonically coupled hot‐nanospaces within the few‐nm cavities play a pivotal role in harnessing catalytic effects for various organic transformations, as demonstrated by “acceptorless dehydrogenation”, “Suzuki–Miyaura cross‐coupling” and “alkynyl annulation” affording clean conversions and turnover frequencies (TOFs) at least one order of magnitude higher than state‐of‐the‐art Au‐nanorod‐based plasmonic catalysts. This work paves the way towards next‐generation nanoreactors for chemical transformations with solar energy.     

Highly Conducting and Flexible Radical Crystals

Together with high conductivity, high flexibility is an important property required for next generation organic electronic components. Both properties are difficult to achieve together especially when the components are crystalline because of the intrinsic high brittleness of organic molecular crystals. We report an organic radical crystal system that has both high flexibility and high conductivity. The crystal consists of 9,10‐bis(phenylethynyl)anthracene radical cation ( BPEA^.+ ) units, and shows flexibility under pressure with high conductivity in ambient condition exhibiting average conductivity of 2.68 S cm^?1 when normal linear shape, as well as 2.43 S cm^?1 when bent. The structural analysis reveals that both a short π–π distance (3.290 Å) between BPEA^.+ units that are aligned along the crystal length direction, and the presence of PF₆^? counter ions induce flexibility and high electrical conductivity.     

Stimuli sensitive polymers for drug delivery systems

Temperature sensitive and electric field sensitive hydrogels were prepared for use in modulated drug release systems. Crosslinked poly(N-isopropyl-acrylamide) and its networks, modified with hydrophobic components by copolymerization or by interpenetrating polymer networks (IPNs) formation, were utilized as temperature sensitive hydrogels. Indomethacin (a model solute)-release from polymer matrix and permeation through polymer membrane demonstrated “on-off” regulation with temperature fluctuation. This was the result of polymer surface properties rather than bulk swelling, as temperature was changed past the swelling transition temperature range of the polymer. The on-off regulation in an electric field was also obtained with a positively charged solute (Edrophonium chloride) release in distilled-deionized water from a matrix of crosslinked poly(2-acrylamido-2-methylpropanesulfonic acid-co-butyl methacrylate). This was attributed to the ion exchange between Edrophonium ion and protons produced at the anode. The swelling changes produced by local pH or ionic strength changes affected non-charged solute release.     

Study on Viscous Fluid Flow in Disordered-Deformable Porous Media Using Hydro-mechanically Coupled Pore-Network Modeling

Transport in Porous Media - We investigate viscous fluid flows and concurrent fluid-driven deformations in porous media. The hydro-mechanically (H-M) coupled pore-network model (PNM) is developed,...     

Preparation and characterization of self-assembled nanoparticles based on glycol chitosan bearing adriamycin

An anthracycline drug, adriamycin, was chemically conjugated onto the backbone of glycol chitosan via an acid-labile cis-aconityl linkage. The physicochemical characteristics of the glycol chitosan–adriamycin (GC–ADR) conjugates were investigated by dynamic light scattering, atomic force microscopy, and fluorescence spectroscopy. The GC–ADR conjugates were capable of forming nano-sized self-aggregates in an aqueous medium, when the adriamycin content in the conjugate was in the range of 2.0–5.0 wt.%. The self-aggregates were spherical in shape, and had mean diameters of 238–304 nm, depending on the adriamycin content. The critical aggregation concentrations of the conjugates, estimated by the fluorescence quenching method, were as low as 1.0–2.5×10⁻² mg/ml. The size of self-aggregates was not affected by the polymer concentration in the range from 50 to 2,000 μg/ml, and was maintained up to 8 days in phosphate-buffered saline (pH 7.4), indicating high colloidal stability. The release of adriamycin from self-aggregates was significantly dependent on the pH of the medium due to the cis-aconityl linkage; e.g., the amount of adriamycin released for 4 days was 7.3±0.3% at pH 7, whereas it was 29.3±1.9% at pH 4. The cell viability results demonstrated that free adriamycin shows more potent cytotoxicity than the conjugates, primarily attributed to the sustained release of adriamycin from self-aggregates. In conclusion, the self-aggregates, formed by GC–ADR conjugates, might be useful for the site-specific delivery of adriamycin in a sustained manner.     

Supramolecular Phthalocyanine Assemblies for Improved Photoacoustic Imaging and Photothermal Therapy

Phototheranostic nanoplatforms are of particular interest for cancer diagnosis and imaging‐guided therapy. Herein, we develop a supramolecular approach to fabricate a nanostructured phototheranostic agent through the direct self‐assembly of two water‐soluble phthalocyanine derivatives, PcS4 and PcN4. The nature of the molecular recognition between PcS4 and PcN4 facilitates the formation of nanostructure (PcS4‐PcN4) and consequently enables the fabrication of PcS4‐PcN4 with completely quenched fluorescence and reduced singlet oxygen generation, leading to the high photoacoustic and photothermal activity of PcS4‐PcN4. In vivo evaluations suggest that PcS4‐PcN4 could not only efficiently visualize a tumor with high contrast through whole‐body photoacoustic imaging but also enable excellent photothermal therapy for cancer.     

Glucose-Responsive Monoolein Cubic Phase Containing Glucose Oxidase

Glucose-responsive monoolein (MO) cubic phase was prepared by immobilizing proteinoid composed of Asp and Leu (PAL) and hydrophobically modified glucose oxidase (HmGOD) onto the MO bilayers. The hydrodynamic mean diameter of PAL aggregate in aqueous solution decreased with increasing the pH value. The number of pamitic acid residue per one molecule of HmGOD was determined to be 6.3 by a calorimetric method. HmGOD could acidify glucose solution in a few hours, possibly because it converted glucose to gluconic acid. PAL- and HmGOD-immobilized MO cubic phase was prepared by hydrating MO melt with the mixture aqueous solution of PAL and HmGOD. The cubic phase exhibited its phase transition around 62.5°C, determined by polarizing microscopy. The release of carboxylic fluorescein (CF) from the cubic phase was suppressed when the pH value of release medium decreased, possibly because PAL can aggregate more at a lower pH value. The release was suppressed when glucose concentration increased, possibly because the release medium can be more acidified and PAL will be more aggregated at a higher glucose concentration. The cubic phase could be used as a drug carrier which releases its content in a sustained manner when the glucose concentration is abnormally high.     

Regulation of Cytokines and Dihydrotestosterone Production in Human Hair Follicle Papilla Cells by Supercritical Extraction-Residues Extract of Ulmus davidiana

This study was conducted to examine the anti-hair loss mechanism of the supercritical fluid extraction-residues extract of Ulmus davidiana by the regulation of cytokine production and hormone function in human dermal follicle papilla cells (HDFPCs). To investigate the modulatory effects on H₂O₂-induced cytokines, we measured transforming growth factor-beta and insulin-like growth factor 1 secreted from HDFPCs. To investigate the regulatory effects of supercritical extraction-residues extract of Ulmus davidiana on dihydrotestosterone hormone production, cells were co-incubated with high concentrations of testosterone. The supercritical extraction-residues extract of Ulmus davidiana significantly inhibited the secretion of transforming growth factor-beta but rescued insulin-like growth factor 1 in a dose-dependent manner. The supercritical extraction-residues extract of Ulmus davidiana markedly reduced dihydrotestosterone production. These results suggest that the supercritical fluid extract residues of Ulmus davidiana and their functional molecules are candidates for preventing human hair loss.     

The effect of a market factor on information flow between stocks using the minimal spanning tree

We empirically investigated the effects of market factors on the information flow created from N(N−1)/2 linkage relationships among stocks. We also examined the possibility of employing the minimal spanning tree (MST) method, which is capable of reducing the number of links to N−1. We determined that market factors carry important information value regarding information flow among stocks. Moreover, the information flow among stocks showed time-varying properties according to the changes in market status. In particular, we noted that the information flow increased dramatically during periods of market crises. Finally, we confirmed, via the MST method, that the information flow among stocks could be assessed effectively with the reduced linkage relationships among all links among stocks from the perspective of the overall market.