Potentiometric studies of oxidation–reduction reactions with redox copolymers

Polymeric oxidants in the bead form that were macroporous styrene/divinylbenzene copolymers containing N‐chlorosulfonamide functional groups (in sodium or hydrogen form) or N‐bromosulfonamide groups (in sodium form) were synthesized and investigated to determine their oxidizing powers. The redox potentials of the N‐chlorosulfonamide/sulfonamide and N‐bromosulfonamide/sulfonamide systems were determined by potentiometric studies at different pH values with aqueous solutions of Na₂SO₃, KCN, and KSCN as reducers. The formal redox potentials of the N‐chlorosulfonamide copolymers were 0.79, 0.44, and ?0.12 V at pH's of 1.8, 8.45, and 13.6, respectively. The formal redox potential of the N‐bromosulfonamide copolymer was about 100 mV higher in comparable conditions and in solutions over pH = 5 (e.g., 0.56 V at pH = 8.56). The comparatively higher oxidizing power of the N‐bromosulfonamide copolymer was particularly evident in a strong alkaline medium (in which the N‐chlorosulfonamide copolymer was not reactive). In contrast, the N‐chlorosulfonamide copolymer showed strong oxidative properties in acidic media (in which the N‐bromosulfonamide copolymer decomposed itself). © 2007 Wiley Periodicals, Inc. J Appl Polym Sci 2008     

Nondegradative microextrusion of resorbable polyesters for pharmaceutical and biomedical applications: The cases of poly‐lactic‐acid and poly‐caprolactone

In recent years biodegradable polymers, particularly polyesters such as the poly(lactic acid) (PLA) and polycaprolactone (PCL), have gained high interests for their applicability in the biomedical and pharmaceutical fields where they're used for manufacturing various different resorbable devices, from tissue engineering scaffolds to controlled drug release systems. Despite many positive characteristics, processability of these materials still remains a critical issue as they easily tend to degrade during manufacturing. In this article we aimed to assess microextrusion as a nondegradative process for manufacturing PLA and PCL. The results we experimentally obtained, that are hereby presented, set a new point in the on‐going debate on degradation during processing of resorbable polymers as they allow to affirm that microextrusion leaves unmodified molecular weight distributions without producing any evident reductions in mean molecular weight. Microextrusion thus represents a risk‐free high molecular weight polymer processing solution for obtaining nondegraded products within pharmaceutical and biomedical production lines, such as for scaffolds for tissue engineering applications or drug delivery. © 2008 Wiley Periodicals, Inc. J Appl Polym Sci, 2008     

Preparation and adsorption behavior of a cellulose‐based,mixed‐mode adsorbent with a benzylamine ligand for expanded bed applications

A novel mixed‐mode expanded bed adsorbent with anion‐exchange properties was explored with benzylamine as the functional ligand. The cellulose composite matrix, densified with stainless steel powder, was prepared with the method of water‐in‐oil suspension thermal regeneration. High activation levels of the cellulose matrix were obtained with allyl bromide because of the relative inertness of the allyl group under the conditions of the activation reaction. After the formation of the bromohydrin with N‐bromosuccinimide and coupling with benzylamine, the activated matrix was derived to function as a mixed‐mode adsorbent containing both hydrophobic and ionic groups. The protein adsorption capacity was investigated with bovine serum albumin as a model protein. The results indicated that the prepared adsorbent could bind bovine serum albumin with a high adsorption capacity, and it showed salt tolerance. Effective desorption was achieved by a pH adjustment across the isoelectric point of the protein. The interactions between the cell and adsorbent were studied, and the bioadhesion was shielded by the adjustment of the salt concentration above 0.1M. Stable fluidization in the expanded bed was obtained even in a 2% (dry weight) yeast suspension. The direct capture of target proteins from a biomass‐containing feedstock without extra dilution steps could be expected with the mixed‐mode adsorbent prepared in this work, and this would be especially appropriate for expanded bed adsorption applications. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci, 2008     

Semiflexible random thermotropic copolymers from 8‐(3‐hydroxy phenyl) octanoic acid and 3‐chloro‐4‐hydroxy benzoic acid/3,5‐dibromo‐4‐hydroxy benzoic acid

Two series of semiflexible random thermotropic copolymers containing 8‐(3‐hydroxy phenyl) octanoic acid (HPOA) with either 3‐chloro‐4‐hydroxy benzoic acid or 3,5‐dibromo‐4‐hydroxy benzoic acid were prepared by melt polycondensation techniques. The copolyesters were characterized with Fourier transform infrared spectroscopy, dilute solution viscometry, hot‐stage polarized light microscopy, differential scanning calorimetry, thermogravimetric analysis, and wide‐angle X‐ray diffraction. Studies revealed that the amount of HPOA as a disruptor incorporated into the backbone of substituted 4‐hydroxy benzoic acids had a detrimental effect on the liquid‐crystalline behavior. Mesophase‐transition temperatures were observed between 210 and 250°C, and the optical textures were of typical nematic phases. The degree of crystallinity decreased with an increase in the HPOA content. The thermal stability of the copolymers was in the range of 310–370°C. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci 2008     

Synthesis,characterization, and redox and electrochromic behaviors of poly(3-n-octyloxythiophene)

Poly(3-n-octyloxythiophene), a conjugated polymer, which possessed solubility in common organic solvents, was synthesized by electrochemical polymerization in the presence of lithium perchlorate as the supporting electrolyte and sodium dodecyl sulfate as the surfactant in an aqueous medium. Characterizations of the intermediate, monomer, and polymer were performed by NMR spectroscopy, Fourier transform infrared spectroscopy, ultraviolet–visible spectroscopy, and gel permeation chromatography. The process of electrochemical polymerization and the electrochemical redox behaviors were investigated by cyclic voltammetry and the potentiostatic method. A poly(3-n-octyloxythiophene) film that was deposited on a platinum electrode was found to exhibit electrochromic behaviors, and it switched electrochemically between blue–green oxidized and dark red reduced states. © 2008 Wiley Periodicals, Inc. J Appl Polym Sci, 2008     

Mixtures of tertiary amine functionalized azo-containing mesogens with acid-functionalized polymers

A tertiary amine functionalized 4-nitro-4′-alkoxy azobenzene mesogen with a 10 or 12 carbon spacer (azo-nN) was synthesized and complexed in equimolar proportions with poly(acrylic acid) (PA-H) and poly(sulfonic acid) (PSS-H), and investigated by thermogravimetric analysis, differential scanning calorimetry, polarizing optical microscopy, Fourier transform infrared spectroscopy and X-ray diffraction. The neat azo-nN is characterized by a partial bilayer S_A mesophase at higher temperatures, and a highly ordered phase, in which the molecules are stacked orthogonally in bilayers, at lower temperatures. As supported by infrared analysis, for the azo-nN/PA-H mixture, the complexation is partial while for the same azo-nN/PSS-H mixture, complete proton transfer occurs. When the azo-nN is blended with the PA-H, regarded as a weak acid, a biphasic system is generated and the thermotropic behavior of neat mesogen is not significantly affected. In contrast, by mixing the same mesogen with a PSS-H (regarded as a strong acid), the thermotropic behavior is significantly influenced: the complexation generated a partial or interdigitated smectic A or tilted smectic C lamellar phase.     

Surface adsorption of comb polymers by Monte Carlo simulations

This paper reports off-lattice Monte Carlo simulations of highly-branched comb homopolymers weakly adsorbed on a flat, featureless surface showing only covolume and dispersion interactions with the adsorbate. A minimal coarse-grained model, described by hard spheres connected by harmonic springs, was employed. The interaction energy of the adsorbed combs and linear chains is first discussed as a function of the molecular mass and of the number of beads in contact with the surface. The molecular size is then investigated as a function of backbone length and branching density at a fixed arm size. The apparent swelling exponents of the adsorbed combs are larger than those of the corresponding linear chains, and much larger than that of the free molecules. This result indicates a surface-induced stiffening of the comb backbone, further studied through the persistence length l_pers. It is found that l_pers increases upon adsorption over the free-molecule value, more so the larger is the branching density. Finally, the thickness of the adsorbed layer, the surface-induced molecular anisotropy and the molecular aspect ratio are investigated as a function of branching density and molecular mass.     

Comparative Study of Models on Confinement of Concrete Cylinders with Fiber-Reinforced Polymer Composites

The use of fiber-reinforced polymer (FRP) composites for strengthening and/or rehabilitation of concrete structures is gaining increasing popularity in the civil engineering community. One of the most attractive applications of FRP materials is their use as confining devices for concrete columns, which may result in remarkable increases of strength and ductility as indicated by numerous published experimental results. Despite a large research effort, a proper analytical tool to predict the behavior of FRP-confined concrete has not yet been established. Most of the available models are empirical in nature and have been calibrated against their own sets of experimental data. On the other hand, the experimental results available in the literature encompass a wide range of values of the significant variables. The objective of this work is a systematic assessment of the performance of the existing models on confinement of concrete columns with FRP materials. The study is conducted in the following steps: the experimental data on confinement of concrete cylinders with FRP available in the technical literature are classified according to the values of the significant variables; the existing empirical and analytical models are reviewed, pointing out their distinct features; the whole set of available experimental results is compared with the whole set of analytical models; and strengths and weaknesses of the various models are analyzed. Finally, a new equation is proposed to evaluate the axial strain at peak stress of FRP-confined concrete cylinders.     

Bile acids as constituents for dental composites: in vitro cytotoxicity of (meth)acrylate and other ester derivatives of bile acids.

Methacrylic derivatives of bile acids have been synthesized for use as monomers in dental composites. Polymeric dental materials are known to leach cytotoxic unreacted monomers and degradation products. In this study, the in vitro cytotoxicity of bile acids and their derivatives towards 3T3 fibroblasts has been evaluated by colorimetric MTT assay and compared with that of the common dental monomers BisGMA, UDMA and TEGDMA. In general, the bile acids and their derivatives induced mitochondrial dysfunction at similar or higher concentrations than the commercial dental monomers. Certain monomers did not influence MTT response over their entire range of solubility.     

Flexural and Shear Rigidity of Composite Sheet Piles

The flexural and shear rigidity of pultruded composite sheet pile panels consisting of E-glass fiber-reinforced polyester are studied in this paper. The analysis consists of an experimental investigation and an analytical modeling to determine the resistance of the sheet pile panels to the deflections for design of composite sheet pile walls. Timoshenko’s beam theory was used to experimentally determine the flexural rigidity (EI) and shear rigidity (kAG) of the panel. Three- and four-point bending tests were performed on six different span lengths and the results were self-compared from the two independent tests. Analytical expressions for the flexural and shear rigidities were derived to allow the prediction based on the layered structure of pultruded shapes. The values computed from the analytical expressions were examined with the experimental results.