Bio-Activation of HA/ß-TCP Porous Scaffolds by High-Pressure CO2 Surface Remodeling: A Novel "Coating-from" Approach.

Biphasic macroporous Hydroxyapatite/ß-Tricalcium Phosphate (HA/ß-TCP) scaffolds (BCPs) are widely used for bone repair. However, the high-temperature HA and ß-TCP phases exhibit limited bioactivity (low solubility of HA, restricted surface area, low ion release). Strategies were developed to coat such BCPs with biomimetic apatite to enhance bioactivity. However, this can be associated with poor adhesion, and metastable solutions may prove difficult to handle at the industrial scale. Alternative strategies are thus desirable to generate a highly bioactive surface on commercial BCPs. In this work, we developed an innovative "coating from" approach for BCP surface remodeling via hydrothermal treatment under supercritical CO2, used as a reversible pH modifier and with industrial scalability. Based on a set of complementary tools including FEG-SEM, solid state NMR and ion exchange tests, we demonstrate the remodeling of macroporous BCP surface with the occurrence of dissolution-reprecipitation phenomena involving biomimetic CaP phases. The newly precipitated compounds are identified as bone-like nanocrystalline apatite and octacalcium phosphate (OCP), both known for their high bioactivity character, favoring bone healing. We also explored the effects of key process parameters, and showed the possibility to dope the remodeled BCPs with antibacterial Cu2+ ions to convey additional functionality to the scaffolds, which was confirmed by in vitro tests. This new process could enhance the bioactivity of commercial BCP scaffolds via a simple and biocompatible approach.

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.

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.

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.