Jérôme Peydecastaing

NIR Study of Chemically Modified Cellulosic Biopolymers

ABSTRACT Near-infrared spectral analysis was useful to quantify the ester content of chemically modified cellulose and lignocellulosics. Two kinds of samples were studied, as long aliphatic-chain cellulose esters and wood sawdust chemically-modified either by anhydrides or by ethylene carbonate. It was possible to determine the degree of substitution (DS) of such samples through a correlation by partial least square (PLS) of second-order derivative of NIR spectra. This technique was efficient even when DS values were low, which is difficult to do by using FTIR. It was also possible to distinguish reagent molecules that were attached to the cellulosic substrate by hydrogen bonding from those linked by covalent bonding.

LCA case study: comparison between independent and coproduction pathways for the production of ethyl and n-butyl acetates

PurposeThe production of ethyl acetate and n-butyl acetate was investigated through two different pathways: either by independent reactions or by coproduction. In the coproduction pathway, the n-butyl acetate was produced by reusing the by-products of the synthesis of ethyl acetate. This study provides a comparison of the environmental impacts of these two pathways using a life cycle assessment (LCA). A discussion about the use of LCA on chemicals and its challenges was also developed.MethodsEthyl acetate and n-butyl acetate were synthesized with maximum respect to the principles of green chemistry (use of heterogeneous catalyst, energy savings, minimum steps). An innovative pathway was developed to avoid waste production, by reusing all the by-products of syntheses. After characterizing the feasibility of using these solvents in paint formulations, their potential impacts on the environment were evaluated through a cradle to gate analysis, up to the synthesis at laboratory scale. Most of the foreground data were directly collected with experimental trials. The background data that were not available in the Ecoinvent 3.1 database were estimated thanks to literature or proxys. Evaluations were then performed on the SimaPro 8.1.1 LCA software, using a derivative of ILCD 2011 1.05 as life cycle impact assessment methodology.Results and discussionThe coproduction of both acetates led to the synthesis of purified ethyl acetate (purity of 92.1% w/w) and n-butyl acetate (purity of 97.1% w/w), after distillation. These results were quite similar to those obtained when independent syntheses were carried out. On an environmental point of view, it was found that the reagents preparation was always the step of the process responsible of the majority of the environmental impacts. The comparison between independent syntheses and coproduction showed that recycling the acetic acid produced during the first esterification (ethyl acetate from ethanol and acetic anhydride) led to a decrease of the impacts from 5 to 23% for all the impact categories.ConclusionsThis innovative coproduction of ethyl and n-butyl acetates led to interesting results from both a technical and environmental perspective, with a clear reduction of the environmental impacts. In a context of sustainable chemistry, this appears to be a very interesting way of production. Concerning the LCA of chemicals, a lot of work is still needed in order to improve the accuracy and the reliability of the assessment.

Soy Protein Microparticles for Enhanced Oral Ibuprofen Delivery: Preparation, Characterization, and In Vitro Release Evaluation

The objective of this work was to evaluate soy protein isolate (SPI) and acylated soy protein (SPA) as spray-drying encapsulation carriers for oral pharmaceutical applications. SPI acylation was performed by the Schotten–Baumann reaction. SPA, with an acylation rate of 41%, displayed a decrease in solubility in acidic conditions, whereas its solubility was unaffected by basic conditions. The drug encapsulation capacities of both SPI and SPA were tested with ibuprofen (IBU) as a model poorly soluble drug. IBU-SPI and IBU-SPA particles were obtained by spray-drying under eco-friendly conditions. Yields of 70 to 87% and microencapsulation efficiencies exceeding 80% were attained for an IBU content of 20 to 40% w/w, confirming the excellent microencapsulation properties of SPI and the suitability of the chemical modification. The in vitro release kinetics of IBU were studied in simulated gastrointestinal conditions (pH 1.2 and pH 6.8, 37°C). pH-sensitive release patterns were observed, with an optimized low rate of release in simulated gastric fluid for SPA formulations, and a rapid and complete release in simulated intestinal fluid for both formulations, due to the optimal pattern of pH-dependent solubility for SPA and the molecular dispersion of IBU in soy protein. These results demonstrate that SPI and SPA are relevant for the development of pH-sensitive drug delivery systems for the oral route.

Mixed acylation of Scots pine sawdust and impact on hydrophobicity

Abstract Acetic–fatty esters of Scots pine sawdust (SPS) were obtained by reaction of SPS with mixtures containing acetic–fatty anhydrides and no solvent or catalyst. Such mixtures were synthesized by reaction between a carboxylic acid and acetic anhydride. The global reaction of acetic anhydride and a fatty acid yields at equilibrium a mixture of five compounds: acetic–fatty anhydride, acetic anhydride, fatty acid, acetic acid and fatty anhydride. The influence of temperature, molar ratio, reaction time and length of the fatty chain on the esterification and on the ratio of grafted acetyl/fatty acyl was investigated. Static contact angles (CAs) with water were measured over 5 min. CA values were dependent on the fatty acyl content and independent of the acetyl content. The minimum ester content of the oleoyl group required to obtain permanent water repellency was 25 mmol kg−1. Water vapour adsorption measurements indicated that in contrast to water repellency, hydrophobicity to water vapour was correlated with the total mass acyl content.