Enhancement of poly(vinyl ester) solubility in supercritical CO2 by partial fluorination: the key role of polymer-polymer interactions.

An enhancement of poly(vinyl ester) solubility in supercritical carbon dioxide (sc-CO(2)) can be achieved by decreasing the strength of the polymer-polymer interactions. To demonstrate this, a library of statistical copolymers of vinyl acetate and vinyl trifluoroacetate was synthesized by RAFT/MADIX polymerization with varying compositions at a given number-average molecular weight. These copolymers exhibited unprecedentedly low cloud-point pressures in sc-CO(2) at 40 °C compared with previously reported poly(vinyl esters). Surface tension measurements combined with a computational approach evidenced the prominent role played by polymer-polymer interactions.

Investigating the Aroma of Syrah Wines from the Northern Rhone Valley Using Supercritical CO2-Dearomatized Wine as a Matrix for Reconstitution Studies.

This study aimed to investigate the key compounds involved in the aroma of French Syrah wines from the northern Rhone valley from two vintages characterized by distinct climatic conditions. The volatile composition of the wines was assessed through the determination of 76 molecules. After identifying the best matrix and best model for aroma reconstitution studies, omission tests were conducted using the Pivot profile method. For both vintages, 35 molecules with odor activity values (OAVs) above 0.5 were identified. While remarkably high levels of 2-furfurylthiol (FFT) were reported in both wines, rotundone and 3-sulfanylhexanol (3SH) enabled the strongest discrimination between the two wines. Wine dearomatized using supercritical carbon dioxide (sCO2) was identified as the best matrix. The best models built using this matrix were composed of molecules with OAV > 5 and OAV > 10 highlighting that this dearomatization approach can be valuable to reconstitute the aroma of wine using a small number of molecules. For the cool vintage wine, the omission of rotundone and FFT had the greatest impact on the olfactive profile for nonanosmic and anosmic respondents to rotundone, respectively. 3SH, whose omission decreased the rating of the "fruity" attribute, was identified as the main contributor to the aroma of Syrah wine produced in the warm vintage.

Supercritical carbon dioxide processing of pyrethrum oleoresin and pale.

Possible refining of crude hexane extract (CHE) from pyrethrum flowers and further refining of Pyrethrum Board of Kenya (PBK) pale product is investigated with both liquid and supercritical carbon dioxide. The experiments were carried out in a small pilot plant with a 200 mL extractor and three cyclonic separators in series. To understand the dynamics of pyrethrin extraction, CHE was extracted in a single step; pyrethrin concentration was found to be improved from 0.16 to 0.50 g/g. The effects of temperature and pressure on the quality of the extract were studied at 29 degrees C and 80 bar and at 40 degrees C and 100 bar. Liquid CO(2) processing (29 degrees C, 80 bar) yielded slightly better product quality. A comparison study of CHE and PBK pale processing with supercritical CO(2) (40 degrees C, 100 bar) showed that the final products were similar in terms of pyrethrin content. Extraction of both PBK pale and CHE in two steps with different operating conditions improved their purity.

Comparison of different methods for extraction from Tetraclinis articulata: yield, chemical composition and antioxidant activity.

In the present study, three techniques of extraction: hydrodistillation (HD), solvent extraction (conventional 'Soxhlet' technique) and an innovative technique, i.e., the supercritical fluid extraction (SFE), were applied to ground Tetraclinis articulata leaves and compared for extraction duration, extraction yield, and chemical composition of the extracts as well as their antioxidant activities. The extracts were analyzed by GC-FID and GC-MS. The antioxidant activity was measured using two methods: ABTS(•+) and DPPH(•). The yield obtained using HD, SFE, hexane and ethanol Soxhlet extractions were found to be 0.6, 1.6, 40.4 and 21.2-27.4 g/kg respectively. An original result of this study is that the best antioxidant activity was obtained with an SFE extract (41 mg/L). The SFE method offers some noteworthy advantages over traditional alternatives, such as shorter extraction times, low environmental impact, and a clean, non-thermally-degraded final product. Also, a good correlation between the phenolic contents and the antioxidant activity was observed with extracts obtained by SFE at 9 MPa.

Comparison between supercritical CO2 extraction and hydrodistillation for two species of eucalyptus: yield, chemical composition, and antioxidant activity.

In this work, 2 Eucalyptus species extracts (Eucalyptus cinerea and Eucalyptus camaldulensis) were prepared by hydrodistillation (HD) and supercritical carbon dioxide extraction (SCE) techniques. The best yields of E. cinerea and E. camaldulensis (27.5 and 8.8 g/kg, respectively) were obtained using SCE at 90 bar, 40 °C compared to HD (23 and 6.2 g/kg, respectively). Extracts were quantified by gas chromatography-flame ionization detection and identified by gas chromatography-mass spectrometry. 1,8-cineole and p-menth-1-en-8-ol were the major compounds of E. cinerea essential oil obtained by HD (64.89% and 8.15%, respectively) or by SCE (16.1% and 31.87%, respectively). Whereas, in case of E. camaldulensis, 1,8-cineole (45.71%) and p-cymene (17.14%) were the major compounds obtained by HD, and 8,14-cedranoxide (43.79%) and elemol (6.3%) by SCE. Their antioxidant activity was assessed using 2 methods: 2,2-azino-di-3-ethylbenzothialozine-sulphonic acid radical cation (ABTS(•+) ) and 2,2-diphenyl-1-picrylhydrazyl radical (DPPH(•) ). In the SCE extracts from both E. cinerea and E. camaldulensis, a promising radical scavenging activity was observed with ABTS(•+) , (65 and 128 mg/L, respectively). The total phenolics composition of the extracts was measured and the range was 2 to 60 mg of gallic acid equivalent/g dry plant material. The SCE method was superior to HD, regarding shorter extraction times (30 min for SCE compared with 4 h for HD), a low environmental impact, allows production of nondegraded compounds and being part of green chemistry.

Selection of CalB immobilization method to be used in continuous oil transesterification: analysis of the economical impact.

Enzymatic transesterification of triglycerides in a continuous way is always a great challenge with a large field of applications for biodiesel, bio-lubricant, bio-surfactant, etc. productions. The lipase B from Candida antarctica (CalB) is the most appreciated enzyme because of its high activity and its non-regio-selectivity toward positions of fatty acid residues on glycerol backbone of triglycerides. Nevertheless, in the field of heterogeneous catalysis, we demonstrated that the medium hydrophilic nature of the support used for its commercial form (Lewatit VPOC1600) is a limitation. Glycerol is adsorbed onto support inducing drastic decrease in enzyme activity. Glycerol would form a hydrophilic layer around the enzyme resulting in diffusional limitations during triglyceride transfer to the enzyme. Accurel MP, a very hydrophobic macroporous polymer of propylene, was found not to adsorb glycerol. Immobilization conditions using this support were optimized. The best support was Accurel MP1001 (particle size<1000 µm) and a pre-treatment of the support with acetone instead of ethanol enables the adsorption rate and the immobilized enzyme quantity to be maximized. An economical approach (maximization of the process net present value) was expanded in order to explore the impact of immobilization on development of an industrial packed bed reactor. The crucial ratio between the quantity of lipase and the quantity of support, taking into account enzyme, support and equipped packed bed reactor costs was optimized in this sense. The biocatalyst cost was found as largely the main cost centre (2-10 times higher than the investments for the reactor vessel). In consequence, optimal conditions for immobilization were a compromise between this immobilization yield (90% of lipase immobilized), biocatalyst activity, reactor volume and total investments.