Poly(butylene adipate-co-terephthalate)/thermoplastic starch/zeolite 5A films: Effects of compounding sequence and plasticizer content.

This work investigated the effect of the compounding sequence and the glycerol content on poly(butylene adipate-co-terephthalate)/thermoplastic starch/zeolite 5A (PBAT/TPS/Z5A) composites. The composite pellets and films were prepared by an extrusion process using a PBAT:TPS ratio of 60:40, Z5A loading of 3 wt%, and glycerol contents of 35 and 40 parts per hundred parts of starch (phs). Prior to blown film extrusion, the composite pellets were produced by two compounding sequences: sequence I (SI)-mixing PBAT with Z5A prior to blending with TPS; sequence II (SII)-mixing TPS with Z5A before blending with PBAT. The SII compounding sequence provided improved mixing between PBAT and TPS, leading to increased continuous phase region and a reduced TPS dispersed phase size. Increasing the glycerol content decreased the viscosity and size of the TPS dispersed phase and gave rise to a more uniform dispersion of the TPS domains and Z5A particles. Compounding Z5A via the SII sequence with a glycerol content of 40 phs effectively improved the mixing and the performance of the PBAT/TPS blend.

The effects of blend ratio and storage time on thermoplastic starch/poly(butylene adipate-co-terephthalate) films.

The objective of this work was to investigate blend ratio and storage time effects on the morphological, mechanical, and thermal properties of thermoplastic starch/poly(butylene adipate-co-terephthalate) (TPS/PBAT) films. TPS was prepared from plasticized cassava starch using a twin-screw extruder. TPS was subsequently melt-blended with PBAT with varied weight ratios (i.e., 20/80, 40/60 and 60/40) and blown to form TPS/PBAT films. It was found that increasing the TPS/PBAT ratio to 40/60 led to improved distributions of polymeric components and increased PBAT crystallization temperatures while reducing TPS melting transitions and tensile properties of TPS/PBAT films. After three months of storage at 30 °C, the tensile strength and secant modulus at 2% strain of TPS/PBAT films increased due to recrystallization of both TPS and PBAT. Blend ratios were the primary determinant for changes in TPS/PBAT film elongation at break with this storage time. Elongation at break decreased at low TPS:PBAT ratios (i.e., 20/80) and increased at high blend ratios (i.e., 60/40). The recrystallization of both TPS and PBAT components were observed from XRD and DSC analyses. Results obtained from both techniques confirmed the formation of additional crystalline structures of individual components during storage. The recrystallization phenomena also affected thermal transition temperatures of blend components. The crystallization temperature of PBAT-rich phase increased as starch could act as nucleating sites for PBAT. Using DMA, the tan δ curve of TPS/PBAT film exhibited two sharp individual peaks corresponding to the glass transitions of PBAT-rich and starch-rich phases. The tan δ of TPS-rich phase shifted to higher temperature due to recrystallization of TPS-rich phase.

Thermoplastic starch/polybutylene adipate terephthalate film coated with gelatin containing nisin Z and lauric arginate for control of foodborne pathogens associated with chilled and frozen seafood.

In order to control foodborne pathogens on seafood products, an antimicrobial, thermoplastic starch/polybutylene adipate terephthalate (TPS/PBAT; 40/60) film was produced by coating gelatin (15% v/v) containing lauric arginate (LAE; 0.8 mg/cm2), alone or combination with nisin Z (69.4 AU/cm2) to produce LAE-Gelatin-TPS/PBAT and Nisin-LAE-Gelatin-TPS/PBAT films, respectively. Both films were investigated for control of Vibrio parahaemolyticus ATCC 17802 and Salmonella Typhimurium ATCC 14028 on bigeye snapper (Lutjanus lineolatus) and tiger prawn (Penaeus monodon) slices during long-term (28 days), refrigerated (4 °C; chilled) and frozen (-20 °C) storage up to 90 days. S. Typhimurium ATCC 14028, experimentally inoculated onto bigeye snapper and tiger prawn slices, treated with the LAE-Gelatin-TPS/PBAT film, and stored at 4 °C was reduced 3.2 log10 CFU/g after 28 days and 7 log10 CFU/g after 21 days, respectively. Nisin-LAE-Gelatin-TPS/PBAT film reduced S. Typhimurium ATCC 14028 on bigeye snapper and tiger prawn slices 3.5 log10 CFU/g after 28 days and 7 log10 CFU/g after 14 days at 4 °C, respectively. The LAE-Gelatin-TPS/PBAT and Nisin-LAE-Gelatin-TPS/PBAT films and storage for 28 days at 4 °C reduced V. parahaemolyticus inoculated on chilled bigeye snapper slices approximately 2.6 and 4.2 log10 CFU/g, respectively. Both films reduced V. parahaemolyticus inoculated on chilled tiger prawn slices approximately 7.1 log10 CFU/g after 28 days at 4 °C. The LAE-Gelatin-TPS/PBAT and Nisin-LAE-Gelatin-TPS/PBAT films also reduced S. Typhimurium, inoculated on bigeye snapper and tiger prawn slices, 5.8 and 5.6 log10 CFU/g, respectively, after 60 days at -20 °C. V. parahaemolyticus was reduced by 5.8 log10 CFU/g on frozen bigeye snapper and tiger prawn slices after treatment with Nisin-LAE-Gelatin-TPS/PBAT film after 14 and 21 days, respectively. However, the LAE-Gelatin-TPS/PBAT film reduced V. parahaemolyticus 5.8 log10 CFU/g on both frozen seafood slices after 28 days. The results obtained from this study indicate the LAE-Gelatin-TPS/PBAT and Nisin-LAE-Gelatin-TPS/PBAT films displayed excellent inhibition against S. Typhimurium and V. parahaemolyticus on chilled and frozen seafood.

Enhancing distributive mixing of immiscible polyethylene/thermoplastic starch blend through zeolite ZSM-5 compounding sequence.

The aim of this work was to explore the effect of zeolite ZSM-5 (ZSM5) incorporation sequence on the phase morphology, microstructure, and performance of polyethylene/thermoplastic starch (PE/TPS) films. Two processing sequences were used for preparing PE/TPS/ZSM5 composites at a weight ratio of PE to TPS of 70:30 and ZSM5 concentrations of 1-5 wt%: (i) melt compounding of PE with ZSM5 prior to melt blending with TPS (SI); and (ii) TPS was compounded with ZSM5 prior to blending with PE (SII). Distributive mixing and mechanical properties of PE/TPS blend were greatly enhanced when ZSM5 was incorporated via SII. These were caused by both the higher affinity between PE and ZSM5, compared to that of TPS and ZSM5, and the reduction of TPS viscosity after compounding with ZSM5, leading to migration of ZSM5 from TPS dispersed phase toward PE matrix and increase in breakup of TPS droplets during SII sequence.

Fabrication of Novel Bioactive Cellulose-Based Films Derived from Caffeic Acid Phenethyl Ester-Loaded Nanoparticles via a Rapid Expansion Process: RESOLV.

Caffeic acid phenethyl ester (CAPE) nanoparticles (NPs) with an average size of ∼40 nm obtained from TEM and binomial average sizes of ∼90 and ∼400 nm obtained from DLS were successfully produced by rapid expansion of subcritical solutions into liquid solvents (RESOLV). The minimum inhibitory concentrations (MICs) and minimum bactericidal concentrations (MBCs) of CAPE and CAPE-NPs were determined by plate count method against 12 pathogenic and spoilage bacteria and 3 strains of yeast. Total phenolic content (TPC) and antioxidant activities of CAPE-NPs were quantified and subsequently investigated using two assays, including 2,2-diphenyl-1-picrylhydrazyl (DPPH) radical scavenging and ferric reducing antioxidant power (FRAP). CAPE-NP-incorporated cellulose-based films were prepared and characterized. MICs and MBCs of CAPE-NPs against most bacteria and Candida albicans were 700 and 1400 µg/mL, respectively. CAPE-NPs yielded a TPC value of 426.74 µgGAE/mg and lower antioxidant activities than those of CAPE in ethanol (CAPE-EtOH), whereas BHT yielded lower FRAP than that of CAPE-NPs. The impregnation of CAPE into cellulose-based films was confirmed by FTIR spectra. Moreover, incorporation of only 0.5 wt % CAPE-NPs into the films resulted in an inhibitory effect against microorganisms. Fortunately, incorporation of higher concentration of CAPE-NPs-MC films led to a significantly higher antioxidant activity and vice versa. This indicated that CAPE-NPs significantly enhanced the antimicrobial and antioxidant activities of CAPE. The results show that the environmentally benign supercritical CO2 technique should be generally applicable to NP fabrication of other important bioactive ingredients, especially in liquid form. In addition, it is suggested that CAPE-NPs can be used to reduce the dosage of CAPE and improve their bioavailability and thus merit further investigation for bioactive packaging film and coating applications.

The formation of fluorinated tetraphenylporphyrin nanoparticles via rapid expansion processes: RESS vs RESOLV.

Organic nanoparticles of a fluorinated tetraphenylporphyrin (TBTPP) were produced by rapid expansion of supercritical CO(2) solutions into both air (RESS) and an aqueous receiving solution containing a stabilizing agent (RESOLV). The effect of processing conditions on both particle size and form was investigated. The size of the porphyrin nanoparticles produced via RESS increased in a well-behaved manner from 40 to 80 nm as the preexpansion temperature increased from 40 to 100 degrees C, independent of porphyrin concentration, degree of saturation, and preexpansion pressure. RESOLV of TBTPP + CO(2) solutions was investigated both for minimizing particle growth in the free jet and for the prevention of particle agglomeration. Anionic, nonionic, and polymeric stabilizing agents for the aqueous receiving solution were considered. Expansion into a 0.05 wt % SDS solution produced nanorods 50-100 nm in diameter with an aspect ratio of 3-5. RESOLV in a 0.025 wt % Pluronic F68 solution produced well-dispersed, individual, spherical nanoparticles averaging 23 +/- 10 to 32 +/- 10 nm in diameter, independent of the rapid expansion processing conditions selected. Furthermore, the resulting nanoparticle suspensions were stable, with particle sizes remaining unchanged after several months. However, some particle agglomeration occurred at higher (i.e., 1 wt % TBTPP in CO(2)) concentrations. Contact-angle measurements on solid TBTPP compacts with the tested receiving solutions indicate that a moderate wetting agent such as Pluronic F68 is most effective for preserving the size and form of the porphyrin nanoparticles produced by RESOLV. Finally, the fact that nanoparticles are produced from RESS of TBTPP, in contrast with other organics for which microparticles are produced, can be explained in terms of the high melting point of TBTPP (388 degrees C), which results in a solid-state diffusion coefficient of TBTPP low enough so that particle coalescence is significantly reduced in the free jet.

RESS for the preparation of fluorinated porphyrin nanoparticles.

Rapid Expansion of Supercritical Solutions (RESS) was used to produce clean, surfactant-free nanoparticles (average size = 60 nm) of a fluorinated tetraphenylporphyrin from supercritical solutions with CO2.

Antioxidant activities of curcumin and ascorbyl dipalmitate nanoparticles and their activities after incorporation into cellulose-based packaging films.

Curcumin (Ccm) and ascorbyl dipalmitate (ADP) nanoparticles (NPs) with average sizes of ∼50 and ∼80 nm, respectively, were successfully produced by rapid expansion of subcritical solutions into liquid solvents (RESOLV). Pluronic F127 was employed as a stabilizer for both Ccm- and ADP-NPs in an aqueous receiving solution. Antioxidant activities of the Ccm-NPs and ADP-NPs were subsequently investigated using four assays, including 2,2-diphenyl-1-picrylhydrazyl (DPPH) radical scavenging, ABTS radical cation decolorization, ß-carotene bleaching, and ferric reducing antioxidant power. Ccm-NPs and ADP-NPs showed higher antioxidant activities than those of Ccm and ADP. Ccm-NPs yielded higher antioxidant activities than those of Ccm in ethanol and water (Ccm-EtOH and Ccm-H(2)O), respectively. ADP-NPs yielded lower antioxidant activities than that of ADP in ethanol (ADP-EtOH) but higher activities than that of ADP in water (ADP-H(2)O). Moreover, incorporation of Ccm-NPs and ADP-NPs into cellulose-based films indicated that Ccm-NPs and ADP-NPs significantly enhanced the antioxidant activities of Ccm and ADP (p < 0.05). Our results show that the environmentally benign supercritical CO(2) technique should be generally applicable to NP fabrication of other important bioactive ingredients, especially in liquid form. In addition, we suggest that Ccm-NPs and ADP-NPs can be used to reduce the dosage of Ccm and ADP and improve their bioavailability, and thus merit further investigation for antioxidant packaging film and coating applications.