Bio-Degradable Polyesters with Rigid Cyclic Diester from Camphor and Tartaric Acid.

Despite their excellent, useful, and stable properties, thermoplastics are constantly subject to environmental risks because of their low degradability under thermal, chemical, and mechanical stresses. To overcome the aforementioned issues, we hereby introduce an eco-friendly camphor (Ct) cyclic diester. The Ct diester is designed as a monomer, including a ketal group from the Ct, and shows high thermal stability via a rigid spiro-ring and a bridged bicyclic structure. A series of polyester was synthesized using the Ct diester, including various types of diols and dimethyl terephthalate. PETxCty copolyesters showed appropriate thermal stability up to 414 °C and a high glass transition temperature. This thermal behavior led to amorphous regions as the Ct diester content increased. Regarding the proportion of the Ct diester in the polyester, it was sensitive to hydrolysis and contributed to the degradation of the polyester in acid buffer conditions.

Hard Coating Materials Based on Photo-Reactive Silsesquioxane for Flexible Application: Improvement of Flexible and Hardness Properties by High Molecular Weight.

EPOSS of polyhedral oligomeric silsesquioxanes (POSS) mixture structure and LPSQ of ladder-like polysilsesquioxane (LPSQ) structure were synthesized via sol-gel reaction. EPSQ had a high molecular weight due to polycondensation by potassium carbonate. The EPSQ film showed uniform surface morphology due to regular double-stranded structure. In contrast, the EPOSS-coated film showed nonuniform surface morphology due to strong aggregation. Due to the aggregation, the EPOSS film had shorter d-spacing (d1) than the EPSQ film in XRD analysis. In pencil hardness and nanoindentation analysis, EPSQ film showed higher hardness than the EPOSS film due to regular double-stranded structure. In addition, in the in-folding (r = 0.5 mm) and out-folding (r = 5 mm) tests, the EPSQ film did not crack unlike the EPOSS coated film.

Change of Characterization and Film Morphology Based on Acrylic Pressure Sensitive Adhesives by Hydrophilic Derivative Ratio.

Hydrophilic acrylic pressure-sensitive adhesives (PSAs) were synthesized by controlling the contents of 2-ethylhexyl acrylate (EHA), isobornyl acrylate (IBOA), and 2-hydroxyethyl acrylate (HEA); especially, the characteristic change of the HEA content was analyzed. Surface contact angle of acrylic PSA film decreased from 77.87° to 70.23° in the case of Acryl-2 to Acryl-8 (below HEA 10 wt %). However, the surface contact angle of Acryl-10 to Acryl-40 (HEA 10 wt % to 40 wt %) increased up to 92.29°, indicating hydrophobicity. All acrylic PSA films showed high adhesive force above 1800 gf/25 mm. According to X-ray diffraction (XRD) measurement, hydrophilic acrylic PSAs exhibited amorphous property and it was confirmed that the morphology of acrylic PSA film was significantly affected by the flexibility of the polymer chain and the strength of hydrogen bonding. The affinity with hydrophilic materials for acrylic PSA films was evaluated by T-type peel test, confirming that the affinity with hydrophilic materials is determined by the hydrophilicity of the acrylic PSA film. The synthesized acrylic PSA film is non-toxic regardless of the hydrophilicity.

Redox-responsive FRET-based polymer dot with BODIPY for fluorescence imaging-guided chemotherapy of tumor.

Redox-responsive polymer dot (PD) were synthesized from disulfide cross-linked polymers in a carbonized process to allow quenching effects by loading of boron-dipyrromethene (BODIPY) onto the matrix. The disulfide linkage facilitated degradation of the PD system by intracellular glutathione (GSH), leading to fluorescence recovery by BODIPY and intracellular drug release. The paclitaxel release profile showed that approximately 100% of the drug escaped from the matrix in response to 10 mM GSH, whereas less than 10% was released in the absence of GSH. In vitro studies showed that quenching produced by BODIPY loading enabled visual monitoring of cancer cell death, as the quenching disappeared when BODIPY was released by GSH inside of cancer cells. The PD contain disulfide bonds representing a GSH-triggered ligand; thus, nanocarriers presented enhanced in vivo chemotherapeutic inhibition in xenograft tumor-bearing mice localized at the cancer location, guided by fluorescent off-on system tracking and measured by the release of BODIPY. This platform reacts to the redox level in sensitive manner and cancer cell death can be monitored by fluorescence, making this platform useful for bio-applications, particularly in vitro and in vivo therapy and diagnosis, while considering the cell physiological environment. This system may be useful for wider medical applications.

Target-specific induced hyaluronic acid decorated silica fluorescent nanoparticles@polyaniline for bio-imaging guided near-infrared photothermal therapy.

We describe a novel synthesis method for silica nanoparticles, which involves a combination of these nanoparticles with targetable and nontargetable fluorescent dopamine-conjugated hyaluronic acid (HA-DA) via rational chemical dehydration. The resulting HA-decorated silica fluorescent nanoparticles, electrostatically linked to polyaniline (PANI) to form ionic complexes, possessed high fluorescence intensity and were monodisperse in solution, near-infrared light responsive, and amenable to specific labeling of cancer cell lines. When exposed to near-infrared irradiation, the fluorescent silica nanoparticles exerted photothermal cytotoxicity guided by bioimaging and distinguished malignant cancer cells from normal cells via receptor CD44. Different heating properties of nanoparticles depend on local interactions between different structures, and determination of their efficacy could lead to new thermal treatment options such as noninvasive photothermal therapy.

Functionalized biocompatible WO3 nanoparticles for triggered and targeted in vitro and in vivo photothermal therapy.

We report on dopamine-conjugated hyaluronic acid (HA-D), a mussel-inspired facile capping material that can modify tungsten oxide (WO3) nanoparticles to be both biocompatible and targetable, allowing precise delivery (WO3-HA) to a tumor site. Near-infrared (NIR) irradiated WO3-HA showed a rapid and substantial rise in photothermal heat to complete in vitro thermolysis of malignant MDAMB and A549 cancer cellsbut was found to be relatively less sensitive to normal MDCK cells. A long-term in vivo investigation of ~10 nm HA thickness on WO3 (WO3-HA) nanoparticles demonstrated efficient photo-thermal conversion with time-dependent tumor target accumulation. This long-termin vivo survival study ofWO3-HA showed promising biocompatibility, with a complete recovery from malignant tumor. Due to the importance of keeping simplicity in the design of therapeutic nanoparticles, we therefore expect that this facile scheme (HA-D) would contribute to the biocompatible development of versatile metallic nanoparticles for photothermal applications.

Facile fabrication of high-efficiency near-infrared absorption film with tungsten bronze nanoparticle dense layer.

An excellent transparent film with effective absorption property in near-infrared (NIR) region based on cesium-doped tungsten oxide nanoparticles was fabricated using a facile double layer coating method via the theoretical considerations. The optical performance was evaluated; the double layer-coated film exhibited 10% transmittance at 1,000 nm in the NIR region and over 80% transmittance at 550 nm in the visible region. To optimize the selectivity, the optical spectrum of this film was correlated with a theoretical model by combining the contributions of the Mie-Gans absorption-based localized surface plasmon resonance and reflections by the interfaces of the heterogeneous layers and the nanoparticles in the film. Through comparison of the composite and double layer coating method, the difference of the nanoscale distances between nanoparticles in each layer was significantly revealed. It is worth noting that the nanodistance between the nanoparticles decreased in the double layer film, which enhanced the optical properties of the film, yielding a haze value of 1% or less without any additional process. These results are very attractive for the nanocomposite coating process, which would lead to industrial fields of NIR shielding and thermo-medical applications. PACS: 78.67.Sc; 78.67.Bf; 81.15.-z.

Spiropyran-conjugated pluronic as a dual responsive colorimetric detector.

Novel spiropyran-conjugated Pluronic [polyethylene oxide (PEO)-b-polypropylene oxide (PPO)-b-polyethylene oxide (PEO)] micelles are developed as a new colorimetric detector showing photo- or thermo-switchable behavior. Facile conjugation of spiropyran to Pluronic was confirmed by (1)H NMR, UV-Vis, and Fluorescence spectroscopy. A switchable photoluminescence is found depending on the irradiation with either UV or visible light, and temperature resulting from structural isomerization of spiropyran between spiropyran (SP) and merocyanine (MC) form. Cytotoxicity of the spiropyran-conjugated Pluronic (SP-PL) was evaluated following an MTT assay, whereas photo responsiveness of spiropyran within the micelles was determined by confocal laser scanning microscopy.

Monodisperse polystyrene-silica core-shell particles and silica hollow spheres prepared by the Stöber method.

Monodisperse polystyrene (PS) bead particles (diameter approximately 750 nm) have been synthesized with an initiator, 2,2'-azobis(2-methylpropionamidine) dihydrochloride (AIBA), using a surfactant-free emulsion polymerization. The PS particles charged positively by the cationic initiator exhibit uniform size with a narrow size distribution. The Stöber method was adopted to coat silica on the surface of the PS particles. The silica coatings were performed on different conditions; pH (10.0-12.5), tetraethylorthosilicate (TEOS) concentration (10-40 mM), and reaction time (1-5 h). The reaction rates are too low at low pH (10.0) so that no or little silica is coated on the PS bead particles. At high pH condition (approximately 12.5) relatively rough silica shell and heterogeneous nucleation of silica colloids were observed due to high reaction rate of TEOS hydrolysis and condensation reaction. Smooth surface with uniform thickness of silica shells were obtained at a pH value around 11. Also, the thickness of silica coated on the PS spheres increases with increase of TEOS concentration and reaction time. Silica hollow spheres were also obtained by calcination of the PS-silica core-shell particles.

A study on the synthesis of polystyrene-silica nanocomposite particles by soap-free emulsion polymerization using cationic initiator in company with colloidal silica sol solution.

Nano-sized polystyrene (PS)-silica nanocomposite particles have been prepared by soap-free emulsion polymerization using a cationic initiator, 2,2'-azobis(isobutyramidine) hydrochloride (AIBA) with a colloidal silica (Ludox SM30, 7 nm diameter). The cationic initiator leads to the formation of the PS-silica nanocomposite particles by electrostatic interaction with negatively charged silica particles. Morphology, particle size distribution, reactivity and silica content of the particles were monitored on different reaction conditions such as pH, the addition time of silica sol and the amount of the silica sol. It is found that the nucleation of styrene monomer depends on the pH of water medium, the addition time of silica, the presence of silica in polymerization system. The reaction whose styrene monomer didn't react in water medium with pH 10 was progressed in the presence of silica sol to give nanocomposite particles. In the condition of constant pH 10 in the polymerization system, the increase of the amount of silica gave little influence to the changes in the particle size and particle size distribution of nanocomposite particles. The changes in the pH of medium gave much influence on the particle size and particle size distribution due to the changes in ionic interaction of silica and initiator. The silica content absorbed on the nanocomposite particles decreases with decreasing the pH values in the polymerization media.

Tracheary element differentiation is correlated with inhibition of cell expansion in xylogenic mesophyll suspension cultures.

To test the hypothesis that xylogenesis is coupled to cell growth suppression, cell expansion in Zinnia elegans L. var. Envy mesophyll suspension cultures was manipulated by varying the extracellular osmolarity and the effect on xylogenesis was examined. Cell expansion and tracheary element differentiation were inversely related along a gradient of extracellular osmolarity ranging from 200 to 400 mOsm, supporting the hypothesis that tracheary element differentiation is coupled to cessation of cell expansion. Above 300 mOsm, reduction in the number of cells that differentiated into tracheary elements coincided with an increase in the number of plasmolyzed cells as extracellular osmolarity was increased, indicating that plasmolysis inhibits tracheary element differentiation, although not specifically. Using the plasmolysis method we showed that cellular osmolarity within populations of isolated Zinnia mesophyll cells ranges from 250 to 600 mOsm with a mean of 425 mOsm. The broad range in cellular osmolarity within Zinnia mesophyll cell populations, coupled with inhibition of differentiation in the low range due to cell expansion and in the high range due to plasmolysis, may help explain why tracheary element differentiation in Zinnia suspension cultures is never complete nor perfectly synchronous and enable further optimization of this culture system.