International Journal of Polymer Science The latest articles from Hindawi Publishing Corporation © 2015 , Hindawi Publishing Corporation . All rights reserved. Third-Order Nonlinear Optical Behavior of Novel Polythiophene Derivatives Functionalized with Disperse Red 19 Chromophore Thu, 23 Apr 2015 07:36:12 +0000 Two copolymers of 3-alkylthiophene (alkyl = hexyl, octyl) and a thiophene functionalized with disperse red 19 (TDR19) as chromophore side chain were synthesized by oxidative polymerization. The synthetic procedure was easy to perform, cost-effective, and highly versatile. The molecular structure, molecular weight distribution, film morphology, and optical and thermal properties of these polythiophene derivatives were determined by NMR, FT-IR, UV-Vis GPC, DSC-TGA, and AFM. The third-order nonlinear optical response of these materials was performed with nanosecond and femtosecond laser pulses by using the third-harmonic generation (THG) and Z-scan techniques at infrared wavelengths of 1300 and 800 nm, respectively. From these experiments it was observed that although the TRD19 incorporation into the side chain of the copolymers was lower than 5%, it was sufficient to increase their nonlinear response in solid state. For instance, the third-order nonlinear electric susceptibility () of solid thin films made of these copolymers exhibited an increment of nearly 60% when TDR19 incorporation increased from 3% to 5%. In solution, the copolymers exhibited similar two-photon absorption cross sections with a maximum value of 8545 GM and 233 GM (1 GM = 10−50 cm4 s) per repeated monomeric unit. Marilú Chávez-Castillo, Arelis Ledesma-Juárez, Marisol Güizado-Rodríguez, Jesús Castrellón-Uribe, Gabriel Ramos-Ortiz, Mario Rodríguez, José-Luis Maldonado, Jorge-Antonio Guerrero-Álvarez, and Victor Barba Copyright © 2015 Marilú Chávez-Castillo et al. All rights reserved. Aminoalkylated Merrifield Resins Reticulated by Tris-(2-chloroethyl) Phosphate for Cadmium, Copper, and Iron (II) Extraction Sun, 19 Apr 2015 17:03:25 +0000 We aimed to synthesize novel substituted polymers bearing functional groups to chelate heavy metals during depollution applications. Three polyamine functionalized Merrifield resins were prepared via ethylenediamine (EDA), diethylenetriamine (DETA), and triethylenetetramine (TETA) modifications named, respectively, MR-EDA, MR-DETA, and MR-TETA. The aminoalkylated polymers were subsequently reticulated by tris-(2-chloroethyl) phosphate (TCEP) to obtain new polymeric resins called, respectively, MR-EDA-TCEP, MR-DETA-TCEP, and MR-TETA-TCEP. The obtained resins were characterized via attenuated total reflectance Fourier transform infrared spectroscopy (ATR-FTIR), elemental analysis (EA), and thermogravimetric (TGA), thermodynamic (DTA), and differential thermogravimetric (DTG) analysis. The synthesized resins were then assayed to evaluate their efficiency to extract metallic ions such as Cd2+, Cu2+, and Fe2+ from aqueous solutions. Mokhtar Dardouri, Fayçel Ammari, and Faouzi Meganem Copyright © 2015 Mokhtar Dardouri et al. All rights reserved. Reducing Water Vapor Permeability of Poly(lactic acid) Film and Bottle through Layer-by-Layer Deposition of Green-Processed Cellulose Nanocrystals and Chitosan Wed, 08 Apr 2015 13:20:06 +0000 Layer-by-layer electrostatic self-assembly technique was applied to improve the barrier properties of poly(lactic acid) (PLA) films and bottles. The LbL process was carried out by the alternate adsorption of chitosan (CH) (polycation) and cellulose nanocrystals (CNC) produced via ultrasonic treatment. Four bilayers (on each side) of chitosan and cellulose nanocrystals caused 29 and 26% improvement in barrier properties in case of films and bottles, respectively. According to the results the LbL process with CH and CNC offered a transparent “green” barrier coating on PLA substrates. Katalin Halász, Yanin Hosakun, and Levente Csóka Copyright © 2015 Katalin Halász et al. All rights reserved. Characterization of Olfactory Ensheathing Glial Cells Cultured on Polyurethane/Polylactide Electrospun Nonwovens Tue, 31 Mar 2015 14:24:54 +0000 The aim of this research was to evaluate novel biomaterials for neural regeneration. The investigated materials were composed of polyurethane (PU) and polylactide (PLDL) blended at three different w/w ratios, that is, 5/5, 6/4, and 8/2 of PU/PLDL. Ultrathin fibrous scaffolds were prepared using electrospinning. The scaffolds were investigated for their applicability for nerve regeneration by culturing rat olfactory ensheathing glial cells. Cells were cultured on the materials for seven days, during which cellular morphology, phenotype, and metabolic activity were analysed. SEM analysis of the fabricated fibrous scaffolds showed fibers of a diameter mainly lower than 600 μm with unimportant volume of protrusions situated along the fibers, with nonsignificant differences between all analysed materials. Cells cultured on the materials showed differences in their morphology and metabolic activity, depending on the blend composition. The most proper morphology, with numerous p75+ and GFAP+ cells present, was observed in the sample 6/4, whereas the highest metabolic activity was measured in the sample 5/5. However, none of the investigated samples showed cytotoxicity or negatively influenced cellular morphology. Therefore, the novel electrospun fibrous materials may be considered for regenerative medicine applications, and especially when contacting with highly sensitive nervous cells. Jakub Grzesiak, Ryszard Fryczkowski, Anna Lis, Dariusz Szarek, Jadwiga Laska, and Krzysztof Marycz Copyright © 2015 Jakub Grzesiak et al. All rights reserved. The Synthesis of the Locating Substitution Derivatives of Chitosan by Click Reaction at the 6-Position of Chitin Mon, 30 Mar 2015 08:17:20 +0000 A novel method to prepare the macrocyclic compound locating substitution derivatives of chitosan was investigated, by using cyclodextrin as the model of macrocyclic compound. The method combines the advantages of activated 6-OH of chitin and high efficiency of click reaction. Chitin C6-OH p-toluenesulfonate (CTN-6-OTs) was generated and subsequently transferred to chitin C6-N3 via nucleophilic substitution. Afterwards, β-cyclodextrin was immobilized at 6-OH of chitin via click reaction to afford CTN-6-CD. Ultimately, CTS-6-CD was obtained by removing the acetyl group of chitin unit. The structures and properties of these products were characterized by FTIR, TG, and XRD, respectively. It was found that CTN-6-CD synthesized at the optimum conditions has an immobilized loading of  mol/g and that of the corresponding CTS-6-CD, generated by removal of the acetyl group, was  mol/g. Yu Chen, Yanchun Ye, Yanyan Jing, YuanYuan Gao, Yanwen Guo, and Huimin Tan Copyright © 2015 Yu Chen et al. All rights reserved. Preparation and Properties of Cross-Linked Starch Nanocrystals/Polylactic Acid Nanocomposites Sun, 29 Mar 2015 12:34:03 +0000 Cross-linked starch nanocrystals (CStN)/polylactic acid (PLA) nanocomposites were prepared by blending CStN and PLA, wherein CStN were homogeneously dispersed in the nanocomposites. The structure and morphology of the nanocomposites were studied through FTIR, XRD, and SEM. The results of mechanical test showed that the strength and toughness of the nanocomposites could be improved when the additive amount of hydrophobic CStN was 3% (weight ratio). Meanwhile, the microstructures of tensile fracture surface showed that CStN were uniformly dispersed in PLA matrix, and the tensile fracture surface was presented as ductile fracture. Moreover, water vapor permeability experiments illustrated that the addition of CStN reduced the water vapor permeability of PLA nanocomposites, so CStN have some resistance to water vapor. Those above indicated that CStN have functions of reinforcement and toughness in PLA matrix; therefore, they are expected to be used as functional additives in polymer matrix such as PLA, polycaprolactone (PCL), and polybutylene succinate (PBS). Zuodong Yin, Jiliang Zeng, Cai Wang, and Zelin Pan Copyright © 2015 Zuodong Yin et al. All rights reserved. Synthesis of Chitosan Oligomers/Propolis/Silver Nanoparticles Composite Systems and Study of Their Activity against Diplodia seriata Sun, 29 Mar 2015 11:39:16 +0000 The synthesis and characterization of composites of oligomeric chitosan with propolis extract which allow the incorporation of a third component (silver nanoparticles) are reported, together with their application in aqueous or hydroalcoholic solutions with a view to the formation of adhesive substances or nanofilms for the protection of vineyards against harmful xylophagous fungi. The antimicrobial properties of the association of the two biological products or those resulting from the incorporation of silver nanoparticles (NPs) are studied and discussed. The efficacy of the chitosan oligomers/propolis/silver NPs ternary system is assessed in vitro for Diplodia fungi. A preliminary study on the convenience of replacing propolis with gentisic acid is also presented. Petruta Mihaela Matei, Pablo Martín-Ramos, Mercedes Sánchez-Báscones, Salvador Hernández-Navarro, Adriana Correa-Guimaraes, Luis M. Navas-Gracia, Cassyo Araujo Rufino, M. Carmen Ramos-Sánchez, and Jesús Martín-Gil Copyright © 2015 Petruta Mihaela Matei et al. All rights reserved. Polyols Prepared from Ring-Opening Epoxidized Soybean Oil by a Castor Oil-Based Fatty Diol Sun, 29 Mar 2015 08:38:08 +0000 Several biorenewable vegetable oil-based polyols with different molecular weights and various hydroxyl functionalities were successfully prepared by ring-opening epoxidized soybean oil with a castor oil-based fatty diol. It was found that several factors, including reaction time, reaction temperature, and molar ratios between epoxidized soybean oil and castor oil diol, affect structures and rheology behaviors of the final polyols. Proton NMR, FT-IR, GPC, and rheometry results revealed that the hydroxyl functionalities, molecular weight, and viscosity of the polyols could be tailored by controlling the above-mentioned factors. Besides, the role of solvents in the epoxy ring-opening process was investigated as well. Jing Zhang, Ji Jun Tang, and Jiao Xia Zhang Copyright © 2015 Jing Zhang et al. All rights reserved. Evaluating Lignin-Rich Residues from Biochemical Ethanol Production of Wheat Straw and Olive Tree Pruning by FTIR and 2D-NMR Thu, 26 Mar 2015 12:56:24 +0000 Lignin-rich residues from the cellulose-based industry are traditionally incinerated for internal energy use. The future biorefineries that convert cellulosic biomass into biofuels will generate more lignin than necessary for internal energy use, and therefore value-added products from lignin could be produced. In this context, a good understanding of lignin is necessary prior to its valorization. The present study focused on the characterization of lignin-rich residues from biochemical ethanol production, including steam explosion, saccharification, and fermentation, of wheat straw and olive tree pruning. In addition to the composition and purity, the lignin structures (S/G ratio, interunit linkages) were investigated by spectroscopy techniques such as FTIR and 2D-NMR. Together with the high lignin content, both residues contained significant amounts of carbohydrates, mainly glucose and protein. Wheat straw lignin showed a very low S/G ratio associated with p-hydroxycinnamates (p-coumarate and ferulate), whereas a strong predominance of S over G units was observed for olive tree pruning lignin. The main interunit linkages present in both lignins were β-O- ethers followed by resinols and phenylcoumarans. These structural characteristics determine the use of these lignins in respect to their valorization. José I. Santos, Raquel Martín-Sampedro, Úrsula Fillat, José M. Oliva, María J. Negro, Mercedes Ballesteros, María E. Eugenio, and David Ibarra Copyright © 2015 José I. Santos et al. All rights reserved. Encapsulation of Phase Change Materials Using Layer-by-Layer Assembled Polyelectrolytes Wed, 25 Mar 2015 14:05:57 +0000 Phase change materials absorb the thermal energy when changing their phases (e.g., solid-to-liquid) at constant temperatures to achieve the latent heat storage. The major drawbacks such as limited thermal conductivity and leakage prevent the PCMs from wide application in desired areas. In this work, an environmentally friendly and low cost approach, layer-by-layer (LbL) assembly technique, was applied to build up ultrathin shells to encapsulate the PCMs and therefore to regulate their changes in volume when the phase change occurs. Generally, the oppositely charged strong polyelectrolytes Poly(diallyldimethylammonium chloride) (PDADMAC) and Poly(4-styrenesulfonic acid) sodium salt (PSS) were employed to fabricate multilayer shells on emulsified octadecane droplets using either bovine serum albumin (BSA) or sodium dodecyl sulfate (SDS) as surfactant. Specifically, using BSA as the surfactant, polyelectrolyte encapsulated octadecane spheres in size of ∼500 nm were obtained, with good shell integrity, high octadecane content (91.3% by mass), and good thermal stability after cycles of thermal treatments. Qiangying Yi, Gleb B. Sukhorokov, Jin Ma, Xiaobo Yang, and Zhongwei Gu Copyright © 2015 Qiangying Yi et al. All rights reserved. Elution of Monomers from Provisional Composite Materials Wed, 25 Mar 2015 12:58:52 +0000 The aim of this study was to evaluate the elution of substances from different materials used for the manufacturing of temporary indirect restorations, after storage in saliva and ethanol 75%. 10 samples of three chemically cured materials (Protemp 3 Garant, Systemp.c&b, and Trim) and one light-cured material (Clip F) were stored in saliva and ethanol 75% for 24 h, 7, and days 28 days. From the storage media at each time period, samples were prepared and analysed by LC-MS/MS, in order to access the elution of monomers. The results differed among the materials ( ≤ 0.05). No monomers were detected in the samples of Protemp 3 Garant and Clip F. Substances were detected only in ethanol samples of Systemp.c&b and Trim. The amount of BisGMA, TEGDMA, and UDMA 2 released from Systemp.c&b was higher compared to Trim. Storage time affected the release of substances ( ≤ 0.05). The highest release was observed within the first 24 h. It can be concluded that provisional resin composite materials do not show high release of monomers and this release is material dependent. However, the detection of additional peaks during the analysis, suggesting the formation of by-products of the eluted substances, may not be in favour of these materials with respect to their toxicity. Simon Daniel Schulz, Tobias Laquai, Klaus Kümmerer, Richard Bolek, Volker Mersch-Sundermann, and Olga Polydorou Copyright © 2015 Simon Daniel Schulz et al. All rights reserved. Characterization of Strong and Crystalline Polyvinyl Alcohol/Montmorillonite Films Prepared by Layer-by-Layer Deposition Method Wed, 18 Mar 2015 09:33:48 +0000 The preparation of a high-strength and highly crystalline nanocomposite with a layered structure by the use of layer-by-layer deposition (LbL) method from polyvinyl alcohol (PVOH) and montmorillonite (MMT) platelets is reported. The crystallinity and interactions between the components were studied by the use of Fourier transform infrared spectroscopy (FT-IR), wide angle X-ray diffraction (WAXD), differential scanning calorimetry (DSC), and thermogravimetric analysis (TGA). The nanocomposite film structure was investigated by the use of scanning electron microscope (SEM) and atomic force microscopy (AFM). The stiffness of the LbL PVOH/MMT film was significantly higher compared to pure PVOH and conventional PVOH/MMT nanocomposite. The structural and thermal studies on thin PVOH/MMT films indicated the enhanced crystallinity of the polymer. S. Gaidukov, I. Danilenko, and G. Gaidukova Copyright © 2015 S. Gaidukov et al. All rights reserved. Improved Mechanical Properties of Compatibilized Polypropylene/Polyamide-12 Blends Mon, 16 Mar 2015 12:09:21 +0000 Compatibilized blends of polypropylene (PP) and polyamide-12 (PA12) as a second component were obtained by direct injection molding having first added 20% maleic anhydride-modified copolymer (PP-g-MA) to the PP, which produced partially grafted PP (gPP). A nucleating effect of the PA12 took place on the cooling crystallization of the gPP, and a second crystallization peak of the gPP appeared in the PA12-rich blends, indicating changes in the crystalline morphology. There was a slight drop in the PA12 crystallinity of the compatible blends, whereas the crystallinity of the gPP increased significantly in the PA12-rich blends. The overall reduction in the dispersed phase particle size together with the clear increase in ductility when gPP was used instead of PP proved that compatibilization occurred. Young’s modulus of the blends showed synergistic behavior. This is proposed to be both due to a change in the crystalline morphology of the blends on the one hand and, on the other, in the PA12-rich blends, to the clear increase in the crystallinity of the gPP phase, which may, in turn, have been responsible for the increase in its continuity and its contribution to the modulus. Nora Aranburu and José Ignacio Eguiazábal Copyright © 2015 Nora Aranburu and José Ignacio Eguiazábal. All rights reserved. Effect of pH and Monomer Dosing Rate in the Anionic Polymerization of Ethyl Cyanoacrylate in Semicontinuous Operation Wed, 11 Mar 2015 06:40:00 +0000 Nanoparticles of poly(ethyl cyanoacrylate) with more than 10% solids content were prepared by semicontinuous heterophase polymerization at monomer-starved conditions varying the initial pH in the interval of 1–1.75 and at two monomer dosing rates. Measurements by scanning-transmission electron microscopy allowed us to identify an inverse dependence of particle size on pH. Furthermore, all the polymerizations conducted at the slower monomer dosing rate rendered two particle populations, with the larger one formed from the aggregation of a fraction of the smaller particles. It was believed that the so slow addition of the monomer caused the formation of very small but instable particles, thereby a fraction of which aggregated to reduce the total interface particles-aqueous phase, increasing the latex stability. An increase in the monomer dosing rate led to larger and more stable particles in such way that only one population of nanoparticles with around 40 nm in average diameter was obtained. Hened Saade, Suleidi Torres, Cynthia Barrera, Julieta Sánchez, Yolanda Garza, and Raúl G. López Copyright © 2015 Hened Saade et al. All rights reserved. Microphase Separation of a PS-b-PFS Block Copolymer via Solvent Annealing: Effect of Solvent, Substrate, and Exposure Time on Morphology Mon, 09 Mar 2015 06:43:35 +0000 Block copolymer (BCP) lithography makes use of the microphase separation properties of BCPs to pattern ordered nanoscale features over large areas. This work presents the microphase separation of an asymmetric polystyrene-block-poly(ferrocenyl dimethylsilane) (PS-b-PFS) BCP that allows ordered arrays of nanostructures to be formed by spin casting PS-b-PFS on substrates and subsequent solvent annealing. The effects of the solvent annealing conditions on self-assembly and structural stability are discussed. Colm T. O’Mahony, Dipu Borah, and Michael A. Morris Copyright © 2015 Colm T. O’Mahony et al. All rights reserved. Viscosity Measurements of Dilute Poly(2-ethyl-2-oxazoline) Aqueous Solutions Near Theta Temperature Analyzed within the Joint Rouse-Zimm Model Tue, 03 Mar 2015 14:12:56 +0000 The steady-state shear viscosity of low-concentrated Poly(2-ethyl-2-oxazoline) (PEOX) aqueous solutions is measured near the presumed theta temperature using the falling ball viscometry technique. The experimental data are analyzed within the model that joins the Rouse and Zimm bead-spring theories of the polymer dynamics at the theta condition, which means that the polymer coils are considered to be partially permeable to the solvent. The polymer characteristics thus depend on the draining parameter h that is related to the strength of the hydrodynamic interaction between the polymer segments. The Huggins coefficient was found to be 0.418 at the temperature 20°C, as predicted by the theory. This value corresponds to h = 2.92, contrary to the usual assumption of the infinite h. This result indicates that the theta temperature for the PEOX water solutions is 20°C rather than 25°C in the previous studies. The experimental intrinsic viscosity is well described coming from the Arrhenius equation for the shear viscosity. Jana Tóthová, Katarína Paulovičová, and Vladimír Lisý Copyright © 2015 Jana Tóthová et al. All rights reserved. Recycling of Waste Streams of the Biotechnological Poly(hydroxyalkanoate) Production by Haloferax mediterranei on Whey Tue, 03 Mar 2015 11:59:39 +0000 For manufacturing “bioplastics” such as poly(hydroxyalkanoates) (PHA), the combination of utilization of inexpensive carbon sources with the application of robust microbial production strains is considered a decisive step to make this process more cost-efficient and sustainable. PHA production based on surplus whey from dairy industry was accomplished by the extremely halophile archaeon Haloferax mediterranei. After fermentative production of PHA-rich biomass and the subsequent cell harvest and downstream processing for PHA recovery, environmentally hazardous, highly saline residues, namely spent fermentation broth and cell debris, remain as residues. These waste streams were used for recycling experiments to assess their recyclability in subsequent production processes. It was demonstrated that spent fermentation broth can be used to replace a considerable part of fresh saline fermentation medium in subsequent production processes. In addition, 29% of the expensive yeast extract, needed as nitrogen and phosphate source for efficient cultivation of the microorganism, can be replaced by cell debris from prior cultivations. The presented study provides strategies to combine the reduction of costs for biomediated PHA production with minimizing ecological risks by recycling precarious waste streams. Overall, the presented work shall contribute to the quick economic success of these promising biomaterials. Martin Koller Copyright © 2015 Martin Koller. All rights reserved. Comparative Analysis of the Effect of Organoclay, Boron Nitride, and Fluoropolymer on the Rheology and Instabilities in the Extrusion of High Density Polyethylene Sat, 28 Feb 2015 10:04:08 +0000 The effect of different processing additives on the extrusion instabilities of high density polyethylene (HDPE) was investigated. The concentration of each processing additive was fixed at 0.05 wt%. Organoclay, boron nitride, and fluoropolymer reduced transient shear and extensional viscosities of HDPE melt. Drop in extrusion pressure occurred during the extrusion experiment. The initial loss of glossiness in HDPE was restored with the addition of these additives. However, the fluoropolymer did not succeed in eliminating the stick-slip fracture. Despite the inclusion of the processing additives, gross-melt fracture in HDPE reappeared at apparent shear rate of 141 s−1. Both moment and distortion factor methods of analyses were employed and their findings support the observed visual trends of the extrudate surface. The quantifying tools indicated that combined organoclay and fluoropolymer reduced the pressure fluctuations and its performance surpassed that of the individual additives. A. A. Adesina, M. S. Nasser, and I. A. Hussein Copyright © 2015 A. A. Adesina et al. All rights reserved. Preparation and Characterization of Biocompatible Polymer Particles as Potential Nanocarriers for Inhalation Therapy Thu, 26 Feb 2015 09:27:08 +0000 Aim. Investigation of the possibility of manufacturing biocompatible polymer particles which have the required properties for pulmonary delivery via inhalation and simultaneously act as vehicles of nanotherapeutics. Methods. Nanostructures were obtained from biocompatible polysaccharides by successive oxidation and reactive coiling in the aqueous phase. The resultant nanosuspensions of PAD (polyaldehyde dextran) and DACMC (dialdehyde carbomethylcellulose) were used as precursors in spray drying production of powders at variable process conditions. The resultant dry microparticles were characterized by SEM observations, and their properties related to delivery by inhalation were determined by laser diffraction spectrometry following the dispersion in the commercial inhaler. Finally, the possibility of the reconstitution of nanosuspensions by powders rehydration was evaluated. Results. Synthesized nanoparticles had size of 120–170 nm. Microparticles after drying had size of 0.5–5 µm and different surface morphology. Aerosolized particles obtained from powder dispersion in the inhaler had the volumetric median diameter of ~2 and ~1 µm for PAD and DACMC, respectively. Hydration of powders led to restoring the nanosuspensions with the average particle size similar to the precursor. Conclusions. PAD and DACMC can be used to obtain nanostructures which, after processing, take a form suitable for effective delivery to the lungs via inhalation. Katarzyna Jabłczyńska, Magdalena Janczewska, Aleksandra Kulikowska, and Tomasz R. Sosnowski Copyright © 2015 Katarzyna Jabłczyńska et al. All rights reserved. Rapid Fabrication of Periodic Patterns on Poly(styrene-co-acrylonitrile) Surfaces Using Direct Laser Interference Patterning Thu, 26 Feb 2015 09:10:39 +0000 Periodic microstructures in styrene-acrylonitrile (SAN) copolymers are fabricated by two-beam direct laser interference patterning using a nanosecond pulsed laser operating at a wavelength of 266 nm. The SAN copolymers are synthesized using different molar ratios (styrene to acrylonitrile) by a free radical polymerization process. The chemical composition of the copolymers and their properties are determined using Fourier transformed infrared spectroscopy (FTIR) and differential scanning calorimetry (DSC). Depending on the composition of the irradiated copolymer films, with weight ratios ranging from 58 to 96.5% of styrene to acrylonitrile, different ablation behaviors are observed. The laser fluence necessary to locally ablate the copolymer is found to be dependent on the copolymer composition. Unlike other dielectric polymers, the laser irradiation produced both direct ablation of the irradiated material and collapse of the surface. It is shown that, by varying the laser fluence and the copolymer composition, the surface structure can be changed from a periodic pattern with a swelled topography to an ablated-like structure. The number of holes does not depend monotonically on the amount of PS or PAN units but shows a more complex behavior which depends on the copolymer composition and the laser fluence. Martin F. Broglia, Diego F. Acevedo, Denise Langheinrich, Heidi R. Perez-Hernandez, Cesar A. Barbero, and Andrés F. Lasagni Copyright © 2015 Martin F. Broglia et al. All rights reserved. In Situ Study of Electropolymerized Poly(3-aminobenzoic acid) Thin Film on BD-R and DVD-R Grating Substrates by Electrochemical-Transmission Surface Plasmon Resonance Spectroscopy Wed, 25 Feb 2015 11:23:23 +0000 The electropolymerization process and doping/dedoping properties of poly(3-aminobenzoic acid) (PABA) thin films on gold-coated commercial BD-R and DVD-R grating substrates were simultaneously studied by the combination of electrochemical technique and transmission surface plasmon resonance (TSPR) spectroscopy. The optical property as a function of the applied potentials and time dependence during electropolymerization were studied. The obtained TSPR wavelength scan spectra after electropolymerization showed that the maximum wavelength slightly shifted to longer wavelength indicating the increase of film thickness. In addition, the change during construction of PABA-based immunosensor for label-free detection of human immunoglobulin G can be observed. Saengrawee Sriwichai, Akira Baba, Sukon Phanichphant, Kazunari Shinbo, Keizo Kato, and Futao Kaneko Copyright © 2015 Saengrawee Sriwichai et al. All rights reserved. Preparation of Chloro Penta Amine Cobalt(III) Chloride and Study of Its Influence on the Structural and Some Optical Properties of Polyvinyl Acetate Sun, 15 Feb 2015 11:27:45 +0000 Chloro penta amine cobalt(III) cloride [Co(NH3)5Cl]Cl2 was prepared and then characterized by Fourier transform infrared spectroscopy and X-ray diffraction. The obtained results indicated the formation of orthorhombic [Co(NH3)5Cl]Cl2 nanoparticles of ≈28.75 nm size. Polymeric films based on polyvinyl acetate (PVAc) doped with chloro penta amine cobalt(III) cloride [Co(NH3)5Cl]Cl2 in different weight percent ratios were prepared using the solvent cast technique. The complexation of the additive with the polymer was confirmed by FTIR and SEM studies. The XRD pattern revealed that the amorphousicity of PVAc polymer matrix increased with raising the [Co(NH3)5Cl]Cl2 content. Parameters such as extinction coefficient, refractive index, real and imaginary parts, and optical conductivity were studied by using the absorbance and measurements from computerized UV-visible spectrophotometer in the spectral range 190–800 nm. This study showed that the optical properties of PVAc were affected by the doping of [Co(NH3)5Cl]Cl2 where the absorption increased by leveling up [Co(NH3)5Cl]Cl2 concentration. The nature of electronic transition from valence band to conduction band was determined and the energy band gaps of the composite films samples were estimated by UV-visible spectrum. It was observed that the optical conductivity increased with photon energy and with the increase of [Co(NH3)5Cl]Cl2 concentration. Nada K. Abbas, Majeed Ali Habeeb, and Alaa J. Kadham Algidsawi Copyright © 2015 Nada K. Abbas et al. All rights reserved. Nanosuspension: An Emerging Trend for Bioavailability Enhancement of Etodolac Thu, 12 Feb 2015 09:05:22 +0000 Etodolac (ET) (poorly soluble drug) nanosuspensions were prepared by both pH shift method and antisolvent techniques in order to increase its dissolution rate. Various stabilizers were used, namely, Tween 20 and 80, HPMC, PVP K44, PVA, PEG 400, NaCMC, and β-cyclodextrin. The prepared nanosuspensions were characterized by Fourier transform infrared spectroscopy (FTIR) and scanning electron microscope (SEM) and evaluated for their particle size, particle size distribution, and in vitro dissolution rate. In general, it was found that the antisolvent method for the preparation of ET nanosuspensions reduced the drug particle size to a higher extent compared to the pH shift method. The dissolution rate of ET in distilled water was markedly enhanced in the nanosized system, as more than 65% of drug dissolved in 10 min from all the nanosuspension formulations except F5 (stabilized with PVP K44) and F8 (stabilized with Tween 20), as compared to less than 20% of crude drug. Nanoparticles prepared by antisolvent method using Tween 80 as a stabilizer were selected for further in vivo study. The in vivo test demonstrated that nanoparticles of ET were well absorbed with a percentage drug absorption value 2.7 times more than that of micrometric size of crude ET. Samar A. Afifi, Maha A. Hassan, Ali S. Abdelhameed, and Kadria A. Elkhodairy Copyright © 2015 Samar A. Afifi et al. All rights reserved. Development of Cutaneous Bioadhesive Ureasil-Polyether Hybrid Films Wed, 11 Feb 2015 13:57:16 +0000 The hydrolysis and condensation reactions involved in synthesis of ureasil-polyether films influence the film formation time and the number of chemical groups able to form hydrogen bonds, responsible for the bioadhesion, with the biological substrate. The objective of this work was to study the influence of the use of an acid catalyst (hydrochloric acid) and a basic catalyst (ammonium fluoride) in the hydrolysis and condensation reactions on the time formation and bioadhesion of ureasil-polyether films. The toxicity of the films was evaluated. The MTT assay has shown cell viability of human skin keratinocytes higher than 70% of all analyzed materials suggesting low cytotoxicity. The bioadhesion of the films is strongly dependent on the viscosity and hydrophilic/hydrophobic balance of the polyether chains used to synthetize the hybrid molecules. The use of acid catalyst promotes the formation of less viscous films with higher bioadhesion. The hybrids formed by more hydrophilic PEO chains are more bioadherent, since they can interact more efficiently with the water present in the stratum corneum increasing the bioadhesion. Due to their low toxicity and high bioadhesion, the ureasil-PEO films obtained by using HCl as catalyst agent are good candidates for application to the skin as bioadhesive films. João Augusto Oshiro Junior, Flávia Chiva Carvalho, Christiane Pienna Soares, Marlus Chorilli, and Leila Aparecida Chiavacci Copyright © 2015 João Augusto Oshiro Junior et al. All rights reserved. Curing Kinetics of Hybrid Networks Composed of Benzoxazine and Multifunctional Novolac Epoxy Mon, 09 Feb 2015 08:03:13 +0000 A novel hybrid network composed of benzoxazines (BZ) and novolac epoxy resin (F-51) was prepared successfully. Thermal properties, curing kinetics, and decomposition process were studied using isothermal differential scanning calorimetry (DSC) and thermogravimetric analysis (TGA) in this paper. The reactive mechanism of F-51/BZ mixture system is different from the BZ homopolymers at low temperatures; two resin systems follow the autocatalytic model mainly at high temperatures. Thermogravimetric analysis indicates that F-51 can have no significant effect on thermal degradation temperatures and on increasing char yield. Wu Ke, Wang Rumin, and Zeng Jinfang Copyright © 2015 Wu Ke et al. All rights reserved. Stress Distribution of CF/EP Laminated Composites under Supercritical Conditions Sun, 08 Feb 2015 10:38:49 +0000 Enormous amounts of wastes have been produced due to extensive use of carbon fiber/epoxy resin (CF/EP) composites. The fact that the supercritical fluid can be used to recycle these composites efficiently has attracted widespread concerns. A three-dimensional model of CF/EP laminates considering the interfacial layers was established. The internal stress distribution of laminates was simulated based on a heat transfer model; and the change of shear stress with supercritical temperature and pressure was investigated. The results show that the shear stress concentration was located in the interfacial layers; the maximum shear stress can be expressed by a curve of convex parabola to the temperature; and the most serious damage occurred in interfacial layers when temperature approached the glass-transition temperature of resin. Haihong Huang, Zhenwen Li, Huanbo Cheng, and Yanzhen Yin Copyright © 2015 Haihong Huang et al. All rights reserved. The Preparation of Graphene Reinforced Poly(vinyl alcohol) Antibacterial Nanocomposite Thin Film Mon, 26 Jan 2015 13:51:35 +0000 Methylated melamine grafted polyvinyl benzylchloride (mm-g-PvBCl) was prepared which was used as additive in poly(vinyl alcohol) (PVA) and graphene nanosheets (GNs) were used to reinforce the mechanical strength. Using casting method, antimicrobial nanocomposite films were prepared with the polymeric biocide loading lever of 1 wt%, 5 wt%, and 10 wt%. Thermogravimetric analysis (TGA) characterization revealed the 2.0 wt% of graphene content in resultant nanocomposites films. XRD showed that the resultant GNs 2 theta was changed from 16.6 degree to 23.3 degree. Using Japanese Industry Standard test methods, the antimicrobial efficiency for the loading lever of 1 wt%, 5 wt%, and 10 wt% was 92.0%, 95.8%, and 97.1%, respectively, against gram negative bacteria E. coli and 92.3%, 99.6%, and 99.7%, respectively, against the gram positive S. aureus. These results indicate the prepared nanocomposite films are the promising materials for the food and drink package applications. Yuan-Cheng Cao, Wenjun Wei, Jiyan Liu, Qingliang You, Feiyan Liu, Qian Lan, Chang Zhang, Chang Liu, and Jinxing Zhao Copyright © 2015 Yuan-Cheng Cao et al. All rights reserved. Synthesis of Well-Defined Three-Arm Star-Branched Polystyrene through Arm-First Coupling Approach by Atom Transfer Radical Polymerization Thu, 22 Jan 2015 13:32:16 +0000 Here we describe a simple route to synthesize three-arm star-branched polystyrene. Atom transfer radical polymerization technique has been utilized to yield branched polystyrene involving Williamson coupling strategy. Initially a linear polymeric chain of predetermined molecular weight has been synthesized which is further end-functionalized into a primary alkyl bromide moiety, a prime requisition for Williamson reaction. The end-functionalized polymer is then coupled using 1,1,1-tris(4-hydroxyphenyl)ethane, a trifunctional core molecule, to give well-defined triple-arm star-branched polystyrene. Syed Shahabuddin, Fatem Hamime Ismail, Sharifah Mohamad, and Norazilawati Muhamad Sarih Copyright © 2015 Syed Shahabuddin et al. All rights reserved. Synthesis and Optical Performances of a Waterborne Polyurethane-Based Polymeric Dye Wed, 21 Jan 2015 12:43:08 +0000 A waterborne polyurethane-based polymeric dye (WPU-CFBB) was synthesized by anchoring 1, 4-bis(methylamino)anthraquinone (CFBB) to waterborne polyurethane chains. The number molecular weight, glass transition temperature, and average emulsion particle size for the polymeric dye were determined, respectively. This polymeric dye exhibited intriguing optical behaviors. The polymeric dye engendered two new absorption bands centered at about 520 nm and 760 nm if compared with CFBB in UV-vis spectra. The 760 nm peak showed hypsochromic shift with the decrease of average particle sizes. The polymeric dye dramatically demonstrated both hypsochromic and bathochromic effects with increasing temperature. The fluorescence intensity of the polymeric dye was much higher than that of CFBB. It was found that the fluorescence intensities would be enhanced from 20°C to 40°C and then decline from 40°C to 90°C. The fluorescence of the polymeric dye emulsion was very stable and was not sensitive to quenchers. Xianhai Hu, Xingyuan Zhang, and Jin Liu Copyright © 2015 Xianhai Hu et al. All rights reserved. Synthesis of New Thiophene Derivatives and Their Use as Photostabilizers for Rigid Poly(vinyl chloride) Tue, 13 Jan 2015 05:51:46 +0000 Five new thiophenes, namely, N-[(3-bromo-2-methylthiophen-5-yl)methylene]-4-methoxyaniline (4a), N-[(3-bromo-2-methylthiophen-5-yl)methylene]-3,4-dimethoxyaniline (4b), N-[(3-bromo-2-methylthiophen-5-yl)methylene]-3,4-dimethylaniline (4c), 3-[(3-bromo-2-methylthiophen-5-yl)methyleneamino]-2-methylquinazolin-4(3H)-one (4d), and 3-[(3-bromo-2-methylthiophen-5-yl)methyleneamino]-2-isopropylquinazolin-4(3H)-one (4e), have been synthesized. All of these materials brought about a reduction in the level of photodegradation of poly(vinyl chloride) (PVC) films containing the synthesized thiophenes (0.5%; by weight). The results obtained showed that the extent of photostabilization of PVC in the presence of an additive was in the order 4e > 4d > 4b > 4a > 4c. For the most favorable additive (4e), the rate of appearance of infrared absorption bands of degradation products was reduced by around two-thirds, while the quantum yield of chain scission was calculated to be reduced by a factor of more than one thousand. It is suggested that the additives may help stabilize PVC by direct absorption of UV radiation and dissipation of the energy as heat or that electrostatic attraction between the additives and PVC may assist transfer of energy from excited state PVC to the additive, from where it can be dissipated. Asim A. Balakit, Ahmed Ahmed, Gamal A. El-Hiti, Keith Smith, and Emad Yousif Copyright © 2015 Asim A. Balakit et al. All rights reserved.