Preparation and characterization of microspheres based on blend of poly(lactic acid) and poly(ɛ-caprolactone) with poly(vinyl alcohol) as emulsifier

In this paper, microspheres were prepared by oil-in-water (o/w) emulsion solvent evaporation method. Biodegradable polymer such as blend of poly (lactic acid) (PLA) and poly(?-caprolactone) (PCL) with certain compositions and characteristics was used to prepare the microspheres with poly(vinyl alcohol) (PVA) as an emulsifier. This study observed the microspheres particle’s size distribution at various concentrations of PVA (1%, 1.5%, 2%, and 2.5% PVA). The PVA volume variations effects during the process (50, 100, 150, 200, and 250 mL) were also observed. The blend of PLA and PCL is formed only by physical interaction between them. This can be seen from the FTIR spectrum which shows both PLA and PCL component. The microspheres physical size and appearance were observed by optical microscope (MO). The overall results of this study showed that the formula which used 50–150 mL of 2.5% polyvinyl alcohol produced the microspheres with the most uniform size distribution.     

Preparation and properties of poly(vinyl alcohol)/exfoliated α-zirconium phosphate nanocomposite films

In this work, poly(vinylalcohol)(PVA)/exfoliated α-zirconium phosphate(e-α-ZrP) nanocomposites of various compositions were created by a solution casting method. The α-ZrP compound was synthesized by refluxing. The characteristic properties of the PVA/e-α-ZrP composite films were examined by thermal gravimetric analysis (TGA), differential scanning calorimetry (DSC), X-ray diffraction (XRD), scanning electron microscopy (SEM) and tensile tests. Tensile tests indicated that with the loading of e-α-ZrP, the tensile strength and the elongation at break were increased by 17.3% and 26.6% compared to neat PVA, respectively. It is noteworthy that optimum film properties were obtained with 0.8 wt% e-α-ZrP, and higher proportions of e-α-ZrP, may be related to the aggregation of e-α-ZrP particles and deterioration of the film properties. On the whole, the nanocomposite PVA/e-α-ZrP systems had mechanical and thermal properties which were superior to that of the neat polymer and its conventionally filled composites.     

Chemical–physical behavior of hydrogels of poly(vinyl alcohol) and poly(ethylene glycol)

New hydrogels based on polyethylene glycol (PEG) and poly(vinyl alcohol) (PVA) of different degrees of hydrolysis were synthesized. To form the network the PEG was modified at their ends with acyl chloride groups to be used as the crosslinking agent. The compositions of the hydrogels were between 50% and 90% by weight of PEG and PVA of various degrees of hydrolysis were used. It was found that the degree of hydrolysis of the PVA and the PEG content influence the equilibrium water content of the hydrogel. The process of swelling of all the hydrogels prepared followed a second-order kinetics.     

Thermal properties and flammability performance of poly (vinyl alcohol)/α-zirconium phosphate nanocomposites

Nanocomposites of poly (vinyl alcohol) with ethylamine modified zirconium phosphate (ZrP-EA) were prepared by solution blending. Their morphologies were elucidated with X-ray diffraction and transmission electron microscopy, while the thermal stability and flammability performance were characterized by thermogravimetric analysis, Fourier transform infrared spectra and microscale combustion calorimetry. It was established that the morphology of the nanocomposites evolved as ZrP-EA content increased. In the nanocomposites, catalytic degradation of the acetate groups remaining in poly (vinyl alcohol) occurred and catalytic carbonization was observed. Microscale combustion calorimetry revealed that the flammability performance of poly (vinyl alcohol) was improved by the introduction of zirconium phosphate nanoplatelets.     

Synthesis and characterization of biodegradable pH-sensitive hydrogels based on poly(?-caprolactone), methacrylic acid, and poly(ethylene glycol)

In this work, a novel biodegradable pH-sensitive hydrogel based on poly(?-caprolactone) (PCL), methoxpoly(ethylene glycol) (MPEG) and methacrylic acid (MAA) was prepared by UV-initiated free radical polymerization. The resulting macromonomers and hydrogels were characterized by FTIR and/or ¹H NMR. Swelling behaviour and pH sensitivity of the hydrogels were studied in detail. With increase in pH of aqueous medium from 1.2 to 7.2, swelling ratio of the hydrogels increased accordingly. The hydrolytic degradation behaviour was also investigated. The prepared biodegradable pH-sensitive hydrogel based on PCL, MPEG, and MAA might have great potential application in smart drug delivery system.     

Studies on Diels–Alder thermoresponsive networks based on ether–urethane bismaleimide functionalized poly(vinyl alcohol)

Thermoreversible networks obtained by the Diels–Alder cycloaddition reaction of poly(vinyl furfural) with urethane bismaleimides containing polyether chain were synthesized. The formation of the networks was confirmed by attenuated total reflectance in conjunction with Fourier transform infrared spectroscopy (ATR–FTIR). The materials thermal properties were investigated using differential scanning calorimetry (DSC) and a coupling of dynamic thermogravimetry with Fourier transform infrared spectroscopy and mass spectrometry (TG–FTIR–MS) for pyrolysis behaviour under nitrogen atmosphere. A thermal decomposition mechanism of the networks and poly(vinyl furfural) was discussed via evolved gas analysis. The thermoreversibility of the networks was demonstrated by the presence of the endothermic peak characteristic to the retrodienic process on the DSC heating curves and also the appearance of the exothermic peak, due to the dienic process, on the DSC cooling curve. The dynamic contact angle and free surface energy values of the networks were determined. Measures of the heterogeneity and roughness of the surfaces suggested that the surfaces of the networks’ films are more homogenous than the initial poly(vinyl furfural) surface. Dynamic water vapour sorption studies were conducted.     

Effect of poly(amid–imide)/Al2O3 hybrid with various ratios on the physicochemical properties of poly(vinyl alcohol) nanocomposites films

To study the effect of the various ratios of poly(amide–imide)/Al₂O₃ nanocomposites (PANC)s on the mechanical and thermal properties of nanocomposites films, poly(vinyl alcohol) (PVA)/PANCs based on various ratios of 2, 4, and 6 wt% were prepared and characterized. In the first step, the surface of alumina nanoparticles was treated with 15 wt% of biosafe diacid and consequently, about 10 wt% of these modified nanoparticles were loaded into the poly(amide–imide) matrix. Then, various contents of the obtained PANCs were incorporated into a PVA solution using a sonochemical treatment. The effects of PANC on the structure and morphology of PVA matrix were studied using powder X-ray diffraction, field emission scanning electron microscopy, transmission electron microscopy, Fourier transform infrared spectroscopy, atomic force microscopy (AFM), and thermal gravimetric analysis (TGA). The results show that the tensile strength and decomposition temperature were improved as the portion of PANC into PVA matrix are increased from 2 to 6 wt%. Also, AFM pictures of the fracture surfaces of PVA/PANCs showed a significantly rougher surface than the neat PVA.     

Preparation of tough hydrogels based on β-chitin nanofibers via NaOH treatment

Cellulose and chitin exist in nature as highly crystalline nanofibers. Previously, we reported preparing unique hydrogels from cellulose nanofibers by a simple NaOH treatment without use of any specific solvents or cross-linking agents. In the present study, a similar gel preparation was applied to β-chitin nanofibers extracted from purified squid pen powder. The crystal structure of chitin nanofibers was transformed from β-chitin to α-chitin by NaOH(aq) treatment above 30 wt%. The crystal conversion involving the interdigitation among adjacent nanofibers caused the formation of stable hydrogels with a α-chitin nanofiber network. The use of ethanol voided the dissolution during neutralization and enabled preparation of a higher crystalline hydrogel with high mechanical strength. It achieved a Young’s modulus of 16.6 MPa, a tensile strength of 7 MPa and a strain at break of 52.2 %, on average. Finally, we note that the shrinkage of the cellulose I and β-chitin nanofibers in aqueous NaOH solutions was caused by the release of tensile residual stress due to the intracrystalline swelling in NaOH solutions.     

Hydrolytic and microbial degradation of multi-block polyurethanes based on poly(?-caprolactone)/poly(ethylene glycol) segments

Biodegradable amphiphilic multi-block poly(ether-ester-urethane)s were prepared by one-step bulk polycondensation of PEG and PCL macro-diols and HMDI. For biomedical or environmental applications of the proposed materials, one of the critical steps is the study of the degradation characteristics under physiological or environmental conditions. Different ratios of PEG/PCL and molecular weights of the resultant copolymers allowed for tuning their hydrophilicity, as evaluated by water uptake measurements. The swelling results were further supported by microgravimetric measurements performed by QCM-D. In vitro hydrolytic biodegradation was carried out under different conditions (i.e., in phosphate buffer solution - with and without Lipase). Total mineralization in the presence of microorganisms from a sample of river water was observed to follow different kinetics, depending upon the composition and the molecular weight of the copolymer.     

Binary blends based on poly(vinyl chloride) and multi-block copolymers containing poly(ϵ-caprolactone) and poly(ethylene glycol) segments

Binary blends based on poly(vinyl chloride) (PVC) were prepared both by casting from tetrahydrofuran (THF) and by mixing in the melt form, in a discontinuous mixer, PVC and multi-block copolymers containing poly(ϵ-caprolactone) (PCDT) and poly(ethylene glycol) (PEG) segments. PCDT-PEG copolymers were synthesized using a polycondensation reaction where the α,ω-bis-chloroformate of an oligomeric poly(ϵ-caprolactone) diol terminated (PCDT) and oligomeric PEG were employed as macromonomers. For comparison purposes, blends PVC with starting oligomers as well as with mixtures containing a typical low molecular plasticizer, dioctylphthalate (DOP), were also prepared. The copolymer miscibility was studied by differential scanning calorimetry (DSC) and FT-IR spectroscopy. The blend morphology was investigated by polarized light microscopy (PLM). A higher miscibility with PVC was observed for copolymers compared to PEG.     

Reentrant behavior of poly(vinyl alcohol)–borax semidilute aqueous solutions

 The reentrant behavior of Poly(vinyl alcohol) (PVA)–borax aqueous semidilute solutions with a PVA concentration of 20 g/l and borax concentrations varies from 0.0 to 0.20 M was investigated using dynamic light scattering (DLS) and dynamic viscoelastic measurements. Two (fast and slow modes) and three (fast, middle, and slow) relaxation modes of PVA semidilute aqueous solutions without and with the presence of borax, respectively, were observed from DLS measurements. The fast and middle relaxation modes were q ²-dependent (q is the scattering vector) characteristic of diffusive behavior; however, the slow modes were q ³-dependent, characteristic of intraparticle dynamics. The experimental results showed that the slow relaxation mode dominates the DLS relaxation. The DLS slow mode relaxation time, τ_s, and the viscoelastic modulus G′(ω) and G′′(ω) data had a similar trend and demonstrated reentrant behavior as the borax concentration was increased from 0.0 to 0.20 M, i.e. τ_s, G′(ω), and G′′(ω) fluctuated with increasing borax concentration. The excluded-volume effect of polymers, charge repulsion among borate ions bound on PVA molecules, and intermolecular cross-linking didiol–borate complexation caused an expansion of the polymer chain; however, the screening effect of free Na⁺ ions on the negative charge of the borate ions bound on PVA and intramolecular cross-linking didiol–borate complexation led to a shrinkage of the polymer chain. The reentrant behavior was the consequence of the balance between expansion and shrinkage of the PVA–borate complex. Received: 26 March 1999/Accepted in revised form: 3 September 1999     

Methylene green-mediated sensor highly sensitive to hydrogen peroxide based on entrapment of horseradish peroxidase in composite membrane of regenerated silk fibroin and poly(vinyl alcohol)

Introduction The detection and quantitative determination of hydrogen peroxide play importantrole in several fields including biochemistry and environmental chemistry.A highlysensitive H202 sensor is useful to fabricate sensor for various substances by combiningit with hydrogen peroxide—producing oxidases.‘Although electrochemical detection ofH202 has been made via its oxidation or reduction at a variety of electrode materials,these electrodes are susceptible to the interference from electr…     

Synthesis and characterization of poly(ethylene glycol) based β-cyclodextrin polymers

A series of novel water soluble β-cyclodextrin (βCD) polymers has been synthesized from functionalized poly(ethylene glycol) (PEG). The chemical composition of the polymers has been characterized by ¹H NMR and the βCD content is found to be between 48 and 33% (w/w). The molecular weight has been determined by Size Exclusion Chromatography (SEC) and depends on the ratio between βCD and PEG, varying from 2.1 × 10⁴ to 8.6 × 10⁴ g mol^?1. The physico chemical properties have been characterized by differential scanning calorimetry (DSC), viscometry and isothermal titration calorimetry (ITC). ITC shows that the polymers have association constants comparable to βCD with different guest molecules, indicating a good accessibility of the CDs.     

Solvent-free esterification of poly（vinyl alcohol） and maleic anhydride through mechanochemical reaction

A solid-state mechanochemical processing,that is,pan-milling,was used to conduct the esterification of poly(vinyl alcohol) (PVA) with maleic anhydride (MA) through stress-induced reaction.FTIR spectrum study indicated the presence of ester linkages and olefinic double bonds in maleic anhydride cross-linked PVA.Thermal properties of the cross-linked product were characterized by DSC.The results showed its glass transition temperature was 20℃higher than the original linear PVA and the thermal stability was also improved.     

Transition behaviors and hybrid nanofibers of poly(vinyl alcohol) and polyethylene glycol–POSS telechelic blends

We report solution properties of the blend solutions of poly(vinyl alcohol) (PVA) and poly(ethylene glycol) (PEG)–POSS telechelic and its corresponding hybrid nanofibers prepared by electrospinning. The morphologies, microstructures, and wettability of the resulting PVA/PEG3.4k–POSS hybrid nanofibers are studied. The morphologies of the resultant PVA/PEG3.4k–POSS nanofibers are regular with the fiber diameter ranging from 610 ± 110 to 810 ± 280 nm. When the content of PEG3.4k–POSS telechelic increases above 20 wt.%, the beaded fiber morphologies are observed due to severe aggregations of the PEG3.4k–POSS telechelics as well as increased viscosity at higher concentration. In addition, the solution properties of pure PEG3.4k–POSS telechelic solution (ca. 3–5 wt.%) and PVA/PEG3.4k–POSS solutions blended with PVA are explored, and found to show the reversible turbid-to-transparent transition behavior with respect to the solution temperature. Water contact angle measurement of the PVA/PEG3.4k–POSS nanofiber membranes demonstrates an enhanced hydrophobic nature due to the incorporated POSS moieties.     

Synthesis and characterization of silver—poly(methylmethacrylate) nanocomposites

The optical properties of silver nanoparticles embedded in poly(methylmethacrylate) (PMMA) was investigated as well as the influence of silver nanoparticles on the thermal properties of polymer matrix. The average size and particle size distribution of silver nanoparticles was determined using transmission electron microscopy. The obtained transparent nanocomposite films were optically characterized using UV-Vis and FTIR spectroscopy. Thermal stability of polymer matrix was improved upon incorporation of small amount of silver nanoparticles. Also, silver nanoparticles have pronounced effect on thermo-oxidative stability of PMMA matrix. The glass transition temperatures of nanocomposites are lower compared to the pure polymer.     

Radiolytically prepared poly(vinyl alcohol) hydrogel containing α-cyclodextrin

α-Cyclodextrin (α-CD) was immobilized by the radiation-induced gelation of poly(vinyl alcohol) (PVA). An aqueous solution of 4-nitrophenol (4-Np) was added upon the PVA hydrogel containing α-CD in a quartz cell. Absorption spectra of the hydrogel phase have demonstrated that 4-Np permeates into the hydrogel and is included by α-CD. When pure toluene was added upon the hydrogel, the rate of the permeation of toluene was affected by the inclusion complexation with α-CD.