Polymers for medical and tissue engineering applications

Recent decades have seen great advancements in medical research into materials, both natural and synthetic, that facilitate the repair and regeneration of compromised tissues through the delivery and support of cells and/or biomolecules. Biocompatible polymeric materials have become the most heavily investigated materials used for such purposes. Naturally‐occurring and synthetic polymers, including their various composites and blends, have been successful in a range of medical applications, proving to be particularly suitable for tissue engineering (TE) approaches. The increasing advances in polymeric biomaterial research combined with the developments in manufacturing techniques have expanded capabilities in tissue engineering and other medical applications of these materials. This review will present an overview of the major classes of polymeric biomaterials, highlight their key properties, advantages, limitations and discuss their applications. © 2014 Society of Chemical Industry     

Emulsifier‐free cationic latexes based on vinylbenzyl chloride and 2‐(dimethylamino)ethyl methacrylate with adjusted hydrophilic–hydrophobic properties

Functional emulsifier‐free cationic latexes based on styrenic monomer vinylbenzyl chloride (VBC) and acrylic monomer 2‐(dimethylamino)ethyl methacrylate (DMA) were successfully prepared with dual quaternary ammonium ions (36–63 mol %) on both monomer moieties in two‐stages. First, [2‐(methacryloyloxy)ethyl]dimethylhexadecylammonium bromide monomer (DMA(C₁₆)), prepared via quaternization of DMA with 1‐bromohexadecane, was utilized as a comonomer (5–20%) as well as a surfactant in the emulsion polymerization of VBC. Next, the quaternization of chloromethyl groups in the VBC moiety in latex particles with trimethylamine and N,N‐dimethylhexadecylamine created a second type of quaternized sites on the latex particles. The percentages of the quaternary ammonium ions of the first‐stage latexes (P[VBC‐DMA(C₁₆‐x)]) and the second‐stage latexes (P[VBC(R)‐DMA(C₁₆‐x)]) were determined using bromide and chloride ion‐selective electrodes. The particles were characterized with a scanning electron microscope, Zetasizer, measuring water contact angles of their pellets. The polymer structure and the alkyl group length in their quaternary ammonium ions played an important role on the sizes, zeta potentials and hydrophilic–hydrophobic balances of the latexes. The water contact angles of the pellets of the latex particles varied from 50.3 to 109.6° depending on both the polymer structure and the alkyl group length. © 2015 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2015 , 132, 42775.     

Revised stratigraphy of the Tertiary deposits of Istanbul and their engineering properties

For over 50 years, the Upper Oligocene–Upper Miocene sedimentary sequence in Istanbul has been considered to be formed of two distinct sequences separated by an unconformity. However, recent field observations and an analysis of numerous borehole data indicate the Gürp?nar, Çukurçe?me and Güngören Formations are in fact a single sequence of alternating clay–sand/sandstone beds/lenses, here named the Avc?lar Formation. The Bak?rköy Formation, which is typically composed of carbonate rocks, conformably overlies the Avc?lar Formation. The paper provides the geotechnical parameters of the units within the Avc?lar Formation which it is hoped will facilitate selecting suitable geotechnical and engineering geological parameters to represent the deposits and minimize errors in the interpretation/evaluation of in-situ conditions.     

Long-term microleakage trends in access cavities conditioned with phosphoric acid and deproteinizing agent for root-canal-treated teeth: an investigation of fluid filtration and microscopy analysis

This study evaluated the long-term microleakage of access cavities conditioned with phosphoric acid and deproteinizing agents for root-canal-treated teeth using fluid filtration and microscopical analysis. Occlusal surfaces of extracted human mandibular premolars (N = 90) were removed leaving a 4 mm coronal length from the cemento-enamel junction. After root canal treatment, the specimens were randomly divided into four experimental groups (n = 21) and the remaining teeth were used for positive control group (n = 6): SB: 35% H₃PO₄ + Adper Single Bond 2; SSB: 35% H₃PO₄ + 5.25% NaOCl + 10% Sodium ascorbate (C₆H₇NaO₆) + Adper Single Bond 2; XP: 35% H₃PO₄₊XP Bond; SXP: 35% H₃PO₄₊5.25% NaOCl + 10% Sodium ascorbate + XP Bond. All cavities were restored with a resin composite (Filtek Z250). After removing the root filling from the apical side, teeth were subjected to fluid filtration test for 1 week, 6 and 12 months followed by ×2500 thermocycling after 1st week and 6th months each. Data were analyzed using one-way ANOVA and Dunnet T3 tests (α = 0.05). SEM analyses were carried out after each microleakage evaluation in two random teeth from all groups. Microleakage values in groups SB and XP presented no significant difference in any of the evaluated period (p > 0.05). Microleakage results of SXP (0.01665) group showed significant difference compared to XP (0.03377) and SB (0.03049) groups after 12 months. SSB group (0.00901) showed significantly less microleakage among all other groups (0.01665–0.03377) (p < 0.05). Prior to endodontic treatment, in access cavities, acid etching with 35% H₃PO₄ followed by the application of NaOCl and sodium ascorbate completely destroyed the collagen layer, reducing the microleakage and resin–dentin interface degradation up to 12 months.     

Capacitor Applications of Nanocomposite Films for Poly(3,4-ethylenedioxythiophene-co-pyrrole)/Multi-Walled Carbon Nanotubes and Poly(3,4-ethylenedioxythiophene-co-pyrrole)/Copper Oxide

Polypyrrole/multi-walled carbon nanotube, poly(3,4-ethylenedioxythiophene)/multi-walled carbon nanotube and their nanocomposites P(EDOT-co-Py)/multi-walled carbon nanotube and P(EDOT-co-Py)/copper (II) oxide, (CuO) in the initial feed ratio of [EDOT]₀/[Py]₀ = 1/5 were electrosynthesized on glassy carbon electrode by cyclic voltammetric method. Their characterizations were performed by cyclic voltammetric, Fourier transform infrared-attenuated total reflectance, scanning electron microscopy, energy dispersion X-ray analysis, and electrochemical impedance spectroscopy. To the best of authors’ knowledge, the first report on polypyrrole/multi-walled carbon nanotube, PEDOT/multi-walled carbon nanotube, P(EDOT-co-Py)/multi-walled carbon nanotube and P(EDOT-co-Py)/CuO nanocomposite films were comparatively examined in 0.1 M NaClO₄/CH₃CN and in 0.1 M sodium dodecyl sulfate solutions. The highest specific capacitance for PEDOT/multi-walled carbon nanotube and polypyrrole/multi-walled carbon nanotube composite films were obtained as C_sp = 306 mF × cm^?2 for 3% multi-walled carbon nanotube and C_sp = 804 mF × cm^?2 for 1% multi-walled carbon nanotube, respectively. The highest specific capacitances were obtained as C_sp = 27.40 mF × cm^?2 and C_sp = 26.90 mF × cm^?2 for P(EDOT-co-Py)/multi-walled carbon nanotube includes the wt percent of 1% multi-walled carbon nanotube and P(EDOT-co-Py)/CuO includes the wt percent of 3% CuO, respectively. The C_sp of P(EDOT-co-Py)/CNT composite films were calculated as 9.43 and 11.49 mF × cm^?2 for 3 and 5% multi-walled carbon nanotube, respectively. In addition, The EIS results were simulated with the equivalent circuit model of R_s(C_dl1(R₁(QR₂)))(C_dl2R₃).     

Raman Spectroscopic Barcode Use for Differentiation of Vegetable Oils and Determination of Their Major Fatty Acid Composition

In this study, differentiation of vegetable oils and determination of their major fatty acid (FA) composition were performed using Raman spectral barcoding approach. Samples from seven different sources (sunflower, corn, olive, canola, mustard, soybean and palm) were analyzed using Raman spectroscopy. Second derivative of the spectral data was utilized to generate unique barcodes of oils. Chemometric analyses, namely, principal component analysis (PCA) and partial least square (PLS) methods were used for data analysis. PCA was applied for classification of the samples according to the differences in their levels arising from their barcode data. A successful differentiation based on second derivative barcodes of Raman spectra (2D‐BRS) of vegetable oils was obtained. In addition, PLS method was applied on 2D‐BRS in order to determine the major FA composition of these samples. Coefficient of determination values for palmitic, stearic, oleic, linoleic, α‐linolenic, cis‐11 eicosenoic, erucic and nervonic acids were in the range of 0.970–0.989. Limit of detection and limit of quantification values were found to be satisfactory (0.09–8.09 and 0.30–26.95 % in oil) for these fatty acids . Advantages of both chemometric analysis and spectral barcoding approach have been utilized in the present study. Taking the second derivative of the Raman spectra has minimized background variability and sensitivity to intensity fluctuations. Spectral conversion to the barcodes has further increased the quality of information obtained from Raman spectra and also made it possible to improve the visualization of the data. Converting Raman spectra of oils into barcodes enables simpler presentation of the valuable information, and still allows further analysis such as classification of vegetable oils and prediction of their major fatty acids with high accuracy.     

Synthesis,characterization and,swelling behavior of semi‐IPN nanocomposite hydrogels of alginate with poly(N‐isopropylacrylamide) crosslinked by nanoclay

pH and temperature responsive nanocomposite hydrogels were synthesized with sodium alginate (NaAlg), N‐isopropylacrylamide (NIPA), and nanoclay. The structure, morphology, thermal behavior, and swelling and deswelling behaviors of the hydrogels were studied. The NaAlgm/PNIPA/Clayn hydrogels revealed a highly porous structure in which the pore sizes decreased and the amount of pores increased with increasing the nanoclay content in the hydrogels. PNIPA retained its own characteristics regardless of the amount of NaAlg and nanoclay. The effect of pH and nanoclay content on the swelling and effect of temperature on the deswelling behavior were investigated. The equilibrium swelling ratios of the nanocomposite hydrogels increased with increasing the pH from 2 to 6. The maximum swelling was attained at pH 6. Deswelling increased with increasing the nanoclay content in the hydrogels. The hydrogels were found to be pH and temperature responsive. © 2015 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2016 , 133, 43222.     

Novel colloidal nanofiber electrolytes from PVA‐organoclay/poly(MA‐alt‐MVE), and their NaOH and Ag‐carrying polymer complexes

Novel multifunctional polymer nanofiber electrolytes with covalence crosslinked structures from various solution blends of reactive intercalated poly(vinyl alcohol)/octadecylamine montmorillonite (as a matrix polymer), poly(maleic anhydride‐alt‐methyl vinyl ether) (as a partner polymer) and their NaOH‐absorbing and Ag‐carrying polymer complexes were fabricated via electrospinning. Chemical, physical, morphological, and electrical properties of nanofiber structures were investigated by FTIR, XRD, SEM, and electrical analysis methods. Ag precursors in fiber composites significantly improved phase separation processing, fiber morphologies, diameter distributions, and electrical properties of the fibers. In situ generation of Ag nanoparticles and their distribution on nanofiber surfaces during fiber formation occurred via complex formation between silver cations and electronegative functional groups from both matrix and partner polymers as stabilizing/reducing agents. Electrical resistance and conductivity strongly depended on matrix/partner polymer ratios and absorption time of NaOH solution on nanofibers. Addition of NaOH changed the electrical properties of fiber structures from almost dielectric state to excellent conductivity form. The fabricated unique nanofiber electrolytes are promising candidates for applications in power and fuel cell nanotechnology, electrochemical, and bioengineering processes as reactive semiconductive platforms. POLYM. ENG. SCI., 56:204–213, 2016. © 2015 Society of Plastics Engineers     

Immobilization Horseradish Peroxidase onto UiO-66-NH2 for Biodegradation of Organic Dyes

Enzymes are extensively used as catalyst in several fields of production such as chemistry, and pharmaceuticals owing to their selectivity, efficiency and environmentally friendliness. However, their applications are often hindered due to their insufficient stability and difficulties in re-use. As a member of porous crystalline materials, metal organic frameworks are a promising enzyme carrier due to their multi-functional pore surfaces and robustness in variety of harsh conditions. In this study, the horseradish peroxidase (HRP) enzyme was immobilized onto UiO-66-NH₂ (Universitetet i Oslo) by a facile incubation method at the room temperature to improve the stability and reusability of enzyme. The prepared HRP@UiO-66-NH₂ bio-composite was characterized by using FT-IR, XRD and SEM. The crystal structure of MOF was well-preserved after enzyme immobilization. A colorimetric assay for enzyme activity after released from UiO-66-NH₂ has been employed based on the catalytic oxidation of phenol coupled with 4-aminoantipyrine. The robustness and activity of immobilized enzyme after released from UiO-66-NH₂ were investigated by biodegradation of methyl orange (MO) and methylene blue (MB) with several parameters such as pH, temperature, the dosage of H₂O₂ and the dye concentration with comparison to its free form. The optimum condition for dye degradation was obtained at basic conditions. The immobilized enzyme maintained its activity at elevated temperature while free enzyme lost its activity at the same conditions, attributed to the armoring effect of UiO-66-NH₂. According to the results of studied various parameters, MO and MB were biodegraded to 60% and 45%, respectively, within 60 min with the optimum conditions at pH 9 and 50 °C at a H₂O₂ dosage of 3%. The superior pH tolerance and stability suggest potential of UiO-66-NH₂ immobilized peroxidase enzyme in industrial applications.

     

Effect of gas permeation temperature and annealing procedure on the performance of binary and ternary mixed matrix membranes of polyethersulfone,SAPO‐34, and 2‐hydroxy 5‐methyl aniline

This study investigated the effect of annealing time and temperature on gas separation performance of mixed matrix membranes (MMMs) prepared from polyethersulfone (PES), SAPO‐34, and 2‐hydroxy 5‐methyl aniline (HMA). A postannealing period at 120°C for a week extensively increased the reproducibility and stability of MMMs, but for pure PES membranes no post‐annealing was necessary for stable and reproducible performance. The effect of operation temperature was also investigated. The permeabilities of H₂, CO₂, and CH₄ increased with increasing permeation temperature from 35°C to 120°C, yet CO₂/CH₄ and H₂/CH₄ selectivities decreased. PES/SAPO‐34/HMA ternary and PES/SAPO‐34 binary MMMs exhibited the highest ideal selectivity and permeability values at all temperatures, respectively. For H₂/CO₂ pair, when temperature increased from 35°C to 120°C, selectivity increased from 3.2 to 4.6 and H₂ permeability increased from 8 to 26.5 Barrer for ternary MMM, demonstrating the advantage of using this membrane at high temperatures. The activation energies were in the order of CH₄ > H₂ > CO₂ for all membranes. PES/SAPO‐34/HMA membrane had activation energies higher than that of PES/SAPO‐34 membrane, suggesting that HMA acts as a compatibilizer between the two phases. © 2014 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2014 , 131, 40679.