Gas sorption and permeation of poly(γ-methyl glutamate)

Sorption, permeation, and diffusion behaviors of poly(γ-methyl glutamate) were examined in the light of superstructure including conformation. Highly crystalline PMG, chloesteric twisted structure, low crystalline PMG, which are all composed of α helix, and β form PMG were prepared using cast solvent of chloroform, dichloromethane–dimethylformamide, and dimethylformamide and treating by formic acid, respectively. The large amount sorbed and the sorption capacity were interpreted by an existence of a microvoid in PMG cast film from chloroform. On the other hand, β form PMG had small amount sorbed. The sorption behavior was remarkably influenced by superstructure as well as conformation, while the effect of only conformation on the permeation behavior was recognized. A peculiar permeation was detected around 100°C for all the samples.     

Surface characteristics of poly(γ‐alkyl α l‐glutamate)s with different alkyl groups

A series of poly(γ‐alkyl α L ‐glutamate)s with different alkyl groups were synthesized by the ring opening polymerization of corresponding α‐amino acid N‐carboxyanhydrides. The characteristics of these polyglutamate surfaces were evaluated by attenuated total reflectance Fourier transform infrared spectroscopy spectra, water contact angle, water absorption, protein adsorption, and platelet adhesion measurements. Changing the length of the alkyl side chain provides a unique opportunity to study the influence of carbon number in the alkyl group on the surface properties of the polyglutamates. Water contact angle and water absorption data show that the hydrophilicity of these polyglutamate surfaces decreases with the increasing of methylene in the alkyl group. Protein adsorption on these polyglutamate surfaces increases with the enhancing of surface hydrophobicity. However, the changes in platelets adhesion could be attributed to the hydrophilicity/hydrophobicity of the polyglutamates and the specific effect of alkyl group. © 2010 Wiley Periodicals, Inc. J Appl Polym Sci, 2011     

Electrospinning of poly(γ‐benzyl–α,L‐glutamate) microfibers for piezoelectric polymer applications

One of the latest developments in the field of piezoelectric polymers is the use of poly(γ‐benzyl‐α,L‐glutamate) (PBLG), a poly(amino acid) that can be poled along its α‐helical axis and fabricated into thermally stable piezoelectric microfibers via electrospinning. This study demonstrates a method for improving the piezoelectricity of electrospun PBLG microfibers by controlling the orientation of fibers using a method based on a concentrated electric field. The piezoelectricity is verified via customized quasi‐static and dynamic measurement methods, while the correlation between fiber alignment and the piezoelectric constant, d₃₃, in the longitudinal mode of the electrospun PBLG fibers is investigated. When the level of alignment was varied from 50% to 90%, the piezoelectric constant increased linearly, showing a maximum d₃₃ of 27 pC N^?1 and a maximum force sensitivity of 65 mV N^?1 at peak alignment. A fabricated flexible prototype based on electrospun PBLG fibers provides a new solution for the use of PBLG fibers in wearable energy harvesters or composites based on piezoelectric polymer fibers. © 2018 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2018 , 135, 46440.     

Dielectric properties of poly(α-methyl α-n-propyl-β-propiolactone)/poly(vinyl chloride) blends

The dielectric properties of miscible blends of poly(vinyl chloride) (PVC) and poly(α-methyl-α-n-propy-β-propiolae-tone) (PMPPL) have been investigated at different temperatures above and below T_g. The results were analyzed using the Cole-Cole representation and lead to the conclusion that this mixture does not exhibit micro-scale heterogeneities. Dielectric constant and dielectric loss master curves were constructed using the stress relaxation shift factors determined previously; the same shift factors could be used for the homopolymers and their blends. Similarities between the dielectric master curves and the stress relaxation master curves of PVC, PMPPL, and their blends, are also discussed.     

Thermoplastic hydrogel based on pentablock copolymer consisting of poly(γ‐benzyl L‐glutamate) and poloxamer

A thermoplastic hydrogel based on a pentablock copolymer composed of poly(γ‐benzyl L ‐glutamate) (PBLG) and poloxamer was synthesized by polymerization of BLG N‐carboxyanhydride, which was initiated by diamine‐terminated groups located at the ends of poly(ethylene oxide) (PEO) chains of the poloxamer, to attain a new pH‐ and temperature‐sensitive hydrogel for drug delivery systems. Circular dichroism measurements in solution and IR measurements in the solid state revealed that the polypeptide block existed in the α‐helical conformation, as in the PBLG homopolymer. The intensity of the wide‐angle X‐ray diffraction patterns of the polymers depended on the poloxamer content in the copolymer and showed basically similar reflections to the PBLG homopolymer. The melting temperature (T_m) of the poloxamer in the copolymer was reduced with an increase of the PBLG block in comparison with the T_m of the poloxamer, which is indicative of a thermoplastic property. The water contents of the copolymers were dependent on the poloxamer content in the copolymers, for example, those for the GPG‐2 (48.7 mol % poloxamer) and GPG‐1 (57.5 mol % poloxamer) copolymers were 31 and 41 wt %, respectively, indicating characteristics of a polymeric hydrogel. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 88: 2649–2656, 2003     

Interface formation of Ca with poly(p-phenylene α,α′-diphenyl vinylene) and poly(p-phenylene α-phenyl vinylene)

We have investigated the interface formation of Ca with poly(p-phenylene α,α′-diphenyl vinylene) (PPV-DP) and poly(p-phenylene α-phenyl vinylene) (PPV-P) using X-ray photoemission spectroscopy (XPS). Similarly to our earlier findings in metal/PPV interface formation, the O 1s peak shifted toward a lower binding energy as soon as Ca was deposited on to the polymers. This was accompanied by the formation of Ca? O, suggesting a chemical origin for the O 1s shift. By contrast, the C 1s peak shift toward a lower binding energy was observed relatively later, after about 4 Å of Ca deposition. At the same time, a new C 1s component became noticable at about ?1.5 eV relative to the initial C 1s peak. This component signifies the possibility of polymer disruption by the Ca atoms to form Ca? C species. The C 1s peak shift is attributed to Ca induced surface band bending and barrier formation as in the case of metal/PPV interface formation. The disruption of the polymer may also induce changes in the interface electronic states and contribute to the C 1s peak shift. From the intensity attenuation analysis, we conclude that the initial 15 Å of Ca overlayer is contaminated by the Ca? O and Ca? C species and the overlayer is pure beyond 15 Å of Ca coverage.     

Crystallization of poly(ε-caprolactone)

The isothermal crystallization behaviour of poly(ε-caprolactone), PCL, has been investigated by dilatometry and optical microscopy. Nucleation rates and spherulitic growth rates have been measured. At all temperatures tested a change in nucleation rate was observed early during the crystallization. Growth rates were linear over the whole of the crystallization range. The experimental results were analysed using the Avrami equation in which the experimentally observed time dependence of nucleation is used. The equation contains integer values of the Avrami exponent and describes adequately the crystallization behaviour of PCL. The difference between the apparent and true nucleation rates is emphasized, and difficulties in the calculation of rate constants are discussed.     

Synthesis of poly(β‐pinene)‐g‐polystyrene from allylic brominated poly(β‐pinene)

Poly(β‐pinene) was brominated by N‐bromosuccinimide on the allylic carbons. Then the brominated product was activated by AlEt₂Cl to initiate the polymerization of styrene to give a β‐pinene/styrene graft copolymer. AlEt₂Cl was selected because it alone could not initiate the polymerization of styrene. The obtained graft copolymer was characterized by GPC, ¹H‐NMR, and DSC measurements, respectively. © 2000 John Wiley & Sons, Inc. J Appl Polym Sci 75: 599–603, 2000     

Crystallization,melting behavior,and wettability of poly(ε‐caprolactone) and poly(ε‐caprolactone)/ poly(N‐vinylpyrrolidone) blends

Both wettability and crystallizability control poly(ε‐caprolactone)'s (PCL) further applications as biomaterial. The wettability is an important property that is governed by both chemical composition and surface structure. In this study, we prepared the PCL/poly(N‐vinylpyrrolidone) (PVP) blends via successive in situ polymerization steps aiming for improving the wettability and decreasing crystallizability of PCL. The isothermal crystallization of PCL/PVP at different PVP concentrations was carried out. The equilibrium melting point (T), crystallization rate, and the melting behavior after isothermal crystallization were investigated using differential scanning calorimetry (DSC). The Avrami equation was used to fit the isothermal crystallization. The DSC results showed that PVP had restraining effect on the crystallizability of PCL, and the crystallization rate of PCL decreased clearly with the increase of PVP content in the blends. The X‐ray diffraction analysis (WAXD) results agreed with that. Water absorptivity and contact angle tests showed that the hydrophilic properties were improved with the increasing content of PVP in blends. The coefficient for the water diffusion into PCL/PVP blends showed to be non‐Fickian in character. © 2009 Wiley Periodicals, Inc. J Appl Polym Sci, 2010     

γ→β Phase transformation induced in poly(vinylidene fluoride) by stretching

The purpose of this work was to show in a conclusive way the γ→β phase transformation induced by uniaxial stretching in poly(vinylidene fluoride). Poly(vinylidene fluoride) films were melted and crystallized at 163°C for 36 h. Under these conditions, a mixture of α and γ phases was formed, with a predominance of the latter. These films were uniaxially stretched at 130°C at a draw ratio of 4. Fourier transform infrared and differential scanning calorimetry analyses showed a γ→β phase transition in the solid state, whereas orientation of the α phase without any transition was observed. Optical microscopy analysis permitted the observation of the transformation of spherulitic structures into oriented lamellae during stretching. © 2008 Wiley Periodicals, Inc. J Appl Polym Sci, 2008     

Blends of poly(3‐hydroxybutyrate) with poly(β‐alanine) and its derivatives

Nanofibers and films of poly(3‐hydroxybutyrate) (PHB)/nylon 3 [poly(β‐alanine) (N3)], PHB/poly(α‐methyl‐β‐alanine) (2mN3), and PHB/poly(β‐methyl‐β‐alanine) (3mN3) blends were prepared by electrospinning and film‐casting techniques, respectively. The miscibility of the blends was studied by Fourier transform infrared spectrometry, differential scanning calorimetry, thermogravimetric analysis, and X‐ray diffraction (XRD). The electrospinnability of the blends was studied by scanning electron microscopy. Some characteristic IR absorption bands of the components in the blends shifted gradually with changes in the compositions. The melting temperature and decomposition temperature of PHB decreased gradually with increasing fractions of N3, 2mN3, and 3mN3. The XRD spectra of all of the blends exhibited peaks with lower intensities compared to those of the neat species. The suppression of PHB crystallinity in the blends after blending was attributed to the disruption of its crystal lattice and the prevention of recrystallization of each component by means of other components and segmental interactions between the components in the amorphous phase. Thermal, spectroscopic, and optical analyses of the polymer blends revealed that the polymers were miscible with good compatibility, and this could have improved the scaffold properties of PHB. © 2014 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2014 , 131, 40484.     

Influence of γ‐irradiation on poly(methyl methacrylate)

Poly(methyl methacrylate) (PMMA) was γ‐irradiated (5–20 kGy) by a ¹³⁷Cs source at room temperature in air. The changes in the molecular structure attributed to γ‐irradiation were studied by mechanical testing (flexure and hardness), size‐exclusion chromatography, differential scanning calorimetry, thermal gravimetric analysis, and both Fourier transform infrared and solution ¹³C‐NMR spectroscopy. Scanning electron microscopy was used to investigate the influence of the dose of γ rays on the fracture behavior of PMMA. The experimental results confirm that the PMMA degradation process involves chain scission. It was also observed that PMMA presents a brittle fracture mechanism and modifications in the color, becoming yellowish. The mechanical property curves show a similar pattern when the γ‐radiation dose increases. © 2002 Wiley Periodicals, Inc. J Appl Polym Sci 85: 886–895, 2002     

A rheo-optical study on the reformation of structure in racemic poly(γ-benzyl glutamate) liquid crystals

Transmitted light intensities were measured by means of the polarized light technique for the nematic liquid crystal phase of racemic poly(γ-benzyl glutamate) (PBG) in m-cresol at 25°C after cessation of steady flow at shear rates ranging from 0.2 to 110 s^?1. Weight-average molecular weights of PBG used were 1.5, 2.1, and 2.6 × 10⁵, while the concentrations varied between 20, 30, and 40 wt percent. Transmitted light intensities with crossed and parallel polarizers, I_x and I_|, show wavy changes with time after cessation of steady flow, indicating the retardation decreases with time. An attempt was made to explain experimental results on the basis of a simple model, in which not only relaxation of molecular orientation but also effects of the wall and disclination were taken into account.     

Preparation and characterization of electrospun poly(ε‐caprolactone)–pluronic–poly(ε‐caprolactone)‐based polyurethane nanofibers

In this study, amphiphilic poly(ε‐caprolactone)–pluronic–poly(ε‐caprolactone) (PCL–pluronic–PCL, PCFC) copolymers were synthesized by ring‐opening copolymerization and then reacted with isophorone diisocyanate to form polyurethane (PU) copolymers. The molecular weight of the PU copolymers was measured by gel permeation chromatography, and the chemical structure was analyzed by ¹H‐nuclear magnetic resonance and Fourier transform infrared spectra. Then, the PU copolymers were processed into fibrous scaffolds by the electrospinning technology. The morphology, surface wettability, mechanical strength, and cytotoxicity of the obtained PU fibrous mats were investigated by scanning electron microscopy, water contact angle analysis, tensile test, and MTT analysis. The results show that the molecular weights of PCFC and PU copolymers significantly affected the physicochemical properties of electrospun PU nanofibers. Moreover, their good in vitro biocompatibility showed that the as‐prepared PU nanofibers have great potential for applications in tissue engineering. © 2016 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2016 , 133, 43643.     

Photosensitivities and rates of photocrosslinking of poly(vinyl α-cyanocinnamate) and poly(vinyl α-cyanocinnamoxy acetate)

The photosensitivities and the rates of photocrosslinking of poly(vinyl α-cyanocinamate) and poly(vinyl α-cyanocinnamoxyacetate) were investigated. The photocrosslinkings of these polymers proceeded mainly through radical addition, and these polymers showed higher photosensitivities than poly(vinyl cinnamate) and poly(vinyl cinnamoxyacetate), in spite of lower rates of photocrosslinking of the former polymers.     

Miscibility of block copolymers of poly(ε‐caprolactone) and poly(ethylene glycol) with poly(3‐hydroxybutyrate) as well as the compatibilizing effect of these copolymers in blends of poly(ε‐caprolactone) and poly(3‐hydroxybutyrate)

Atactic poly(3‐hydroxybutyrate) (a‐PHB) and block copolymers of poly(ethylene glycol) (PEG) with poly(ε‐caprolactone) (PCL‐b‐PEG) were synthesized through anionic polymerization and coordination polymerization, respectively. As demonstrated by differential scanning calorimetry (DSC) and dynamic mechanical thermal analysis (DMTA) measurements, both chemosynthesized a‐PHB and biosynthesized isotactic PHB (i‐PHB) are miscible with the PEG segment phase of PCL‐b‐PEGs. However, there is no evidence showing miscibility between both PHBs and the PCL segment phase of the copolymer even though PCL has been block‐copolymerized with PEG. Based on these results, PCL‐b‐PEG was added, as a compatibilizer, to both the PCL/a‐PHB blends and the PCL i‐PHB blends. The blend films were obtained through the evaporation of chloroform solutions of mixed components. Excitingly, the improvement in mechanical properties of PCL/PHB blends was achieved as anticipated initially upon the addition of PCL‐b‐PEG. © 2001 John Wiley & Sons, Inc. J Appl Polym Sci 80: 2600–2608, 2001     

Crystallization behavior of poly(lactide)/poly(β‐hydroxybutyrate)/talc composites

The morphology and miscibility of commercial poly(lactide) (PLA)/poly(β‐hydroxybutyrate) (PHB, from 5 to 20 wt %) blends prepared by melt extrusion method, were investigated using differential scanning calorimetry (DSC) and Fourier transform infrared spectroscopy (FTIR) observations. The results show that for all the studied blend contents, PLA/PHB blends are immiscible. The effects of PHB and talc on the nonisothermal cold crystallization kinetics of PLA were examined using a differential scanning calorimetry (DSC) at different heating rates. PHB acted as a nucleating agent on PLA and the addition of talc to the blend yielded further improvement, since significant increase in the enthalpy peak was observed for samples containing 10 wt % PHB and talc (from 0.5 to 5 phr). The crystallization kinetics were then examined using the Avrami–Jeziorny and Liu–Mo approach. The simultaneous presence of PHB and talc induced a decrease of the crystallization half time. The evolution of activation energies determined with Kissinger's equation suggests that blending with PHB and incorporating talc promote nonisothermal cold crystallization of PLA. The synergistic nucleating effect of PHB and talc was also observed on isothermal crystallization of PLA from the melt. © 2013 Wiley Periodicals, Inc. J. Appl. Polym. Sci., 2013     

Dynamic light-scattering studies of poly(γ-benzyl α, l-glutamate)–benzyl alcohol system

We report the concentration and temperature dependencies of the diffusion coefficients obtained from dynamic light-scattering studies for the poly(γ-benzyl α, l-glutamate)-benzyl alcohol (PBLG–BA) system. These studies were made at dilute and semidilute polymer concentrations, mainly in the isotropic phase. The measured translational and rotational diffusion coefficients in dilute solutions are consistent with predictions based on wormlike chain models. The mutual diffusion coefficient in semidilute solutions shows a marked deviation from scaling predictions, demonstrating the strong coupling between the translational and rotational motions. The measured time evolution of the scattered intensity after the PBLG–BA system is suddenly quenched into the gel phase demonstrates that aggregation is a significant mechanism in the formation of the gel phase.     

Biodegradable studies of poly(trimethylenecarbonate‐ε‐caprolactone)‐block‐poly(p‐dioxanone), poly(dioxanone), and poly(glycolide‐ε‐caprolactone) (Monocryl®) monofilaments

The aim of the study was to investigate the mechanical properties and biodegradability of poly(trimethylenecarbonate‐ε‐caprolactone)‐block‐poly(p‐dioxanone) [P(TMC‐ε‐CL)‐block‐PDO] in comparison with poly(p‐dioxanone) and poly(glycolide‐ε‐caprolactone) (Monocryl®) monofilaments in vivo and in vitro. P(TMC‐ε‐CL)‐block‐PDO copolymer and poly(p‐dioxanone) were prepared by using ring‐opening polymerization reaction. The monofilament fibers were obtained using conventional melt spun methods. The physicochemical and mechanical properties, such as viscosity, molecular weight, crystallinity, and knot security, were studied. Tensile strength, breaking strength retention, and surface morphology of P(TMC‐ε‐CL)‐block‐PDO, poly(p‐dioxanone), and Monocryl monofilament fibers were studied by immersion in phosphate‐buffered distilled water (pH 7.2) at 37°C and in vivo. The implantation studies of absorbable suture strands were performed in gluteal muscle of rats. The polymers, P(TMC‐ε‐CL)‐block‐PDO, poly(p‐dioxanone), and Monocryl, were semicrystalline and showed 27, 32, and 34% crystallinity, respectively. Those mechanical properties of P(TMC‐ε‐CL)‐block‐PDO were comparatively lower than other polymers. The biodegradability of poly(dioxanone) homopolymer is much slower compared with that of two copolymers. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 102: 737–743, 2006     

Miscibility,thermal behaviour,morphology and mechanical properties of binary blends of poly[(R)‐3‐hydroxybutyrate] with poly(γ‐benzyl‐L‐glutamate)+

The miscibility, thermal behaviour, morphology and mechanical properties of poly[(R)‐3‐hydroxybutyrate] (PHB) with poly(γ‐benzyl‐L ‐glutamate) (PBLG) are investigated by means of differential scanning calorimetry (DSC), scanning electron microscopy (SEM) and tensile tests. The DSC results show that PHB and PBLG are immiscible in the melt state. Such immiscibility also exists in the amorphous state due to a clear two‐phase separated structure observed by SEM measurements. The blend samples with different thermal history, namely as original and melt samples separately, display differences in thermal behaviour such as the DSC scan profile, the crystallinity and the melting temperature of PHB. The crystallization of PHB both from the molten state and the amorphous state is retarded on addition of the second component. The SEM measurements reveal that a phase inversion occurs between the PHB/PBLG (60/40) and PHB/PBLG (40/60) blends. Except for the PHB/PBLG (40/60) blend, a microphase separated structure is observed for all blend compositions. The mechanical properties vary considerably with blend composition. Compared with pure components, the PHB/PBLG (20/80) blend shows a certain improvement in mechanical properties. © 2001 Society of Chemical Industry