Preparation and Characterization of Chitosan‐Gellan Hybrid Capsules Formed by Self‐Assembly at an Aqueous Solution Interface

Summary: True spherical capsules are formed by electrostatic polysaccharide interaction between chitosan and gellan gum via polyion complex (PIC) formation in aqueous solutions. Dropwise addition of a chitosan solution into the gellan solution gave spherical capsules whose outside surface was gellan and whose inside was chitosan (chitosanⁱⁿ‐gellan^out capsule). Conversely, the addition of gellan into chitosan yields chitosan^out‐gellanⁱⁿ capsules. SEM observation revealed a fibrous network spreading along the capsule membrane of the chitosanⁱⁿ‐gellan^out capsule. The releasing properties of the capsules were examined using low molecular weight substances and high molecular weight proteins. For low molecular weight substances, the releasing kinetics were affected by the attractive and repulsive interactions between the substances and the inside component of the capsule. The molecular weight of the encapsulated substances also affects the releasing kinetics. These results, together with a simple preparation procedure, indicate the applicability of chitosan‐gellan capsules as drug‐carrier materials having a controlling release mechanism. As an application example, preparation of an actually eatable artificial roe was also described.

Illustrative drawing of PIC capsule formation.     

Poly(oxyethylene)diamine‐derived hydrophilic copolymers for emulsifying diglycidylether of bisphenol‐A

A series of reactive surfactants were synthesized by the reaction of hydrophilic poly(oxyethylene)diamines of 2000–6000 g/mol molecular weight and diglycidylether of bisphenol‐A resin. The synthesized surfactants consisted of multiple functionalities including tertiary amines, hydrophobic alkylphenoxys, and reactive oxirane groups. After treatment with hydrochloric acid, the surfactants consisted of two different hydrophilic groups: cationic quaternary ammonium salts and nonionic oxyethylene segments. By prudent selection of the proper hydrophile–lipophile balance, the surfactant can be highly effective for solubilizing the epoxy resin in water to form a stable emulsion at a fine particle size of 350 nm. Another advantage is that the surfactant may participate in a curing process through the built‐in oxirane reaction and become a nonextractable component in polymer matrix. © 2004 Wiley Periodicals, Inc. J Appl Polym Sci 94: 1797–1802, 2004     

Polyion Complex Nanofibrous Structure Formed by Self‐Assembly of Chitosan and Poly(acrylic acid)

Summary: An ideal scaffold design has a nanofibrous structure that can replace the natural extracellular matrix (ECM) until host cells can repopulate and resynthesize a new natural matrix. In this study, chitosan (CS)‐poly(acrylic acid) (PAA) nanofibers with diameters that range from 50 to 150 nm are synthesized successfully by a modified dropping method. Exactly how various carboxylic acid solvents affect the formation of CS‐PAA nanofibrous complex is also discussed. The results show that using adipic acid as a solvent to dissolve CS, adjusting the final pH value of the CS solution to 3, and then dropping the CS solution into the PAA solution at a ratio of 3:1, cause a significant reaction of CS with PAA and the nanofibers are dispersed uniformly. After freeze‐drying, a 3‐D interconnected CS‐PAA nanofibrous scaffold with a fiber diameter that ranges from 50 to 200 nm can be obtained. The CS‐PAA nanofibrous matrix is of particular interest in tissue engineering for controlled drug release and tissue remodeling.

Nanofibrous structure via polyion complex formation between chitosan and poly(acrylic acid).     

Mass Ratio of CdS/Poly(ethylene oxide) Controlled Photoluminescence of One‐Dimensional Hybrid Fibers by Electrospinning

One‐dimensional high‐quality CdS/poly(ethylene oxide) (PEO) hybrid nanoparticle‐polymer fibers were fabricated by an electrospinning method, followed by self‐assemble technologies with co‐fed H₂S atmosphere at 60 °C. The structural and spectral information of the resulting hybrid nanofibers was characterized by field emission scanning electron microscopy, transmission electron microscopy, X‐ray photoelectron spectroscopy and X‐ray diffractometer. The diameters of CdS/PEO hybrid nanofibers ranged from 90 to 200 nm and the average dimension of CdS nanoparticle within fibers from 4 to 12 nm. An interesting aspect of the CdS/PEO nanofibers shown in photoluminescence spectra and fluorescence images is that the fluorescence peaks of CdS/PEO were shifted along with changing the mass ratio of CdS/Poly(ethylene oxide), and consequently the size and phase of nanocrystal CdS.

     

Lead(II) Adsorption from Aqueous Solution by Poly(ethylene terephthalate)-g-Acrylamide Fibers

In this study, a reactive fibrous adsorbent was prepared by graft copolymerization of Acrylamide (AAm) onto poly(ethylene terephthalate) (PET) fibers and the adsorption properties of Pb(II) ion from aqueous solution by the reactive fibers were examined by batch equilibration technique. The effects of graft yield, pH, adsorption time, initial ion concentration and adsorption temperature on the adsorption amount of Pb(II) ion was studied. The results show that the adsorption amounts of Pb(II) ion increased with grafting yield, shaking time, initial ion concentration and adsorption temperature. Adsorption of Pb(II) ion was strongly affected by pH. A Lagergren pseudo-second-order was the model that best described the adsorption mechanism. It was found that the adsorption isotherm of the Pb(II) ion fit Langmuir-type isotherms. From the Langmuir equation the adsorption capacity was found as 39.57 mg/g fiber for Pb(II) ion for the copolymer with a graft yield of 15.7%. Quantitative desorption of Pb(II) from reactive fibers were found to be 96% by 5 M HNO₃. Five adsorption–desorption cycles demonstrated that the reactive fibers were suitable for repeated use without considerable change in adsorption capacity. The results of the thermodynamic study indicated that the adsorption processes was endothermic and spontaneous.     

A study on solution properties of poly(N,N‐diethylacrylamide‐co‐acrylic acid)

Poly(N,N‐diethylacrylamide) (PDEA), poly(acrylic acid) (PAA), and a series of (N,N‐diethylacrylamide‐co‐acrylic acid) (DEA‐AA) random copolymers were synthesized by the method of radical polymerization. The measurement of turbidity showed that the phase behaviors of the brine solutions of the copolymers changed dramatically with the mole fraction of DEA (x) in these copolymers. Copolymers cop6 (x = 0.06) and cop11 (x = 0.11) in which acrylic acid content was higher presented the upper critical solution temperature (UCST) phase behaviors similar to PAA. Copolymer cop27 (x = 0.27) presented the lower critical solution temperature (LCST) behavior similar to PDEA. While copolymer cop18 (x = 0.18) in which acrylic acid content was moderate presented both UCST and LCST behaviors. The solution properties of the polymers were investigated by measurements of viscosity, fluorescence, and pH. It is reasonable to suggest that the sharp change of the phase behavior may be attributed to the interaction between acrylamide group and carboxylic group in the (DEA‐AA) copolymers. © 2008 Wiley Periodicals, Inc. J Appl Polym Sci, 2008     

Dynamic Mechanical Properties of Poly(propylene) Blends with Poly[ethylene‐co‐(methyl acrylate)]

Summary: Blends of poly(propylene) (PP) were prepared with poly[ethylene‐co‐(methyl acrylate)] (EMA) having 9.0 and 21.5% methyl acrylate comonomer. A similar series of blends were compatibilized by using maleic anhydride grafted PP. The morphology and mechanical properties of the blends were investigated using differential scanning calorimetry (DSC) and dynamic mechanical analysis (DMA) in tensile mode. The DMA method and conditions were optimized for polymer film specimens and are discussed in the experimental section. The DSC results showed separate melting that is indicative of phase‐separated blends, analogous to other PP‐polyethylene blends but with the added polarity of methyl acrylate pendant side groups that may be beneficial for chemical resistance. Heterogeneous nucleation of PP was decreased in the blends because of migration of nuclei into the more polar EMA phase. The crystallinity and peak‐melting temperature did not vary significantly, although the width of the melting endotherm increased in the blends indicating a change had occurred to the crystals. DMA analysis showed the crystal‐crystal slip transition and glass transition (T_g) for PP as well as a T_g of the EMA copolymer occurring chronologically toward lower temperatures. The storage modulus of PP and the blends was generally greater with annealing at 150 °C compared with isothermal crystallization at 130 °C. The storage modulus of the blends for isothermally crystallized PP increased with 5% EMA, then decreased for higher amounts of EMA. Annealing caused a decrease with increasing copolymer content. The extent of the trend was greater for the compatibilized blends. The T_g of the blends varied over a small range, although this change was less for the compatibilized blends.

Storage modulus for PP and EMA9.0 blends annealed at 150 °C.     

Poly(amide‐ester)s derived from dicarboxylic acid and aminoalcohol

A series of alternating aliphatic poly(amide‐ester)s, derived from dicarboxylic acid and aminoalcohols, were obtained by polycondensation in melt. All poly(amide‐ester)s were characterized by FTIR and ¹H/¹³C‐NMR spectroscopies. The synthesized polymers showed an inherent viscosity ranging from 0.4 to 1.0 dL g^?1. Thermal analysis showed melting points within the range 100–115°C and glass transition within the range 30–60°C. Decomposition temperatures were more than 200°C higher than the corresponding melting temperatures. The polymers can thus be processed from the melt. The processed polymers were partially crystalline with good thermal stability. © 2004 Wiley Periodicals, Inc. J Appl Polym Sci 95: 362–368, 2005     

Crystalline and Conductive Poly(3‐hexylthiophene) Fibers

Intrinsically conducting polymer fibers are prepared from P3HT by melt spinning. High crystallinity is achieved by drawing the fibers after the spinning process, applying a draw ratio of 1:2. DSC and XRD measurements confirm the continuous increase of crystalline phases with drawing. For comparison, poly(ethylene terephthalate) fibers are coated with P3HT and drawn as well. Again, the drawing of the coated fiber results in a significant increase in crystallinity of the P3HT coating. The high amount of crystalline phases is associated with a dramatic increase in conductivity (350 S · cm^?1) after doping with FeCl₃ in nitromethane.

     

Polyion complex fiber and capsule formed by self‐assembly of poly‐L‐Lysine and gellan at solution interfaces

Different characteristic surface structures such as capsules, regularly spaced droplets, and fibers are formed by electrostatic interaction between poly‐L ‐lysine (PLL) and gellan gum via polyion complex (PIC) formation. Spherical droplet PIC capsules of varying diameters form in solutions. Some dyes adsorb on the surface of the capsules, and other dyes penetrate into the capsules. The strong PIC fiber can be spinnable by gravity and by wet spinning in ethanol. This fiber possesses a counterion pairing structure and exhibits the nervation/veining pattern and hollow yarn. The tensile strength of the fiber is 27.8 kg/mm² [1.40 g/denier (d)] and the knotting strength is 9.98 kg/mm² (1.13 g/d). By using an organic crosslinking agent, epichlorohydrin, the tensile strength can be increased to 38.5 kg/mm² (2.46 g/d) and the knotting strength can be increased to 12.2 kg/mm² (1.99 g/d). The PIC fiber can be dyed by five different dyeing procedures such as direct and vat dyeings. The PLL PIC fiber is water insoluble and has potential as a new synthetic polypeptide fiber technology. © 2000 John Wiley & Sons, Inc. J Appl Polym Sci 79: 437–446, 2001     

Photodegradation of Poly(L‐lactic acid): Effects of Photosensitizer

Summary: Amorphous and crystallized poly(L ‐lactic acid) (PLLA‐A and PLLA‐C, respectively) films with different contents of N,N,N′,N′‐tetramethyl‐1,4‐phenylenediamine (TMPD) as a photosensitizer were prepared, and the effects of the addition of TMPD on the photodegradation of PLLA films were investigated. It was found that the addition of TMPD effectively enhanced the photodegradation of PLLA films and thereby decreased their molecular weight of PLLA films regardless of their crystallinity, and that PLLA films with different molecular weights can be prepared by the addition of different amounts of TMPD and subsequent UV irradiation. Too high contents of TMPD however caused the brittleness of PLLA films due to a large decrease in molecular weight. The PLLA chains in crystalline regions as well as those in amorphous regions are photodegradable even at an early stage, in marked contrast to their hydrolytic degradation, where the chains in the amorphous regions are selectively degraded. The basic changes in glass transition, cold crystallization, and melting temperatures (T_g, T_cc, and T_m, respectively) of PLLA films during UV irradiation can be ascribed to low‐temperature annealing effects; i.e., annealing‐induced stabilization in chain packing should have elevated T_g, and annealing‐induced formation of crystallite nuclei should have lowered T_cc and increased T_m. The exceptional large decreases in T_cc and T_m of UV‐irradiated PLLA‐A films and in T_g of UV‐irradiated PLLA‐C films at high TMPD contents are attributable to the large decrease in molecular weight, whereas the exceptional decrease in T_m of PLLA‐C films at high TMPD contents can be due to the folding surface structural change of crystalline regions or to the lattice disorder caused by molecular structural changes.

of PLLA‐A films before UV irradiation and after UV irradiation for 60 h as a function of TMPD content.     

Synthesis and thermal properties of poly(methyl methacrylate)‐poly(L‐lactic acid)‐poly(methyl methacrylate) tri‐block copolymer

Poly(methyl methacrylate)‐poly(L ‐lactic acid)‐poly(methyl methacrylate) tri‐block copolymer was prepared using atom transfer radical polymerization (ATRP). The structure and properties of the copolymer were analyzed using infrared spectroscopy, gel permeation chromatography, nuclear magnetic resonance (¹H‐NMR, ¹³C‐NMR), thermogravimetry, and differential scanning calorimetry. The kinetic plot for the ATRP of methyl methacrylate using poly(L ‐lactic acid) (PLLA) as the initiator shows that the reaction time increases linearly with ln[M]₀/[M]. The results indicate that it is possible to achieve grafted chains with well‐defined molecular weights, and block copolymers with narrowed molecular weight distributions. The thermal stability of PLLA is improved by copolymerization. A new wash‐extraction method for removing copper from the ATRP has also exhibits satisfactory results. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2012     

Novel polyion complex films from chitosan and quarternized poly(4‐vinyl‐N‐carboxymethylpyridine) containing zwitterion structure units

Novel polyion complexes films of chitosan and quarternized poly(4‐vinyl‐N‐carboxymethylpyridine) containing zwitterion structure units were prepared by casting method. The aim of this work was to produce a hydrophilic film with the potential use as a hydrophilic membranes of the types used in membranes distillation and osmotic distillation for separating azeotropic, close‐boiling, and aqueous organic mixtures. Their structure and properties were studied by infrared, wide‐angle X‐ray diffraction, scanning electron microscopy, thermogravimetric analysis, tensile tester, and swelling measurements. The results indicated that polyion complexes occurred between chitosan and quarternized poly (4‐vinyl‐N‐carboxymethylpyridine) containing zwitterion structure units. The thermostability of these blends decreased with the increase of quarternized poly(4‐vinyl‐N‐carboxymethylpyridine) content. Initially, appreciable improvement in tensile strength and breaking elongation were achieved with increase of quarternized poly(4‐vinyl‐N‐carboxymethyl‐pyridine) content to 30%, the maximum value of 46.65 MPa tensile strength and 25.67% breaking elongation were achieved, respectively. The maximum degree of swelling was achieved when the weight ratio of chitosan versus poly(4‐vinyl‐N‐carboxymethylpyridine) was 50 : 50. Meanwhile, the relationship between their structure and properties was also discussed. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci, 2007     

Propylene/1‐Hexene Copolymer as a Tailor‐Made Poly(propylene) for Membrane Preparation via the Thermally Induced Phase Separation (TIPS) Process

Summary: Poly[propylene‐co‐(1‐hexene)], one example of a “tailor‐made poly(propylene)”, was synthesized using an iso‐specific metallocene catalyst in order to study the influence of copolymer composition on the pore size of isotactic poly(propylene) (iPP) membranes prepared by the TIPS process. The structure of the copolymers and their properties in solution were analyzed and discussed in relation to the polymer‐diluent phase diagram, the droplet growth kinetics during the TIPS process, the viscosity of the system and the final pore size of the membranes. The crystallization curve in the phase diagram was found to shift significantly as comonomer content increased and thus the droplet growth period was drastically increased. The resulting increase of the characteristic pore size in the membranes demonstrated that it is possible to use tailor‐made poly(propylene)s to control the pore size in porous membranes prepared via the TIPS process (under otherwise constant conditions).

Porous size is controlled by the polymer and the TIPS process.     

Fabrication of Aligned Poly(L‐lactide) Fibers by Electrospinning and Drawing

A new target collector was designed for taking up aligned nanofibers by electrospinning. The collector consists of a rotor around which several fins were attached for winding electrospun filaments continuously in large amounts. The alignment of the nanofibers wound on the collector was affected by the electrospinning conditions, such as the needle‐to‐collector distance and the applied voltage, but not by the rotation speed of the collector. At a voltage of 0.5 kV · cm^?1, about 60% of the fibers were found to be aligned within an angle of ± 5° relative to the rotational direction of the collector. The fiber alignment was improved to 90% by drawing the fiber bundle 2–3 times at 110 °C. The drawing was also effective for crystal orientation of the fibers as revealed by WAXD. The drawn fibers show improved mechanical properties.

     

Poly(ethylene‐co‐vinyl acetate)‐graft‐poly(methyl methacrylate) (EVA‐graft‐PMMA) as a modifier of epoxy resins

Conventional approaches to toughen thermosets are: (1) the polymerization‐induced phase separation of a rubber or a thermoplastic, or (2) the use of a dispersion of preformed particles in the initial formulation. In the present study it is shown that it is possible to combine both techniques by using graft copolymers with one of the blocks being initially immiscible and the other that phase separates during polymerization. This is illustrated by the use of poly(ethylene‐co‐vinyl acetate)‐graft‐poly(methyl methacrylate) (EVA‐graft‐PMMA) as modifier of an epoxy resin. EVA is initially immiscible and PMMA phase separates during polymerization. Blends of an epoxy monomer based on diglycidylether of bisphenol A (DGEBA, 100 parts by weight), piperidine (5 parts by weight), and PMMA (5 parts by weight), showed the typical polymerization‐induced phase separation of PMMA‐rich domains before gelation of the epoxy network. Replacing PMMA by EVA‐graft‐PMMA (5 parts by weight), yielded stable dispersions of EVA blocks, favoured by the initial solubility of PMMA blocks. Phase separation of PMMA blocks in the course of polymerization led to a dispersion of in situ generated biphasic particles (plausibly composed of EVA cores surrounded by PMMA shells), with average diameters varying from 0.3 to 0.6 µm with the cure temperature. This procedure may be used to generate stable dispersions of biphasic particles for toughening purposes. © 2002 Society of Chemical Industry     

Properties of Injection Molded Composites Containing Corn Fiber and Poly(Vinyl Alcohol)

Composites based on natural polymers alone are extremely sensitive to moisture and their mechanical properties deteriorate upon the absorption of water, limiting their usefulness in practical applications. Ongoing research cooperation between USDA and the University of Pisa, Italy, has yielded several composites based on poly(vinyl alcohol) (PVA) and corn fibers (CF). In this study, variable amounts of CF and PVA were processed in the presence of both dry and liquid plasticizers, glycerol and pentaerythritol. Cornstarch was introduced in the formulation to reduce the cost and to further increase the composition of natural components in the composites. Composites made with as low as 30% PVA were injection molded into tensile bars and evaluated. The addition of starch moderately reduced the tensile properties of the composites, lowering the elongation (∼600% to 400%) and increasing Young's modulus (∼36 MPa to ∼100 MPa) while the ultimate tensile strength remained constant at about 8 MPa. Composites prepared from CF and PVA showed little change in their mechanical properties even after conditioning them at various relative humidities, or after soaking in water. Composites tested after storage for one year, at 50% relative humidity and 23°C, exhibited mechanical properties similar to those of freshly prepared composites. *Names are necessary to report factually on available data; however the USDA neither guarantees nor warrants the standards of the product and the use of the name USDA implies no approval of the product to the exclusion of others that may also be suitable.     

Effect of poly(n‐isopropyl acrylamide‐co‐itaconic acid) on the chemical polymerization of pyrrole with (NH4)2[Ce(NO3)6]

The chemical oxidative polymerization of pyrrole (Py) by ceric ammonium nitrate (CAN) in the presence of polyitaconic acid and its copolymers (Polymer) containing 75 and 50 mole% N‐isopropylacrylamide were investigated. The effects of copolymer composition and addition order of the components on the reaction mechanism were studied by following the absorption spectra of the soluble reaction products between 200 and 1100 nm. As to the UV‐visible, FTIR and conductivity results of soluble products obtained from Polymer‐CAN‐Py system, it was assumed that the pyrrole polymerization by chemical oxidation was inhibited in the presence of the water‐soluble polyelectrolyte because an important part of ceric ammonium nitrate was consumed to produce radicals on the chains. On the other hand, the role of the copolymers in the case of Py‐CAN was mainly to prevent precipitation of polypyrrole. Consequently, the reaction prepared according to the first order of addition of the reactants favour the formation of oligomeric pyrrole, while the second order of addition yields solution of colloidal polypyrrole interacting with polyelectrolytes. © 1999 Society of Chemical Industry     

In vitro Degradation of Poly[(L‐lactide)‐co‐(trimethylene carbonate)] Copolymers and a Composite with Poly[(L‐lactide)‐co‐glycolide] Fibers as Cardiovascular Stent Material

TMC/LLA copolymers with several TMC/LLA ratios are synthesized and a composite is obtained by reinforcing with short PLGA fibers. In vitro degradation is studied at 37 °C in pH = 7.4 buffer and compared with a PLLA homopolymer. The degradation of the copolymers appears slower than that of PLLA, showing that TMC units are more resistant to hydrolysis than LLA. Compositional changes indicate a preferential degradation of LLA units as compared to TMC ones. Morphological changes with crystallization of degradation by‐products are observed. The composite degrades much faster than the neat copolymer and PLLA because the faster degradation of PLGA fibers speeds up the degradation of the matrix. The composite appears promising for the fabrication of totally bioresorbable stents.

     

Poly(para‐dioxanone) and poly(L‐lactic acid) blends: thermal,mechanical, and morphological properties

Blends of two semicrystalline polymers, poly(L ‐lactic acid) (PLLA) and poly‐p‐dioxanone (PPD) have been prepared by solvent casting in different compositions. Thermal, morphological, and mechanical properties of the blends were studied using modulated differential scanning calorimetry, wide‐angle X‐ray diffractometry, scanning electron microscopy (SEM), polarizing light microscopy (PLM), and tensile tests. Thermal analysis showed two glass transition temperatures nearly constant and equal to the values of the homopolymers and constant values of melting temperature (T_m) for all blend compositions, suggesting that both polymers are immiscible. The PLM and SEM observations validated these results, and showed the different morphology obtained by changing the composition of the blend. The blends 40/60, 50/50, and 60/40 presented a clearly macroseparated system, while the 20/80 and 80/20 blends presented better homogeneity, probably due to the low amount of one component in the other. It was found by PLM that PPD is able to crystallize according to a spherulitic morphology when its content is above 40%. Under this content, the crystallization of PPD is hardly observed. The blend 20/80 is more flexible, and tough material and neck formation during elongation is also observed, due to PPD, which may act as a plasticizer. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 12: 2744–2755, 2003