Characterization of Poly(ε-caprolactone)-Based Nanocomposites Containing Hydroxytyrosol for Active Food Packaging

Antioxidant nano-biocomposites based on poly(ε-caprolactone) (PCL) were prepared by incorporating hydroxytyrosol (HT) and a commercial montmorillonite, Cloisite®30B (C30B), at different concentrations. A full structural, thermal, mechanical and functional characterization of the developed nano-biocomposites was carried out. The presence of the nanoclay and HT increased PCL crystallinity, whereas some decrease in thermal stability was observed. TEM analyses corroborated the good dispersion of C30B into the PCL macromolecular structure as already asserted by XRD tests, since no large aggregates were observed. A reduction in oxygen permeability and increase in elastic modulus were obtained for films containing the nanoclay. Finally, the presence of the nanoclay produced a decrease in the HT release from films due to some interaction between HT and C30B. Results proved that these nano-biocomposites can be an interesting and environmentally-friendly alternative for active food packaging applications with antioxidant performance.

Development of novel nano-biocomposite antioxidant films based on poly (lactic acid) and thymol for active packaging

Novel nano-biocomposite films based on poly (lactic acid) (PLA) were prepared by incorporating thymol, as the active additive, and modified montmorillonite (D43B) at two different concentrations. A complete thermal, structural, mechanical and functional characterization of all nano-biocomposites was carried out. Thermal stability was not significantly affected by the addition of thymol, but the incorporation of D43B improved mechanical properties and reduced the oxygen transmission rate by the formation of intercalated structures, as suggested by wide angle X-ray scattering patterns and transmission electron microscopy images. The addition of thymol decreased the PLA glass transition temperature, as the result of the polymer plasticization, and led to modification of the elastic modulus and elongation at break. Finally, the amount of thymol remaining in these formulations was determined by liquid chromatography (HPLC-UV) and the antioxidant activity by the DPPH spectroscopic method, suggesting that the formulated nano-biocomposites could be considered a promising antioxidant active packaging material.

Characterization and ageing study of poly(lactic acid) films plasticized with oligomeric lactic acid

Poly(lactic acid) (PLA) was melt-blended with a bio-based oligomeric lactic acid (OLA) plasticizer at different concentrations between 15 wt% and 25 wt% in order to enhance PLA ductility and to get a fully biodegradable material with potential application in films manufacturing. OLA was an efficient plasticizer for PLA, as it caused a significant decrease on glass transition temperature (Tg) while improving considerably ductile properties. Only one Tg value was observed in all cases and no apparent phase separation was detected. Films obtained by compression moulding were stored during 3 months under ambient controlled conditions and thermal, mechanical, structural and oxygen barrier properties were studied in order to evaluate the stability of the PLA–OLA films over time. Blends with 20 and 25 wt% OLA remained stable and compatible with PLA within the ageing period. Besides, PLA–20 wt% OLA formulation was the only one which maintained its amorphous state with adequate thermal, mechanical and oxygen barrier properties for flexible films manufacturing.

Development of a novel pyrolysis-gas chromatography/mass spectrometry method for the analysis of poly(lactic acid) thermal degradation products

Thermal degradation of PLA is a complex process since it comprises many simultaneous reactions. The use of analytical techniques, such as differential scanning calorimetry (DSC) and thermogravimetry (TGA), yields useful information but a more sensitive analytical technique would be necessary to identify and quantify the PLA degradation products. In this work the thermal degradation of PLA at high temperatures was studied by using a pyrolyzer coupled to a gas chromatograph with mass spectrometry detection (Py-GC/MS). Pyrolysis conditions (temperature and time) were optimized in order to obtain an adequate chromatographic separation of the compounds formed during heating. The best resolution of chromatographic peaks was obtained by pyrolyzing the material from room temperature to 600 °C during 0.5 s. These conditions allowed identifying and quantifying the major compounds produced during the PLA thermal degradation in inert atmosphere. The strategy followed to select these operation parameters was by using sequential pyrolysis based on the adaptation of mathematical models. By application of this strategy it was demonstrated that PLA is degraded at high temperatures by following a non-linear behaviour. The application of logistic and Boltzmann models leads to good fittings to the experimental results, despite the Boltzmann model provided the best approach to calculate the time at which 50% of PLA was degraded. In conclusion, the Boltzmann method can be applied as a tool for simulating the PLA thermal degradation.

Structure, gas-barrier properties and overall migration of poly(lactic acid) films coated with hydrogenated amorphous carbon layers

Hydrogenated amorphous carbon (a-C:H) films were grown on a poly(lactic acid) (PLA) substrate by means of a radiofrequency plasma-enhanced chemical vapour deposition (rf-PECVD) technique with different deposition times (5, 20 and 40 min). The main goal of this treatment was to increase the barrier properties of PLA, maintaining its original transparency and colour as well as controlling interactions with food simulants for packaging applications. Morphological, chemical, and mechanical properties of PLA/a-C:H systems were evaluated while permeability and overall migration tests were performed in order to determine the effect of the plasma treatment on the gas-barrier properties of PLA films and their application in food packaging. Morphological results suggested a good adhesion of the deposited layers onto the polymer surface and the samples treated for 5 and 20 min only slightly darkened the PLA film. X-ray photoelectron spectroscopy revealed that the structural properties of the carbon layer deposited onto the PLA film depend on the exposure time. PLA/a-C:H system treated for 5 min showed the highest barrier properties, while none of the studied samples exceeded the migration limit established by the current legislation, suggesting the suitability of these materials in packaging applications.

Surface modification of cellulose nanocrystals by grafting with poly(lactic acid)

The use of biopolymers obtained from renewable resources is currently growing and they have found unique applications as matrices and/or nanofillers in ‘green’ nanocomposites. Grafting of polymer chains to the surface of cellulose nanofillers was also studied to promote the dispersion of cellulose nanocrystals in hydrophobic polymer matrices. The aim of this study was to modify the surface of cellulose nanocrystals by grafting from L-lactide by ring-opening polymerization in order to improve the compatibility of nanocrystals and hydrophobic polymer matrices. The effectiveness of the grafting was evidenced by the long-term stability of a suspension of poly(lactic acid)-grafted cellulose nanocrystals in chloroform, by the presence of the carbonyl peak in modified samples determined by Fourier transform infrared spectroscopy and by the modification in C1s contributions observed by X-ray photoelectron spectroscopy. No modification in nanocrystal shape was observed in birefringence studies and transmission electron microscopy.

Combined Effect of Poly(hydroxybutyrate) and Plasticizers on Polylactic acid Properties for Film Intended for Food Packaging

Poly(lactic acid) PLA, and poly(hydroxybutyrate) PHB, blends were processed as films and characterized for their use in food packaging. PLA was blended with PHB to enhance the crystallinity. Therefore, PHB addition strongly increased oxygen barrier while decreased the wettability. Two different environmentally-friendly plasticizers, poly(ethylene glycol) (PEG) and acetyl(tributyl citrate) (ATBC), were added to these blends to increase their processing performance, while improving their ductile properties. ATBC showed higher plasticizer efficiency than PEG directly related to the similarity solubility parameters between ATBC and both biopolymers. Moreover, ATBC was more efficiently retained to the polymer matrix during processing than PEG. PLA–PHB–ATBC blends were homogeneous and transparent blends that showed promising performance for the preparation of films by a ready industrial process technology for food packaging applications, showing slightly amber color, improved elongation at break, enhanced oxygen barrier and decreased wettability.

Synthesis and Characterization of Lactic Acid Oligomers: Evaluation of Performance as Poly(Lactic Acid) Plasticizers

The use of fully bio-based and biodegradable materials for massive applications, such as food packaging, is an emerging tendency in polymer research. But the formulations proposed in this way should preserve or even increase the functional properties of conventional polymers, such as transparency, homogeneity, mechanical properties and low migration of their components to foodstuff. This is not always trivial, in particular when brittle biopolymers, such as poly(lactic acid) (PLA), are considered. In this work the formulation of innovative materials based on PLA modified with highly compatible plasticizers, i.e. oligomers of lactic acid (OLAs) is proposed. Three different synthesis conditions for OLAs were tested and the resulting additives were further blended with commercial PLA obtaining transparent and ductile materials, able for films manufacturing. These materials were tested in their structural, thermal and tensile properties and the best formulation among the three materials was selected. OLA with molar mass (Mn) around 1,000 Da is proposed as an innovative and fully compatible and biodegradable plasticizer for PLA, able to replace conventional plasticizers (phthalates, adipates or citrates) currently used for films manufacturing in food packaging applications.

Bok Is Not Pro-Apoptotic But Suppresses Poly ADP-Ribose Polymerase-Dependent Cell Death Pathways and Protects against Excitotoxic and Seizure-Induced Neuronal Injury.

UNLABELLED Bok (Bcl-2-related ovarian killer) is a Bcl-2 family member that, because of its predicted structural homology to Bax and Bak, has been proposed to be a pro-apoptotic protein. In this study, we demonstrate that Bok is highly expressed in neurons of the mouse brain but thatbokwas not required for staurosporine-, proteasome inhibition-, or excitotoxicity-induced apoptosis of cultured cortical neurons. On the contrary, we found thatbok-deficient neurons were more sensitive to oxygen/glucose deprivation-induced injuryin vitroand seizure-induced neuronal injuryin vivo Deletion ofbokalso increased staurosporine-, excitotoxicity-, and oxygen/glucose deprivation-induced cell death inbax-deficient neurons. Single-cell imaging demonstrated thatbok-deficient neurons failed to maintain their neuronal Ca(2+)homeostasis in response to an excitotoxic stimulus; this was accompanied by a prolonged deregulation of mitochondrial bioenergetics.bokdeficiency led to a specific reduction in neuronal Mcl-1 protein levels, and deregulation of both mitochondrial bioenergetics and Ca(2+)homeostasis was rescued by Mcl-1 overexpression. Detailed analysis of cell death pathways demonstrated the activation of poly ADP-ribose polymerase-dependent cell death inbok-deficient neurons. Collectively, our data demonstrate that Bok acts as a neuroprotective factor rather than a pro-death effector during Ca(2+)- and seizure-induced neuronal injuryin vitroandin vivo SIGNIFICANCE STATEMENT Bcl-2 proteins are essential regulators of the mitochondrial apoptosis pathway. The Bcl-2 protein Bok is highly expressed in the CNS. Because of its sequence similarity to Bax and Bak, Bok has long been considered part of the pro-apoptotic Bax-like subfamily, but no studies have yet been performed in neurons to test this hypothesis. Our study provides important new insights into the functional role of Bok during neuronal apoptosis and specifically in the setting of Ca(2+)- and seizure-mediated neuronal injury. We show that Bok controls neuronal Ca(2+)homeostasis and bioenergetics and, contrary to previous assumptions, exerts neuroprotective activitiesin vitroandin vivo Our results demonstrate that Bok cannot be placed unambiguously into the Bax-like Bcl-2 subfamily of pro-apoptotic proteins.

Synthesis and degradation of poly alkyl alpha cyanoacrylates;

Technical report 6520. AD 627 210.

Poly (ADP-ribose) : an international symposium, National Institutes of Health, Bethesda, Maryland, June 11-13, 1973 /

Includes bibliographies.

The Poly-Olbion: a chorographicall description of Great Britain.

Each of the thirty songs is preceded by a double map of the countries referred to, in which the towns, rivers, etc. are represented by allegorical figures.

Chain scission and branching in irradiated poly(tetrafluoroethylene-co-hexafluoropropylene)

The radiation chemistry of poly(tetrafluoroethylene-co-hexafluoropropylene) (FEP) with a TFE mole fraction of 0.90 has been studied under vacuum using Co-60 gamma-radiation over a range of temperatures and absorbed doses. The radiolysis temperatures were 300, 363, 423, 523 and 543 K. New structure formation in the copolymers was analysed by solid-state F-19 NMR spectroscopy. The new structures formed in the copolymers have been identified and the G-values for the formation of new chemical structures have been investigated at 363 and 523 K. These two temperatures are just above and just below the polymer T-g and T-m, respectively. At the lower temperature, there was no evidence for any chain branching and an estimate of G(S) of 1.0 was obtained. A value of G(S) of 1.3 and a minimum value of G(X)(Y) of 1.3 were obtained at 523 K. (C) 2003 Society of Chemical Industry.

Analysis of the phase behavior of the aqueous poly(ethylene glycol)-Ficoll system

The PEG-Ficoll polymer phase system is one that has been overlooked in the past for biotechnology applications because of the stability of its emulsions. However, new applications, such as emulsion coating of cells, are appearing that rely on this very property. Ficoll is highly polydisperse and multimodal with three distinct Ficoll peaks in gel permeation chromatography. As a result, the transition between one-phase and two-phase systems is blurred and the binodials obtained through turbidometric titration and tie-line analysis differ significantly. Moreover, since the three Ficoll peaks partition differently, tie-line analysis cannot be described by a simple model of the aqueous two-phase system. A simple modification to the model allowed for excellent fit, and this modification may prove well-suited for the many practical cases where aqueous two-phase systems fail to display parallel tie-lines as implicitly assumed in the simpler model.

Poly(hydroxyether of phenolphthalein) and its blends with poly(ethylene oxid)

Poly(hydroxyether of phenolphthalein) (PPH) was synthesized through the polycondensation of phenolphthalein with epichlorohydrin. It was characterized by Fourier transform infrared (FTIR) spectroscopy, NMR spectroscopy, and differential scanning calorimetry (DSC). The miscibility of the blends of PPH with poly(ethylene oxide) (PEO) was established on the basis of the thermal analysis results. DSC showed that the PPH/PEO blends prepared via casting from N,N-dimethylformamide possessed single, composition-dependent glass-transition temperatures. Therefore, the blends were miscible in the amorphous state for all compositions. FTIR studies indicated that there were competitive hydrogen-bonding interactions with the addition of PEO to the system, which were involved with (OHO)-O-. . .=C