Recent Advances in Reactive Extrusion Processing of Biodegradable Polymer‐Based Compositions

This review reports on recent advances in the design of biodegradable polymers built from petroleum and renewable resources using reactive extrusion processing. Reactive extrusion represents a unique tool to manufacture biodegradable polymers upon different types of reactive modification in a cost‐effective way. Partially based on our ongoing research, ring‐opening polymerization of biodegradable polyesters will be approached as well as the chemical modification of biodegradable polymers, particularly natural polymers. The development of environmentally friendly polymer blends as well as (nano)composites from natural polymers, including natural fibers and nanoclays, through reactive extrusion, as an efficient way to improve the interfacial adhesion between these components, will be also discussed.

     

The impact of polypropylene‐graft‐maleic anhydride on the crystallization and dynamic mechanical properties of isotactic polypropylene

Differential scanning calorimetry (DSC) and dynamic mechanical analysis (DMA) were used to identify the mechanisms that lead to differences in the mechanical behavior of formulations of polypropylene blended with maleated polypropylene (MAPP) copolymers. MAPP lowered the melting temperature of PP indicating that less stable crystals were formed possibly because of cocrystallization of PP and MAPP. Crystallization kinetics revealed that copolymers do not change the rate of crystal growth, but may retard nucleation leading to a more spherulitic morphology. The dynamic storage modulus slightly increased in the glassy region with the small addition amounts of MAPP, while mechanical dampening systematically decreased with MAPP addition. An analysis of the viscoelastic behavior did not reveal any real differences in molecular coupling around the β‐transition of PP with the addition of the MAPP copolymer. At low addition levels, MAPP does not appear to have a significant impact on the viscoelastic properties of the polymer blend. © 2008 Wiley Periodicals, Inc. J Appl Polym Sci, 2009     

Melt‐stable poly(1,4‐dioxan‐2‐one) (co)polymers by ring‐opening polymerization via continuous reactive extrusion

Bulk polymerization of ?‐caprolactone (CL), 1,4‐dioxan‐2‐one (PDX), and mixtures of PDX and CL was carried out by initiation with Al(O^secBu)₃ in a co‐rotating twin‐screw extruder through a fast single‐step process. Both homopolymerizations and copolymerization of PDX and CL proceed very rapidly and reach almost complete (co)‐ monomer(s) conversion as soon as 8 mol% of CL are added in the feed. Even though poly(1,4‐dioxan‐2‐one) (PPDX) is known to thermally degrade mainly through unzipping depolymerization promoted from the hydroxyl end‐groups and yielding PDX monomer, it turns out that the thermal stability of PPDX chains is substantially improved by the copolymerization of PDX with limited amounts of CL. Interestingly, DSC analysis of the so‐obtained P(PDX‐co‐CL) copolymers has demonstrated that a CL molar fraction as high as 11 mol% does not prevent the crystallization of the resulting copolymer, which retains a melting temperature close to 95°C. This last observation has been explained by the formation of a blocky‐like copolymer structure, in which short PPDX and PCL sequences are randomly distributed. POLYM. ENG. SCI., 45:622–629, 2005. © 2005 Society of Plastics Engineers.     

Microkinetic model for the pyrolysis of methyl esters: From model compound to industrial biodiesel

A tool for the generation of decomposition schemes of large molecules has been developed. These decomposition schemes contain radicals which can be eliminated from the model equations if both the μ‐hypothesis and the pseudosteady‐state approximation are valid. The reaction rate coefficients and thermodynamic parameters have been calculated by incorporating a comprehensive group additive framework. A microkinetic model for the pyrolysis of methyl esters with a carbon number of up to 19 has been generated using this tool. It is validated by comparing calculated and experimental yields of the pyrolysis of methyl decanoate and novel rapeseed methyl ester pyrolysis data in the temperature range from 800 to 1100 K and methyl ester partial pressure range from 1 × 10^?3 to 1 × 10^?2 MPa. This modeling frame work allows to not only assess the use of methyl ester mixtures as potential feedstock for olefin production but also their effect as blend‐in or trace impurity. © 2015 American Institute of Chemical Engineers AIChE J, 61: 4309–4322, 2015     

Transformation of Free and Dipeptide‐Bound Glycated Amino Acids by Two Strains of Saccharomyces cerevisiae

The yeast Saccharomyces cerevisiae transforms branched‐chain and aromatic amino acids into higher alcohols in the Ehrlich pathway. During microbiological culturing and industrial fermentations, this yeast is confronted with amino acids modified by reducing sugars in the Maillard reaction (glycation). In order to gain some preliminary insight into the physiological “handling” of glycated amino acids by yeasts, individual Maillard reaction products (MRPs: fructosyllysine, carboxymethyllysine, pyrraline, formyline, maltosine, methylglyoxal‐derived hydroimidazolone) were administered to two strains of S. cerevisiae in a rich medium. Only formyline was converted into the corresponding α‐hydroxy acid, to a small extent (10 %). Dipeptide‐bound pyrraline and maltosine were removed from the medium with concomitant emergence of several metabolites. Pyrraline was mainly converted into the corresponding Ehrlich alcohol (20–60 %) and maltosine into the corresponding α‐hydroxy acid (40–60 %). Five specific metabolites of glycated amino acids were synthesized and characterized. We show for the first time that S. cerevisiae can use glycated amino acids as a nitrogen source and transform them into new metabolites, provided that the substances can be transported across the cell membrane.     

Antifungal Activity of Lactic Acid Bacteria Isolated from Peanuts,Gari, and Orange Fruit Juice against Food Aflatoxigenic Molds

This study aims to evaluate the antifungal activity of lactic acid bacteria (LAB) from some Cameroonian food commodities against mycotoxigenic and spoilage molds. Following LAB isolation, the antifungal activity of the isolates was assessed. The organic acids were quantified using high-performance liquid chromatography and the ability of the LAB to reduce mold biomass and aflatoxin production was evaluated. The LAB were identified and the biopreservative potential of strain LO3 was evaluated on tomato paste. Nine percent of the strains isolated showed broad antifungal activity. The activity was due to the effect of organic acids comprising lactic, acetic, 4-hydroxy-3-phenyllactic and 3-phenyllactic acids. Lactobacillus plantarum LO3 exhibiting the highest and broadest antifungal activity was selected and showed the capacity to inhibit fungal growth and aflatoxin production in vitro. Moreover, this strain and its cell-free supernatant showed the ability to prevent aflatoxigenic mold growth in tomato paste without altering its physico-chemical and organoleptic properties.     

Cytotoxicity of CeO2 nanoparticles for Escherichia coli. Physico-chemical insight of the cytotoxicity mechanism

The production of nanoparticles (NPs) is increasing rapidly for applications in electronics, chemistry, and biology. This interest is due to the very small size of NPs which provides them with many interesting properties such as rapid diffusion, high specific surface areas, reactivity in liquid or gas phase, and a size close to biomacromolecules. In turn, these extreme abilities might be a problem when considering a potentially uncontrolled exposure to the environment. For instance, nanoparticles might be highly mobile and rapidly transported in the environment or inside the body through a water or air pathway. Accordingly, the very fast development of these new synthetic nanomaterials raises questions about their impact on the environment and human health. We have studied the impact of a model water dispersion of nanoparticles (7 nm CeO2 oxide) on a Gram-negative bacteria (Escherichia coli). The nanoparticles are positively charged at neutral pH and thus display a strong electrostatic attraction toward bacterial outer membranes. The counting of colony forming units (CFU) after direct contact with CeO2 NPs allows for the defining of the conditions for which the contact is lethal to Escherichia coli. Furthermore, a set of experiments including sorption isotherms, TEM microscopy, and X-ray absorption spectroscopy (XAS) at cerium L3 edge is linked to propose a scenario for the observed toxic contact.     

Extraction of Bitter Acids from Hops and Hop Products Using Pressurized Solvent Extraction (PSE)

The EBC method 7.7, currently used for determination of bitter acids in hop products, is a time‐consuming and laborious extraction technique. In this paper, our aim was to propose a new extraction method based on Pressurized Solvent Extraction (PSE) sometimes also called Pressurized Fluid Extraction (PFE) or Accelerated Solvent Extraction (ASE). Compared to conventional extractions, PSE offers a number of important benefits. PSE on OnePSE^® automated extractor was used for extraction of α‐ and β‐acids from hops and hop products and the parameters influencing extraction efficiency and the influence of the sample preparation method were studied. The quantitative determination of α‐ and β‐acids in the extracts was accomplished by using an HPLC apparatus equipped with diode array detector. The experimental results were compared with those obtained by the standard EBC 7.7 method and the two methods were found to be fully compatible