Wood Esterification by Fatty Acids Using Trifluoroacetic Anhydride as an Impelling Agent and Its Application for the Synthesis of a New Bioplastic.

Fatty acids (FA) and their derivatives with long alkyl chain structures are good candidates for wood esterification to confer thermoplastic properties to wood. Nevertheless, they do not react easily with hydroxyl groups of wood. In this study, we investigated the reactivity of wood with various fatty acids of different chain lengths using trifluoroacetic anhydride (TFAA) as the impelling agent in various reaction conditions. Generally, the esterification of fatty acids without solvents resulted in higher Weight Percentage Gain (WPG) and ester content than the reaction in the presence of CH2Cl2. The esterification reaction could be performed effectively at room temperature, though an increased reaction temperature provoked degradation of the esterified wood. WPG of 67% was obtained for the C3 and 253% for the C16 alkyl chain analogs, respectively. Nevertheless, the ester content was fairly uniform, with values between 10.60 and 11.81 mmol ester/gram of wood for all chain lengths. A higher quantity of reagent led to higher ester content, which tended to stabilize after a ratio of 1:4 wood and TFAA/FA. The esterification reaction was performed rapidly, with an ester content between 7.65 and 9.94 mmol ester/gram of wood being achieved only after 15 min of reaction. Fourier transform infrared spectroscopy (FTIR) analysis was performed to confirm the drastic chemical changes of wood before and after esterification. Morphological observation by scanning electron microscope (SEM), softening measurement by thermomechanical analysis (TMA), and contact angle measurements demonstrated the possibility of esterified spruce wood being applied as a new bioplastic.

Effect of Tannins Addition on Thermal Stability of Furfurylated Wood.

This article presents the effect of the addition of condensed tannins, used as a reticulation agent, on the polymerization of furfuryl alcohol during wood furfurylation, as well as the effect of these condensed tannins on the thermal stability of modified wood. Three kinds of dicarboxylic acids (adipic acid, succinic acid, and tartaric acid), as well as glyoxal, used as model of a wood reticulation agent, were used to catalyze the polymerization of furfuryl alcohol or tannin-furfuryl alcohol solutions. Impregnation of furfuryl alcohol or tannin-furfuryl alcohol solution into the wood, followed by curing at 103 °C for a specific duration, was performed for the wood modification. The thermal stability of the obtained tannin-furfuryl alcohol polymers and their corresponding modified woods was investigated. The leaching resistance and dimensional stability of the modified woods were also evaluated. Results indicated that the partial substitution of furfuryl alcohol by the tannins improved the polymerization reactivity in conditions where furfuryl alcohol alone did not lead to the formation of a solid polymeric material. The thermal stability and leaching resistance of the furfurylated wood in the presence of tannins were improved. Dimensional stability was also improved for furfurylated samples, but the effect of tannin addition was not so obvious, depending on the acidic catalyst used.

Fully wood based novel translucent and thermoplastic materials by solvent-free esterification.

Wood has been investigated for bioplastic production because of its abundance and biorenewability to reduce dependence on petro-based plastics. A series of experiments have been carried out to graft myristic acid, chosen as the fatty acid model, onto spruce sawdust using trifluoroacetic anhydride (TFAA) as the impelling agent without any solvent. The reaction was performed rapidly, leading to high ester content. Most of the hydroxyl groups in wood structure reacted with myristic acid, as demonstrated by FTIR and CPMAS 13C NMR. XRD measurements indicated a decrease in wood crystallinity. Myristic acid-esterified wood showed higher thermal stability by TGA and DSC and delivered several softening temperatures, as observed by TMA. Thermoplastic and translucent films were obtained after pressing at a high temperature. Scanning electron micrographs revealed that pressed esterified wood at the high temperature showed complete disappearance of fibrous structure to a smooth and homogenous surface, indicating that thermal fluidity was achieved during pressing. Esterified sawdust film also showed surface hydrophobicity by contact angle measurements.

Differences between ß-Ala and Gly-Gly in the design of amino acids-based hydrogels.

Despite the continuous interest in organogels and hydrogels of low molecular weight gelators (LMWG), establishing the relationship between the molecular structure and the gelation mechanism is still a challenge. In this paper our interest focuses on the consequences of slight molecular modifications on the self-assembling behaviour of ß-Ala vs Gly-Gly-based hydrogelators. Previously, in our group, amino acid based amphiphiles i.e. Gly-Gly-His-EO2-Alk, a trimodular amphiphile (containing three domains: H-bond donor and acceptor/hydrophilic/hydrophobic domain, respectively) were reported to act as hydrogelators and that the gelation properties were related to hydrogen bonding, hydrophobic interactions and π-π stacking. Herein, ß-Ala-His-EO2-Alk was fully characterised by FT-IR, NMR, SAXS and SEM and the gelation mechanism is discussed. It appears that the number of amide groups determines the self-assembling behaviour into 1D or 2D/3D networks as a result of intimate interactions between gelator molecules.

Synthetic Rhamnolipid Bolaforms trigger an innate immune response in Arabidopsis thaliana.

Stimulation of plant innate immunity by natural and synthetic elicitors is a promising alternative to conventional pesticides for a more sustainable agriculture. Sugar-based bolaamphiphiles are known for their biocompatibility, biodegradability and low toxicity. In this work, we show that Synthetic Rhamnolipid Bolaforms (SRBs) that have been synthesized by green chemistry trigger Arabidopsis innate immunity. Using structure-function analysis, we demonstrate that SRBs, depending on the acyl chain length, differentially activate early and late immunity-related plant defense responses and provide local increase in resistance to plant pathogenic bacteria. Our biophysical data suggest that SRBs can interact with plant biomimetic plasma membrane and open the possibility of a lipid driven process for plant-triggered immunity by SRBs.

Interactions of sugar-based bolaamphiphiles with biomimetic systems of plasma membranes.

Glycolipids constitute a class of molecules with various biological activities. Among them, sugar-based bolaamphiphiles characterized by their biocompatibility, biodegradability and lower toxicity, became interesting for the development of efficient and low cost lipid-based drug delivery systems. Their activity seems to be closely related to their interactions with the lipid components of the plasma membrane of target cells. Despite many works devoted to the chemical synthesis and characterization of sugar-based bolaamphiphiles, their interactions with plasma membrane have not been completely elucidated. In this work, two sugar-based bolaamphiphiles differing only at the level of their sugar residues were chemically synthetized. Their interactions with membranes have been investigated using model membranes containing or not sterol and with in silico approaches. Our findings indicate that the nature of sugar residues has no significant influence for their membrane interacting properties, while the presence of sterol attenuates the interactions of both bolaamphiphiles with the membrane systems. The understanding of this distinct behavior of bolaamphiphiles towards sterol-containing membrane systems could be useful for their applications as drug delivery systems.