Cytotoxic 5‐Hydroxyindole Alkaloids from the Marine Sponge Scalarispongia sp.

Three new 5‐hydroxyindole alkaloids ( 1 , 2 , 3 ) along with seven known analogs ( 4 , 5 , 6 , 7 , 8 , 9 , 10 ) were isolated from a Dokdo marine sponge Scalarispongia sp. The elucidation of the structures of the new compounds by spectroscopic analyses indicated that these compounds were an indole glyoxylate ( 1 ), a mono‐indole analog of hyrtinadine A ( 2 ), and a symmetrical bis‐indole with pyridine linker ( 3 ). The comparison of IC₅₀ values for obtained compounds against a human leukemia cell line revealed that the bis‐indole structure is a requirement for cytotoxicity.     

Mild and Efficient Deoxygenation of Sulfoxides with a WCl6/Indium System

Dialkyl, diaryl, and aryl alkyl sulfoxides can be rapidly converted to the corresponding sulfides with a WCl₆/In system in excellent yields under mild conditions.     

Total synthesis of (+)-valienamine and (−)-1-epi-valienamine via a highly diastereoselective allylic amination of cyclic polybenzyl ether using chlorosulfonyl isocyanate

The total synthesis of (+)-valienamine and (−)-1-epi-valienamine was concisely accomplished from readily available d-glucose via a highly diastereoselective amination of chiral benzylic ether using chlorosulfonyl isocyanate, intramolecular olefin metathesis, and diastereoselective reduction of cyclic enone using l-Selectride as the key steps.     

New regioisomeric naphthol–thiazole based ‘turn-on’ fluorescent chemosensor for Al

Two new reactive and highly selective turn-on fluorescent chemosensors based on the position of ring annulation of the naphthalene–thiazole moiety for aluminum ions in ethanol, were synthesized and investigated. It was found that sensors 2 and 4 exhibited a remarkable enhancement of emission upon complexation with Al³⁺. A TD-B3LYP/6-31G(d,p) calculation was performed to characterize the nature of the fluorescence behavior of sensors 2 and 4 upon Al³⁺ complexation. The mechanism of fluorescence was based on the cation promoted hydrolysis of ester and subsequent complexation. The combination of experimental and computational analyses provides a more complete understanding of the molecular level origin of these types of unique photophysical properties.     

Dual‐micropillar‐based microfluidic platform for single embryonic stem cell‐derived neuronal differentiation

We developed the dual‐micropillar‐based microfluidic platform to direct embryonic stem (ES) cell fate. 4 × 4 dual‐micropillar‐based microfluidic platform consisted of 16 circular‐shaped outer micropillars and 8 saddle‐shaped inner micropillars in which single ES cells were cultured. We hypothesized that dual‐micropillar arrays would play an important role in controlling the shear stress and cell docking. Circular‐shaped outer micropillars minimized the shear stress, whereas saddle‐shaped inner micropillars allowed for docking of individual ES cells. We observed the effect of saddle‐shaped inner micropillars on cell docking in response to hydrodynamic resistance. We also demonstrated that ES cells cultured for 6 days within the dual‐micropillar‐based microfluidic platform differentiated into neural‐like cells. Therefore, this dual‐micropillar‐based microfluidic platform could be a potentially powerful method for screening of lineage commitments of single ES cells.     

Core/Shell Structured PCM Nanocapsules Obtained by Resin Fortified Emulsion Process

Phase change material (PCM, octadecane) nanocapsules were successfully prepared by resin fortified emulsion (RFE) polymerization using the alkali soluble resin (ASR) of poly(ethylene‐co‐acrylic acid) (EAA) and poly(styrene‐co‐acrylic acid) (SAA). Stable PCM nanocapsules were obtained by resin fortified emulsion polymerization, which could be attributed to the prevention of Ostwald ripening due to PCM being hydrophobic. Analysis of online FTIR measurements throughout the reaction confirmed that the nanocapsules contained octadecane as a PCM. TEM imaging of the PCM nanocapsules showed spherical and core/shell morphology. The characteristics of PCM nanocapsules can be controlled by process parameters. As a result, the particle size and particle size distribution (i.e., polydispersity index (Dw/Dn)) of the PCM nanocapsules were created by adjusting manufacturing conditions. The PCM nanocapsules exhibited thermal energy storage (～49.8 J/g) and release (～47.9 J/g) behavior.     

Self-assembled discotic nematic liquid crystals formed by simple hydrogen bonding between phenol and pyridine moieties

New discotic nematic liquid crystals have been prepared through intermolecular hydrogen bonding between the core of 1,3,5-trihydroxybenzene (phloroglucinol, PG) or 1,3,5-tris(4-hydroxyphenyl)benzene (THPB) and the peripheral molecules of stilbazole derivatives. The various nematic phases formed by new hydrogen bonding building blocks were investigated by differential scanning calorimetry, polarising optical microscopy and X-ray diffraction. The first discotic complexes of PG and trans-4-alkoxy-4′-stilbazoles exhibited nematic columnar (N_C) and hexagonal columnar phases depending on the length of alkyl chains, which were considered as the basic discotic structure. Several structural variations on the building blocks were attempted to examine their effects on the liquid crystalline properties of discotic complexes. The nematic lateral phase (N_L) with enhanced intercolumnar order was observed for the complexes of PG and trans-4-cyanoalkoxy-4′ stilbazoles due probably to the strong dipole interactions between cyano groups at the end of alkoxy chains. By introducing the nonlinear structure in three arms of supramolecular discotic mesogen, a discotic nematic phase (N_D) was observed for the complex of THPB and trans-4-octyloxy-4 -stilbazole. The single hydrogen bonding between phenol and pyridine moieties in this study provides a simple and effective method for preparing the rarely found discotic nematic liquid crystals.     

Investigation on ion movement in the fringe-field switching mode depending on resistivity of alignment layer and dielectric anisotropic sign of liquid crystal

Adsorption and desorption of ions at interface between liquid crystal and alignment layer in liquid crystal displays play a crucial role in residual direct current voltage associated with image sticking. In this article, the dependency of such adsorption and desorption of ions on resistivity of alignment layer and sign of liquid crystal dielectric anisotropy in the fringe-field liquid crystal cell has been investigated. Our studies show that the time constant of ions during adsorption and desorption depends upon resistivity and dielectric constant of liquid crystal and alignment layer, and most strongly influenced by the resistivity of alignment layer such that the one with lower resistivity in two orders shows much faster adsorption and desorption at the interface than that of the one with higher resistivity.     

Silaffin Peptides as a Novel Signal Enhancer for Gravimetric Biosensors

Application of biomimetic silica formation to gravimetric biosensors has been conducted for the first time. As a model system, silaffin peptides fused with green fluorescent protein (GFP) were immobilized on a gold quartz crystal resonator for quartz crystal microbalances using a self-assembled monolayer. When a solution of silicic acid was supplied, silica particles were successfully deposited on the Au surface, resulting in a significant change in resonance frequency (i.e., signal enhancement) with the silaffin–GFP. However, frequency was not altered when bare GFP was used as a control. The novel peptide enhancer is advantageous because it can be readily and quantitatively conjugated with sensing proteins using recombinant DNA technology. As a proof of concept, this study shows that the silaffin domains can be employed as a novel and efficient biomolecular signal enhancer for gravimetric biosensors.     

Enhancement of Enzymatic Hydrolysis and Klason Lignin Removal of Corn Stover Using Photocatalyst-Assisted Ammonia Pretreatment

Photocatalyst-assisted ammonia pretreatment was explored to improve lignin removal of the lignocellulosic biomass for effective sugar conversion. Corn stover was treated with 5.0–12.5 wt.% ammonium hydroxide, two different photocatalysts (TiO₂ and ZnO) in the presence of molecular oxygen in a batch reactor at 60 °C. Various solid-to-liquid ratios (1:20–1:50) were also tested. Ammonia pretreatment assisted by TiO₂-catalyzed photo-degradation removed 70 % of Klason lignin under the optimum condition (12.5 % ammonium hydroxide, 60 °C, 24 h, solid/liquid?=?1:20, photocatalyst/biomass?=?1:10 with oxygen atmosphere). The enzymatic digestibilities of pretreated corn stover were 85 % for glucan and 75 % for xylan with NH₃-TiO₂-treated solid and 82 % for glucan and 77 % for xylan with NH₃-ZnO-treated solid with 15 filter paper units/g-glucan of cellulase and 30 cellobiase units/g-glucan of β-glucosidase, a 2–13 % improvement over ammonia pretreatment alone.