Christian Gardrat

Biobased composites from glyoxal-phenolic resins and sisal fibers.

Lignocellulosic materials can significantly contribute to the development of biobased composites. In this work, glyoxal-phenolic resins for composites were prepared using glyoxal, which is a dialdehyde obtained from several natural resources. The resins were characterized by (1)H, (13)C, 2D, and (31)P NMR spectroscopies. Resorcinol (10%) was used as an accelerator for curing the glyoxal-phenol resins in order to obtain the thermosets. The impact-strength measurement showed that regardless of the cure cycle used, the reinforcement of thermosets by 30% (w/w) sisal fibers improved the impact strength by one order of magnitude. Curing with cycle 1 (150 degrees C) induced a high diffusion coefficient for water absorption in composites, due to less interaction between the sisal fibers and water. The composites cured with cycle 2 (180 degrees C) had less glyoxal resin coverage of the cellulosic fibers, as observed by images of the fractured interface observed by SEM. This study shows that biobased composites with good properties can be prepared using a high proportion of materials obtained from natural resources.

Valorization of an industrial organosolv–sugarcane bagasse lignin: Characterization and use as a matrix in biobased composites reinforced with sisal fibers

In the present study, the main focus was the characterization and application of the by‐product lignin isolated through an industrial organosolv acid hydrolysis process from sugarcane bagasse, aiming at the production of bioethanol. The sugarcane lignin was characterized and used to prepare phenolic‐type resins. The analysis confirmed that the industrial sugarcane lignin is of HGS type, with a high proportion of the less substituted aromatic ring p‐hydroxyphenyl units, which favors further reaction with formaldehyde. The lignin–formaldehyde resins were used to produce biobased composites reinforced with different proportions of randomly distributed sisal fibers. The presence of lignin moieties in both the fiber and matrix increases their mutual affinity, as confirmed by SEM images, which showed good adhesion at the biocomposite fiber/matrix interface. This in turn allowed good load transference from the matrix to the fiber, leading to biobased composites with good impact strength (near 500 J m−1 for a 40 wt% sisal fiber‐reinforced composite). The study demonstrates that sugarcane bagasse lignin obtained from a bioethanol plant can be used without excessive purification in the preparation of lignocellulosic fiber‐reinforced biobased composites displaying high mechanical properties. Biotechnol. Bioeng. 2010;107:612–621.

Intramolecular homolytic displacements 7 — Free radical additions to unsaturated peroxy compounds : Synthesis of oxygenated heterocycles

Abstract Free radical additions of hydrogen donor solvents to tert-butyl perpent-4-enoate have given 4-substituted γ-butyrolactones, with yields of 50 % or greater. Such reactions applied to allyl-tert-butyl peroxide have produced 2,3-epoxypropanation of these solvents. Similar addition-elimination processes occurred with tert-butyl 4-methyl-perpent-4-enoate, tert-butyl 2,2-dimethyl-perpent-4-enoate and tert-butyl-methallyl peroxide, but they failed with tert-butyl 5-methyl-perhex-4-enoate and tert-butyl-3-methyl-but-2-enyl peroxide.

Synthesis and complexation properties of two new curcuminoid molecules bearing a diphenylmethane linkage

Abstract Bis-curcuminoids 3 and 4 , bearing a diphenylmethane bridge for both compounds and a crown ether chain adapted to complex Li + for compound 4 , were synthesized and characterized by mass and NMR spectroscopies. By their preorganized geometry, they represent a new class of curcuminoids able to complex transition metal cations. Their absorption spectra in DMF by comparison with those of curcumin 1 and dimethylcurcumin 2 have shown that the phenolate forms in the two halves are in interaction in compound 3 and are independent in compound 4 . Complexation studies have revealed a poor selectivity of curcuminoids for transition metals. Nevertheless complexation of Cu (II), studied by UV–visible absorption spectroscopy, has shown subtle differences between curcumin 1 and bis-curcuminoid 3 . These observations were supported by quantum mechanic calculations to establish the most probable structures of non- and complexed compounds.

Biocompósitos de matriz glioxal-fenol reforçada com celulose microcristalina

Glyoxal, which can be obtained from biomass (as by lipids oxidation), is non-toxic and non-volatile. It was used as a substitute of formaldehyde, which does not have these properties, in the synthesis of a novolac-type phenolic resin, using oxalic acid as a catalyst, which can also be obtained from renewable sources. The glyoxal-phenol resin was used in the preparation of composites reinforced with microcrystalline cellulose (MCC 30, 50, and 70% w/w). Scanning electron microscopy (SEM) images of the fractured surfaces showed that the composites presented a good reinforcement/matrix interface. This can be attributed to the high surface area of the MCC and also to the presence of polar groups (hydroxyl) in both cellulose and matrix, which allowed the formation of hydrogen bonds, leading to a good adhesion between the components present at the interface. Dynamic mechanical thermoanalysis (DMTA) showed that all of the obtained composites have high storage modulus at room temperature. Moreover, the composite reinforced with 30% of MCC showed the lowest water absorption, almost the same as that of the phenolic thermoset, which is used in industrial applications. The results showed that composites with good properties can be prepared using high proportions of materials obtained from biomass.

Photodegradation of sugarcane bagasse fibers: influence of acetylation or grafting UV-absorber and/or hindered nitroxide radical on their photostability

Unbleached (SCB) and peroxide bleached (PB-SCB) sugarcane bagasse fibers were grafted with hydroxyphenylbenzotriazole UV absorber (1) and/or hindered nitroxide radical of piperidinyloxy type (3). PB-SCB fibers were also acetylated with acetic anhydride. The photosensitivity of the various fibers to UV light was comparatively evaluated using Lab color coordinates and by monitoring their UV-Visible diffuse reflectance spectra. SCB fibers were found to be photostable whereas PB-SCB fibers presented some sensitivity to UV light. The stability of SCB fibers was attributed to the presence of photostable para-hydroxyphenylpropane units in SCB lignin. The grafted and non-grafted SCB fibers showed similar behaviors against UV-Visible light whereas grafted PB-SCB were photostabilized by the presence of 2 or 4 or both. Acetylation of PB-SCB fibers induced photostabilization in addition to some photobleaching effect. The photobleaching was also revealed by fluorescence emission studies. As a consequence of these observations, SCB fibers might be considered to have a high potential for lignocellulosic materials to be used outdoors.

Active naringin-chitosan films: impact of UV irradiation.

Bioactive citrus extract-chitosan films were prepared through solvent casting-evaporation method. The impact of near UV irradiation was studied to reach a better understanding of the film behavior. The antimicrobial activity of films against Listeria innocua was maintained after UV irradiation. To study the interaction between chitosan and citrus extract components, naringin (main component) was selected as the model compound. UV treatment caused modifications of the flavanone regardless of the solvent used for its dissolution, depending on the concentration of naringin in the film: the greater the concentration the lower the modification. DSC results suggested cross-links due to UV irradiation and interactions between naringin and chitosan. This was confirmed by a decrease in the naringin release from the irradiated samples. Naringin- and citrus extract-chitosan films showed an increased absorbance in the UV region compared to pure chitosan films, showing potentiality for decreasing the lipid oxidation induced by UV light in foodstuffs.

In vitro inhibitory effect of tetrahydrocurcuminoids on Fusarium proliferatum growth and fumonisin B1 biosynthesis

Many plant pathogens produce toxic metabolites when growing on food and feed. Some antioxidative components seem to prevent fungal growth and mycotoxin formation. Recently, we synthesized a new class of powerful antioxidative compounds, i.e. tetrahydrocurcuminoids, and its structure/antioxidant activity relationships have been established. The South West of France produces large amounts of corn, which can be infected by Fusarium species, particularly F. proliferatum. In this context, the efficiency of tetrahydrocurcuminoids, which can be obtained from natural curcuminoids, was investigated to control in vitro the growth of F. proliferatum and the production of its associated mycotoxin, fumonisin B1. The relation between structure and antifungal activity was studied. Tetrahydrocurcumin (THC1), with two guaiacyl phenolic subunits, showed the highest inhibitory activity (measured as radial growth on agar medium) against the F. proliferatum development (67% inhibition at a concentration of 13.6 µmol ml−1). The efficiencies of THC2 (36% at a concentration of 11.5 µmol ml−1), which contains syringyl phenolic units, and THC3 (30% at a concentration of 13.6 µmol ml−1), which does not have any substituent on the aromatic rings, were relatively close. These results indicate that the simultaneous presence of guaiacyl phenols and the enolic function of the β-diketone moiety play an important role in the inhibition mechanisms. The importance of this combination was confirmed using n-propylguaiacol and acetylacetone as molecular models. Under the same conditions, ferulic acid and eugenol, other natural phenolic antioxidants, were less efficient in inhibiting fungal growth. THC1 also reduced fumonisin B1 production in liquid medium by approximately 35, 50 and 75% at concentrations of 0.8, 1.3, and 1.9 µmol ml−1, respectively. These very low inhibitory concentrations show that tetrahydrocurcuminoids could be one of the most promising biobased molecules for the control of mycotoxinogen fungal strains.

The use of lysozyme to prepare biologically active chitooligomers

Two types of crustacean commercial chitosans (CS1, CS2) were dissolved in lactic acid solutions, hydrolysed by lysozyme and finally fractioned by methanol solutions into two parts containing chito-oligomers (CS-O1, CS-O2). The antioxidant power and antimicrobial properties of both fractions were studied and compared with non-hydrolysed CS1 and CS2. The antioxidant properties were determined by the ferric ion reducing antioxidant power (FRAP) method while the bioactive properties were evaluated against a strain of Listeria monocytogenes. CS-O obtained from the solid fraction of the chito-oligomers solid fractions treated with 90% methanol showed the highest reducing power. Microbiological tests showed that CS-O exhibit higher antilisterial activity than CS.

Styrene-Spaced Copolymers Including Anthraquinone and β-O-4 Lignin Model Units: Synthesis, Characterization and Reactivity Under Alkaline Pulping Conditions

A series of random copoly(styrene)s has been synthesized via radical polymerization of functionalized anthraquinone (AQ) and β-O-4 lignin model monomers. The copolymers were designed to have a different number of styrene spacer groups between the AQ and β-O-4 lignin side chains aiming at investigating the distance effects on AQ/β-O-4 electron transfer mechanisms. A detailed molecular characterization, including techniques such as size exclusion chromatography, MALDI-TOF mass spectrometry, and (1)H, (13)C, (31)P NMR and UV-vis spectroscopies, afforded quantitative information about the composition of the copolymers as well as the average distribution of the AQ and β-O-4 groups in the macromolecular structures. TGA and DSC thermal analysis have indicated that the copolymers were thermally stable under regular pulping conditions, revealing the inertness of the styrene polymer backbone in the investigation of electron transfer mechanisms. Alkaline pulping experiments showed that close contact between the redox active side chains in the copolymers was fundamental for an efficient degradation of the β-O-4 lignin model units, highlighting the importance of electron transfer reactions in the lignin degradation mechanisms catalyzed by AQ. In the absence of glucose, AQ units oxidized phenolic β-O-4 lignin model parts, mainly by electron transfer leading to vanillin as major product. By contrast, in presence of glucose, anthrahydroquinone units (formed by reduction of AQ) reduced the quinone-methide units (issued by dehydration of phenolic β-O-4 lignin model part) mainly by electron transfer leading to guaiacol as major product. Both processes were distance dependent.