Influence of Thiol-Functionalized Polysilsesquioxane/Phosphorus Flame-Retardant Blends on the Flammability and Thermal, Mechanical, and Volatile Organic Compound (VOC) Emission Properties of Epoxy Resins.

In this study, thiol-functionalized ladder-like polysesquioxanes end-capped with methyl and phenyl groups were synthesized via a simple sol-gel method and characterized through gel permeation chromatography (GPC), Fourier transform infrared spectroscopy (FTIR), nuclear magnetic resonance (NMR), and thermogravimetric analysis (TGA). Additionally, epoxy blends of different formulations were prepared. Their structural, flame-retardant, thermal, and mechanical properties, as well as volatile organic compound (VOC) emissions, were determined using differential scanning calorimetry (DSC), dynamic mechanical analysis (DMA), TGA, scanning electron microscopy (SEM), limiting oxygen index (LOI), cone calorimetry, and a VOC analyzer. Compared to epoxy blends with flame retardants containing elemental phosphorus alone, those with flame retardants containing elemental phosphorus combined with silicon and sulfur exhibited superior thermal, flame-retardant, and mechanical properties with low VOC emissions. SEM of the residual char revealed a dense and continuous morphology without holes or cracks. In particular, LOI values for the combustion of methyl and phenyl end-capped polysilsesquioxane mixtures were 32.3 and 33.7, respectively, compared to 28.4% of the LOI value for the blends containing only phosphorus compounds. The silicon-sulfur-phosphorus-containing blends displayed reduced flammability concerning the blends using a flame retardant containing only phosphorus. This reflects the cooperative effects of various flame-retardant moieties.

Biomimetic lipid-fluorescein probe for cellular bioimaging.

Fluorescence probe is one of the most powerful tools for cellular imaging. Here, three phospholipid-mimicking fluorescent probes (FP1-FP3) comprising fluorescein and two lipophilic groups of saturated and/or unsaturated C18 fatty acids were synthesized, and their optical properties were investigated. Like in biological phospholipids, the fluorescein group acts as a hydrophilic polar headgroup and the lipid groups act as hydrophobic non-polar tail groups. Laser confocal microscope images illustrated that FP3, which contains both saturated and unsaturated lipid tails, showed great uptake into the canine adipose-derived mesenchymal stem cells.

Turn-on fluorescent naphthalimide-benzothiazole probe for cyanide detection and its two-mode aggregation-induced emission behavior.

Naphthalimide-benzothiazole conjugate (NBTZ) linked by cinnamonitrile was designed, synthesized, and fully characterized by NMR (1H, 13C, DEPT, HSQC) and high-resolution mass spectrometry. NBTZ exhibited unique turn-on fluorescence in the presence of CN- with relatively high selectivity compared to other anions such as SCN-, HSO4-, ClO4-, NO3-, Cl-, Br-, I-, and PO4-3 in tetrahydrofuran (THF). The detection limit for CN- was found to be 3.35 × 10-8 M in THF. The sensing mechanism was analyzed through 1H, 13C, DEPT, and mass spectroscopy. NBTZ also showed two-mode aggregation-induced emission (AIE) in THF-H2O mixtures. In a 30:70 THF-H2O (v/v) mixture, the maximum AIE was observed at 430 nm (blue) because of the rotation of the CC bond between the naphthalimide ring and the phenyl ring was restricted. In 10:90 THF-H2O (v/v), a new red-shifted AIE appeared at 490 nm (cyan), due to the extended π-conjugation induced by restriction of rotation of the CC bond between the benzothiazole and naphthalimide rings.

Preparation and Electrochemical Properties of Porous Carbon Nanofiber Electrodes Derived from New Precursor Polymer: 6FDA-TFMB.

Porous carbon nanofibers (CNFs) with high energy storage performance were fabricated with a single precursor polymer, 6FDA-TFMB, without the use of any pore-generating materials. 6FDA-TFMB was synthesized, electrospun, and thermally treated to produce binder-free CNF electrodes for electrochemical double-layer capacitors (EDLCs). Highly porous CNFs with a surface area of 2213 m2 g-1 were prepared by steam-activation. CNFs derived from 6FDA-TFMB showed rectangular cyclic voltammograms with a specific capacitance of 292.3 F g-1 at 10 mV s-1. It was also seen that CNFs exhibit a maximum energy density of 13.1 Wh kg-1 at 0.5 A g-1 and power density of 1.7 kW kg-1 at 5 A g-1, which is significantly higher than those from the common precursor polymer, polyacrylonitrile (PAN).

Influence of Metal Ions on the Immobilization of ß-Glucosidase Through Protein-Inorganic Hybrids.

Immobilization of enzymes through metal-based system is demonstrated as a promising approach to enhance its properties. In this study, the influence of metals ions, including copper, cobalt and zinc (Zn) on the immobilization of ß-glucosidase (BGL) through the synthesis of protein-inorganic hybrid was evaluated at 4 °C. Among these metal ions-based hybrids, Zn showed the highest encapsulation yield and relative activity of 87.5 and 207%, respectively. Immobilized BGL exhibited higher pH and temperature stability compared to free form. Thermal stability of hybrid improved up to 26-fold at 60 °C. After 10 cycles of reuse, immobilized enzyme retained 93.8% of residual activity. These results suggested that metal ions played a significant role in the enzyme immobilization as a protein-inorganic hybrid. Overall, this strategy can be potentially applied to enhance the properties of enzymes though effective encapsulation for the broad biotechnological applications.

Low-Temperature Solution-Processed Gate Dielectrics for High-Performance Organic Thin Film Transistors.

A low-temperature solution-processed high-k gate dielectric layer for use in a high-performance solution-processed semiconducting polymer organic thin-film transistor (OTFT) was demonstrated. Photochemical activation of sol-gel-derived AlOx films under 150 °C permitted the formation of a dense film with low leakage and relatively high dielectric-permittivity characteristics, which are almost comparable to the results yielded by the conventionally used vacuum deposition and high temperature annealing method. Octadecylphosphonic acid (ODPA) self-assembled monolayer (SAM) treatment of the AlOx was employed in order to realize high-performance (>0.4 cm²/Vs saturation mobility) and low-operation-voltage (<5 V) diketopyrrolopyrrole (DPP)-based OTFTs on an ultra-thin polyimide film (3-µm thick). Thus, low-temperature photochemically-annealed solution-processed AlOx film with SAM layer is an attractive candidate as a dielectric-layer for use in high-performance organic TFTs operated at low voltages.

Three-dimensional gastric cancer cell culture using nanofiber scaffold for chemosensitivity test.

A three-dimensional (3D) culture of cancer cells has long been advocated as a better model of the malignant phenotype that is most closely related to tumorigenicity in vivo. To investigate the sensitivity of cancer cells to anticancer drugs, nanofiber scaffolds composed of PHBV and collagen peptide were fabricated by electrospinning. A 3D culture of cancer cells was successfully achieved by the use of nanofiber scaffolds. From the result of a chemosensitivity test, it was found that higher concentrations of anticancer drugs were required to achieve a comparable cytotoxic effect in 3D culture due to their structural architecture. These data demonstrate that the electrospun nanofiber scaffolds can provide a 3D model particularly appropriate for investigating mechanisms involved in cancer cell sensitivity to anticancer drugs.

Bioinspired molecular design of light-harvesting multiporphyrin arrays.

Recent progress in fundamental studies on multiporphyrin arrays has provided structural parameters for the molecular design of artificial light-harvesting antennae which mimic the wheel-like antenna complexes of photosynthetic purple bacteria. Covalent and noncovalent approaches have been employed for the construction of artificial light-harvesting multiporphyrin arrays. Such arrays are categorized into ring-shaped, windmill-shaped, star-shaped, and dendritic architectures. In particular, dendritic multiporphyrin arrays have been proven to be promising candidates for both providing a large absorption cross-section and enabling the vectorial transfer of energy over a long distance to a designated point. Such molecular and supramolecular systems are also expected to be potent components for molecular electronics and photonic devices.

Dendritic multiporphyrin arrays as light-harvesting antennae: effects of generation number and morphology on intramolecular energy transfer.

A series of star- and cone-shaped dendritic multiporphyrin arrays, (nPZn)4PFB and (nPZn)1PFB, respectively, that contain energy-donating dendritic zinc porphyrin (PZn) wedges of different numbers (n = 1, 3, and 7) of the PZn units, attached to an energy-accepting free-base porphyrin (PFB) core, were synthesized by a convergent growth approach. For the cone-shaped series ((nPZn)1PFB), the efficiency of energy transfer (phi ENT) from the photoexcited PZn units to the focal PFB core, as evaluated from the fluorescence lifetimes of the PZn units, considerably decreased as the generation number increased: (1PZn)1PFB (86%), (3PZn)1PFB (66%), and (7PZn)1PFB (19%). In sharp contrast, the star-shaped series ((nPZn)4PFB) all showed high phi ENT values: (1PZn)4PFB (87%), (3PZn)4PFB (80%), and (7PZn)4PFB (71%). Energy transfer efficiencies of (3PZn)4-ester-PFB, (1PZn)4-ester-PFB, and (3PZn)1-ester-PFB, whose dendritic PZn wedges are connected by an ester linkage to the PFB core, were almost comparable to those of the corresponding ether-linked versions. Fluorescence depolarization (P) studies showed much lower P values for star-shaped (7PZn)4PFB and (3PZn)4PFB than cone-shaped (7PZn)1PFB and (3PZn)1PFB, respectively, indicating a highly efficient energy migration among the PZn units in the star-shaped series. Such a morphology-assisted photochemical event is probably responsible for the excellent light-harvesting activity of large (7PZn)4PFB molecules.

A Large Dendritic Multiporphyrin Array as a Mimic of the Bacterial Light-Harvesting Antenna Complex: Molecular Design of an Efficient Energy Funnel for Visible Photons.

π-Electronic conjugation is not necessary to facilitate long-range energy migration and transfer: A rapid (kENT =1.04×109 s-1 ) and efficient (ΦEXT =71 %) energy transfer from the 28 photoexcited zinc porphyrin units to the focal free-base porphyrin unit occurs in a large, star-shaped dendritic multiporphyrin array in which the chromophore units are linked through flexible ether groups.