Structural control in radical polymerization with 1,1 diphenylethylene: 2. Behavior of MMA-DPE copolymer in radical polymerization

Copolymers of 1,1-diphenylethylene (DPE) behave in a very special way in radical polymerization. Particularly, the behavior of MMA-DPE copolymers in radical polymerization is investigated. The results reveal that the semiquinoid structure of the precursor polymer identified in a previous contribution is activated by the attack of free radicals and thus, in a second stage polymerization with a second monomer, block copolymers are formed. The block copolymer yield depends strongly on the ratio between the amount of DPE-containing precursor polymer and the initiator and monomer concentration used in the second stage. The mechanism proposed is able to explain at least qualitatively all experimental results including the restriction of this mode of control of radical polymerization to the formation of diblock copolymers only.     

Valorization of waste thermoset material as a filler in thermoplastic: Mechanical properties of phenolic molding compound waste‐filled PP composites

As most thermoset material, phenolic molding compound (PMC) wastes are an environmental problem. Very few recycling solutions have been proposed so far for this type of material. A mechanical recycling method to valorize these materials is proposed in this work. It relies on the use of phenolic waste as filler in thermoplastic. Such phenolic filler can increase mechanical properties (tensile, flexural) of the matrix, and be used in substitution of traditional particulate fillers such as calcium carbonate or talc. In this study, several morphological parameters influencing the final mechanical properties of a PMC‐filled polypropylene (PP) micro‐composite are studied, such as filler loading rate, particles size distribution of the filler, and interfacial adhesion between the filler and the matrix. Some structural parameters are also studied and linked with mechanical properties, such as dispersion of the filler and crystallinity of the matrix. Finally, the properties of PMC‐filled PP are compared with CaCO₃‐ and talc‐filled PP. © 2017 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2018 , 135, 45849.     

Miscibility of poly (etherimide) and poly (butylene naphthalate) blends

Summary Differential scanning calorimeter (DSC), optical microscopy (OM) and scanning electron microscopy (SEM) were performed to characterize the miscibility of a blend system comprising poly (butylene naphthalate) (PBN) and poly (ether imide) (PEI). DSC scans showed there was only one single Tg for each blend and the glass transitions increase monotonously with the increase of PEI content. The glass transition temperatures of the blends fitted the Fox equation well implying that the blends exhibited fine segmental scale of mixing. No lower critical solution temperature (LCST) was observed by OM for the blends. SEM micrographs showed the fracture surface of quenched sample exhibited a homogeneous structure. No obvious IR peak shift of C=O absorption at 1780 cm⁻¹ was observed suggesting a relatively low level of specific interaction between two molecules. It was concluded that these blends were miscible with non-specific intermolecular interactions. Received: 5 January 2001/Accepted: 27 February 2001     

Water–alcohol separation by pervaporation through zeolite‐modified poly(amidesulfonamide)

Pervaporation membranes were fabricated by blending different amount of zeolite NaA or NaX with three types of poly(amidesulfonamide) (PASA). The zeolite‐filled membranes were characterized by IR spectroscopy, SEM, sorption measurements, and wide‐angle X‐ray diffraction. By adding the proper amount of NaA into the polymer casting solutions, the resultant zeolite‐filled membranes exhibited improvement in both selectivity and permeability in the separation of 10% aqueous solutions of ethanol and propan‐1‐ol, as compared with the zeolite free membrane. © 2001 John Wiley & Sons, Inc. J Appl Polym Sci 82: 1323–1329, 2001     

Preparation and characterization of methoxy‐poly(ethylene glycol) side chain grafted onto chitosan as a wound dressing film

Chitosan has received extensive attention as a biomedical material; however, the poor solubility of chitosan is the major limiting factor in its utilization. In this study, chitosan‐based biomaterials with improved aqueous solubility were synthesized. Two molecular weights (750 Da and 2000 Da) of methoxypoly(ethylene glycol) (mPEG) were grafted onto chitosan (mPEG‐g‐chitosan) to form a ～100‐μm‐thick plastic film as a wound dressing. The chemical structures of the mPEG‐g‐chitosan copolymers were confirmed using Fourier transform infrared spectroscopy (FTIR), and the thermal properties were characterized using thermogravimetry analysis (TGA). Their microstructures were observed using scanning electron microscopy (SEM). The other properties were analyzed via the swelling ratio, tensile strength, elongation, and water vapor transmission rate (WVTR). Biocompatibility evaluations through biodegradability, cytotoxicity, and antimicrobial effect studies were also performed. The obtained mPEG‐g‐chitosan copolymers were soluble in slightly acidic aqueous solutions (pH～6.5) at a concentration of 10 wt %. The optimal mPEG‐g‐chitosan hydrogels had swelling ratios greater than 100% and WVTRs greater than 2000 g/m²/day. Their performance against Staphylococcus aureus will be subjected to further improvements with respect to medical applications. © 2015 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2015 , 132, 42340.     

Comparative In Vitro Osteoinductivity Study of HA and α‐TCP/HA Bicalcium Phosphate

A bicalcium phosphate (BCP) bioceramic comprising α‐tricalcium phosphate (α‐TCP) and hydroxyapatite (HA) was prepared by a two‐step sintering. The microstructure of the BCP bioceramic was investigated using scanning electron microscopy (SEM), transmission electron microscopy (TEM), and X‐ray diffraction. The in vitro osteoinductivity was evaluated by culturing MG63 osteoblast‐like cells on the BCP bioceramic. Results showed that the BCP bioceramic comprising α‐TCP and HA in a moderate ratio possessed a hardness of 93.7 Hv. The cells spread faster on the BCP bioceramic than those on the commercial HA. It suggested that the BCP bioceramic can enhance osteoinductivity in vivo.     

Sinterability of Forsterite Prepared via Solid‐State Reaction

In this work, the sinterability of forsterite powder synthesized via solid‐state reaction was investigated. X‐ray diffraction (XRD) analyses indicate that the synthesized powder possessed peaks that correspond to stoichiometric forsterite. Scanning electron micrographs revealed that the powders were formed agglomerates, which were made up of loosely packed fine particles. Subsequently, the forsterite powders were cold isostatically pressed into a disk shape under 200 MPa and sintered in air at temperature ranging from 1200°C to 1500°C (interval of 50°C) with ramp rate of 10°C/min and dwelling time of 2 h. The sinterability of each sintered samples was examined in terms of phase stability, relative density, Vickers hardness, fracture toughness, and microstructural examination. XRD examination on all the sintered samples exhibited pure forsterite, in which the generated peaks were found to be in a good agreement with JCPDS card no. 34‐0189. The densification of forsterite progressed to reach a maximum relative density of ~91% at 1500°C. This study also revealed that high‐strength forsterite ceramic can be synthesized via solid‐state reaction as forsterite attained favorable mechanical properties, having fracture toughness of 4.88 MPam^1/2 and hardness of 7.11 GPa at 1400°C.     

Characterizations of TiO2/SiO2/Ni–Cu–Zn Ferrite Composite for Magnetic Photocatalysts

The TiO₂/SiO₂/Ni–Cu–Zn ferrite composite for magnetic photocatalysts with high photocatalytic activity is successfully prepared in this study. The composite are composed of spherical or elliptical Ni–Cu–Zn ferrite nanoparticles about 20–60 nm as magnetic cores, silica as barrier layers with thickness of 15 nm between the magnetic cores and titania shells with thickness approximately 1.5 nm. Photodegradation examination of TiO₂/SiO₂/ Ni–Cu–Zn ferrite composite was carried out in methylene blue (MB) solutions illuminated under a Xe arc lamp with 35 W and color temperature of 6000 K. The results indicated that about 47.1% of MB molecules adsorbed on the TiO₂/SiO₂/Ni–Cu–Zn ferrite composite within 30 min mixing due to it higher pore volume of 0.034 cm³/g, and after 6 h Xe lamp irradiation, 83.9% of MB 16.1% was photodegraded. Compared with the TiO₂ /Ni–Cu–Zn ferrite composite, the TiO₂/SiO₂/Ni–Cu–Zn ferrite composite with silica barrier layer prohibited the photodissolution and enhanced the photocatalytic ability. The magnetic photocatalyst shows high photocatalytic efficiency that the apparent first‐order rate constant k_obs is 0.18427 h^?1, and good magnetic property that the saturation magnetization (M_s) of is 37.45 emu/g, suggesting the magnetic photocatalyst can be easily recovered by the application of an external magnetic field.     

Development of Potent Adenosine Monophosphate Activated Protein Kinase (AMPK) Activators

Previously, we reported the identification of a thiazolidinedione‐based adenosine monophosphate activated protein kinase (AMPK) activator, compound 1 (N‐[4‐({3‐[(1‐methylcyclohexyl)methyl]‐2,4‐dioxothiazolidin‐5‐ylidene}methyl)phenyl]‐4‐nitro‐3‐(trifluoromethyl)benzenesulfonamide), which provided a proof of concept to delineate the intricate role of AMPK in regulating oncogenic signaling pathways associated with cell proliferation and epithelial–mesenchymal transition (EMT) in cancer cells. In this study, we used 1 as a scaffold to conduct lead optimization, which generated a series of derivatives. Analysis of the antiproliferative and AMPK‐activating activities of individual derivatives revealed a distinct structure–activity relationship and identified 59 (N‐(3‐nitrophenyl)‐N′‐{4‐[(3‐{[3,5‐bis(trifluoromethyl)phenyl]methyl}‐2,4‐dioxothiazolidin‐5‐ylidene)methyl]phenyl}urea) as the optimal agent. Relative to 1 , compound 59 exhibits multifold higher potency in upregulating AMPK phosphorylation in various cell lines irrespective of their liver kinase B1 (LKB1) functional status, accompanied by parallel changes in the phosphorylation/expression levels of p70S6K, Akt, Foxo3a, and EMT‐associated markers. Consistent with its predicted activity against tumors with activated Akt status, orally administered 59 was efficacious in suppressing the growth of phosphatase and tensin homologue (PTEN)‐null PC‐3 xenograft tumors in nude mice. Together, these findings suggest that 59 has clinical value in therapeutic strategies for PTEN‐negative cancer and warrants continued investigation in this regard.