Synthesis of chemically modified chitosans with a higher fatty acid glycidyl and their adsorption abilities for anionic and cationic dyes

Novel chitosan‐based materials with a higher fatty acid glycidyl as the chemically modified agent were synthesized and the adsorption ability of the resulting polymers has been evaluated for typical anionic and cationic dyes. The successful modification was confirmed by the infrared spectroscopic measurements. As the degree of substitution was decreased, the adsorption ability of the chemically modified chitosans for anionic dyes at the higher dye concentration was increased, and the modified chitosans with a lower degree of substitution showed a higher adsorption ability than that of an activated carbon at the higher dye concentration. For cationic dyes, the chemically modified chitosan showed a good adsorption power, especially when the adsorption power was evaluated by the flow methods. The improved adsorption ability of a chemically modified chitosan material was also confirmed by comparing it with that of a crosslinked chitosan material. © 2005 Wiley Periodicals, Inc. J Appl Polym Sci 96: 2423–2428, 2005     

Metastatic Voyage of Ovarian Cancer Cells in Ascites with the Assistance of Various Cellular Components

Epithelial ovarian cancer (EOC) is the most lethal gynecologic malignancy and has a unique metastatic route using ascites, known as the transcoelomic root. However, studies on ascites and contained cellular components have not yet been sufficiently clarified. In this review, we focus on the significance of accumulating ascites, contained EOC cells in the form of spheroids, and interaction with non-malignant host cells. To become resistant against anoikis, EOC cells form spheroids in ascites, where epithelial-to-mesenchymal transition stimulated by transforming growth factor-β can be a key pathway. As spheroids form, EOC cells are also gaining the ability to attach and invade the peritoneum to induce intraperitoneal metastasis, as well as resistance to conventional chemotherapy. Recently, accumulating evidence suggests that EOC spheroids in ascites are composed of not only cancer cells, but also non-malignant cells existing with higher abundance than EOC cells in ascites, including macrophages, mesothelial cells, and lymphocytes. Moreover, hetero-cellular spheroids are demonstrated to form more aggregated spheroids and have higher adhesion ability for the mesothelial layer. To improve the poor prognosis, we need to elucidate the mechanisms of spheroid formation and interactions with non-malignant cells in ascites that are a unique tumor microenvironment for EOC.     

MicroRNA-331-3p Suppresses Cervical Cancer Cell Proliferation and E6/E7 Expression by Targeting NRP2

Aberrant expression of microRNAs (miRNAs) is involved in the development and progression of various types of cancers. In this study, we investigated the role of miR-331-3p in cell proliferation and the expression of keratinocyte differentiation markers of uterine cervical cancer cells. Moreover, we evaluated whether neuropilin 2 (NRP2) are putative target molecules that regulate the human papillomavirus (HPV) related oncoproteins E6 and E7. Cell proliferation in the human cervical cancer cell lines SKG-II, HCS-2, and HeLa was assessed using the 3-(4,5-dimethylthiazol-2-yl)-5-(3-carboxymethoxyphenyl)-2-(4-sulfophenyl)-2H-tetrazolium, inner salt (MTS) assay. Cellular apoptosis was measured using the TdT-mediated dUTP nick end labeling (TUNEL) and Annexin V assays. Quantitative RT-PCR was used to measure the messenger RNA (mRNA) expression of the NRP2, E6, E7, p63, and involucrin (IVL) genes. A functional assay for cell growth was performed using cell cycle analyses. Overexpression of miR-331-3p inhibited cell proliferation, and induced G2/M phase arrest and apoptosis in SKG-II, HCS-2 and HeLa cells. The luciferase reporter assay of the NRP2 3′-untranslated region revealed the direct regulation of NRP2 by miR-331-3p. Gene expression analyses using quantitative RT-PCR in SKG-II, HCS-2, and HeLa cells overexpressing miR-331-3p or suppressing NRP2 revealed down-regulation of E6, E7, and p63 mRNA and up-regulation of IVL mRNA. Moreover, miR-331-3p overexpression was suppressed NRP2 expression in protein level. We showed that miR-331-3p and NRP2 were key effectors of cell proliferation by regulating the cell cycle, apoptosis. NRP-2 also regulates the expression of E6/E7 and keratinocyte differentiation markers. Our findings suggest that miR-331-3p has an important role in regulating cervical cancer cell proliferation, and that miR-331-3p may contribute to keratinocyte differentiation through NRP2 suppression. miR-331-3p and NRP2 may contribute to anti-cancer effects.     

Efficient electrochemical decomposition of perfluorocarboxylic acids by the use of a boron-doped diamond electrode

The electrochemical decomposition of environmentally persistent perfluorooctanoic acid (PFOA) was achieved by the use of a boron-doped diamond (BDD) electrode. The PFOA decomposition follows pseudo-first-order kinetics, with an observed rate constant (k₁) of 2.4 × 10^− 2 dm³ h^− 1. Under the present reaction conditions, k₁ increased with increasing current density and saturated at values over 0.60 mA cm^− 2. Therefore, the rate-limiting step for the electrochemical decomposition of PFOA was the direct electrochemical oxidation at lower current densities. In the proposed decomposition pathway, direct electrochemical oxidation cleaves the C-C bond between the C₇F₁₅ and COOH in PFOA and generates a C₇F₁₅ radical and CO₂. The C₇F₁₅ radical forms the thermally unstable alcohol C₇F₁₅OH, which undergoes F⁻ elimination to form C₆F₁₃COF. This acid fluoride undergoes hydrolysis to yield another F⁻ and the perfluorocarboxylic acid with one less CF₂ unit, C₆F₁₃COOH. By repeating these processes, finally, PFOA was able to be totally mineralized to CO₂ and F⁻. Moreover, whereas the BDD surface was easily fluorinated by the electrochemical reaction with the PFOA solution, medium pressure ultraviolet (MPUV) lamp irradiation in water was able to easily remove fluorine from the fluorinated BDD surface.     

Preparation of avidin-containing polyelectrolyte microcapsules and their uptake and release properties

Avidin-containing polyelectrolyte microcapsules were prepared by a layer-by-layer deposition technique and uptake and release of biotin-labelled fluorescein (b-FITC) was studied. The polyelectrolyte microcapsules were prepared by coating the surface of calcium carbonate (CaCO₃) microparticles containing avidin-poly(styrene sulfonate) (PSS) conjugate, followed by dissolution of CaCO₃ core in an ethylenediaminetetraacetic acid solution. Release of avidin from the microcapsules was markedly suppressed due to formation of a high molecular weight of avidin-PSS conjugate in the microcapsules. The uptake of b-FITC into the microcapsules was highly enhanced through a strong binding of b-FITC to avidin, as compared to the uptake into avidin-free microcapsules. Release of b-FITC from the microcapsules was accelerated upon addition of biotin, 2-iminobiotin, or lipoic acid in the solution due to the competitive binding of the additives to the binding site of avidin.     

Evaluation and fabrication of pore‐size‐tuned silica membranes with tetraethoxydimethyl disiloxane for gas separation

Organic/inorganic hybrid silica membranes were prepared from 1,1,3,3‐tetraethoxy‐1,3‐dimethyl disiloxane (TEDMDS) by the sol‐gel technique with firing at 300–550°C in N₂. TEDMDS‐derived silica membranes showed high H₂ permeance (0.3–1.1 × 10^?6 mol m^?2 s^?1 Pa^?1) with low H₂/N₂ (～10) and high H₂/SF₆ (～1200) perm‐selectivity, confirming successful tuning of micropore sizes larger than TEOS‐derived silica membranes. TEDMDS‐derived silica membranes prepared at 550°C in N₂ increased gas permeances as well as pore sizes after air exposure at 450°C. TEDMDS had an advantage in tuning pore size by the “template” and “spacer” techniques, due to the pyrolysis of methyl groups in air and Si? O? Si bonding, respectively. For pore size evaluation of microporous membranes, normalized Knudsen‐based permeance, which was proposed based on the gas translation model and verified with permeance of zeolite membranes, reveals that pore sizes of TEDMDS membranes were successfully tuned in the range of 0.6–1.0 nm. © 2011 American Institute of Chemical Engineers AIChE J, 2011     

Preparation of surfactant-free vinyl polymers by conventional emulsion polymerization using hydrolysable emulsifiers

Emulsion polymerizations of several vinyl monomers, styrene, methyl methacrylate, butyl methacrylate, butyl acrylate, and vinyl acetate, in water using alkali–hydrolysable cationic surfactants with a betaine ester group (1-alkoxycarbonylmethyl)trimethylammonium chlorides, as emulsifiers were carried out and properties of the resulting latices and the polymers recovered by hydrolysis and salting out were investigated. There were little influences of the surfactants and monomers used here on the polymerizations, forming stable and monodisperse latices with a mean diameter of ca. 70 nm and giving a high molecular weight of polymers at high yields. All polymers were precipitated and recovered by adding a small amount of sodium hydroxide into the latex solutions contained little amount of ionic species. Solvent-cast films of the polymers were found to have surfaces as hydrophobic as those for the corresponding pure polymers prepared by bulk polymerization.     

Synthesis and characterization of chitosan/poly(acrylic acid) polyelectrolyte complex

Polyelectrolyte complex based on chitosan and acrylic acid monomer by photoinitiated free‐radical polymerization in the absence of crosslinker showed a large transition in swelling in response to changes in pH of surrounding medium. Their ability to swell arises from polyelectrolyte interactions and molecular structure of the complex. The main properties of interest that related to the molecular structure, swelling volumes, glass transition temperature, and elastic modulus of the complex were investigated. The effect of water content, the only variable in the sample component, played an important role in molecular structure of the complex and as a consequence, the extent of intermolecular linkage, especially amide bonds which in turn governed the degree of swelling of the polyelectrolyte complex in this study. The decreased degree of swelling and higher temperature shift of glass transition temperature was found with increased water content, whereas increased modulus of elasticity of dry complex was found in lower water content of synthesis component. © 2002 Wiley Periodicals, Inc. J Appl Polym Sci 83: 1025–1035, 2002     

Enhanced strain hardening in elongational viscosity for HDPE/crosslinked HDPE blend. I. Characteristics of crosslinked HDPE

Blending a crosslinked high‐density polyethylene (xHDPE) enhances melt strength and strain hardening behavior in elongational viscosity of high‐density polyethylene (HDPE) to a great degree. Gel fraction of xHDPE has a stronger effect on the strain hardening than sol fraction, although sol fraction also enhances the strain hardening to some degree. Further, the xHDPE crosslinked by peroxide in a compression mold exhibits more pronounced effect than xHDPE by radiation, which is attributed to the difference in the amount of the gel fraction. The xHDPE, which enhances the strain hardening, has sparse crosslink points in the network. Moreover, it was found from linear viscoelastic measurements, such as oscillatory modulus and relaxation modulus, that the xHDPE is characterized as a critical gel, which was also supported by the result of tensile testing. © 2002 Wiley Periodicals, Inc. J Appl Polym Sci 86: 73–78, 2002     

Synthesis of AlPO4 Molecular Sieves with AFI and AEL Structures by Dry-Gel Conversion Method and Catalytic Application of Their SAPO Counterparts on Isopropylation of Biphenyl

AlPO₄-5 and AlPO₄-11 were synthesized by dry-gel conversion (DGC) method. Steam-assisted conversion (SAC) and vapor-phase transport (VPT) techniques were applied for this purpose. The synthesis was successful in presence of a certain minimum amount of external bulk water, without which the crystallization failed. Crystallization by VPT method was slower than corresponding SAC and HTS method. SAPO analogs of the samples, SAPO-5 and SAPO-11 were also synthesized by DGC method. Samples made by DGC methods had higher yield than the conventional hydrothermal synthesis (HTS); otherwise the samples showed similar characteristics as that made by HTS. XRD, SEM and N₂-adsorption results showed high crystallinity and purity of the samples made by DGC, and ²⁷Al MAS NMR spectra indicated the tetrahedral framework nature of Al. SAPO-5 and SAPO-11 were tested for their catalytic activity in isopropylation of biphenyl, and in terms of conversion and selectivity, SAPO-5 was found to be suitable for this application.