Influence of pretreatments for extraction of lipids from yeast by using supercritical carbon dioxide and ethanol as cosolvent

Saccharomyces cerevisiae is one of the most studied and industrially exploited yeast. It is a non-oleaginous yeast whose lipids are mainly phospholipids. In this work, the extraction of yeast lipids by supercritical carbon dioxide (SCCO₂) and ethanol as a co-solvent was studied. In particular our attention was focused on the selectivity toward triglycerides, and in a subsequent extraction of the phospholipids present in the yeast. Indeed CO₂ is a non-polar solvent and is not an efficient solvent for the extraction of phospholipids. However, SCCO₂ can be used to extract neutral lipids, as triglycerides, and the addition of polar co-solvents like ethanol, at different compositions, allows a more efficient extraction of triglycerides, and also an extraction-fractionation of phospholipids. In this work SCCO₂ extractions of a specific membrane complex of S. cerevisiae, obtained from an industrial provider, were carried out at 20 MPa and 40 °C, using ethanol as a co-solvent (9%, w/w). It was shown that different pretreatments are necessary to obtain good extraction yields and have a great impact on the extraction. The kinetic of the extractions were successfully modeled using Sovova's model. From the fitting of the main parameters of the model it was possible to compare the effects of the pretreatments over the yeast material, and to better understand the extraction process. Among the seven tested pretreatments the more appropriate was found to be an acid hydrolysis followed by a methanol maceration.     

Micro and nano cellular amorphous polymers (PMMA, PS) in supercritical CO2 assisted by nanostructured CO2-philic block copolymers - One step foaming process

Microcellular foaming of commodity amorphous polymers, poly(methyl methacrylate) (PMMA), and poly(styrene) (PS) was studied in supercritical CO₂ via a batch one-step process in the presence of block copolymers able to change their foaming behaviour and therefore the porous structures. Triblock (styrene-co-butadiene-co-methylmethacrylate SBM, methylmethacrylate-co-butylacrylate-co-methylmethacrylate MAM) terpolymers were blended to PS or PMMA by extrusion. They showed advantages compared to classical PS-PMMA polymer blends in terms of cell size control and reduction of cell size. Foaming is carried out on bulk injection molded samples which were saturated under high pressures of CO₂ (300 bars) at different temperatures (25° C to 80 °C) and different depressurization rates (pressure drop rates from 150 bar/min to 12 bar/min). Very distinct cellular structures and densities were controlled by varying either the copolymer type or the foaming conditions (T,P). Cell sizes ranged from 0.2 μm to 200 μm, and densities from 0.30 g/cm³ to 1 g/cm³ in the polymers considered. Particularly, when triblock copolymers were able to self organize (nanostructuring) in a polymer matrix, they became phase separated at a nanometer level, presenting nanostructured polymers matrixes. To conclude the study, a possible nanostructuring mechanism is suggested based on the interplay between rubbery and highly CO₂-philic blocks/rigid and less CO₂-philic blocks. It is demonstrated that block copolymer additives are a good pathway towards micro and ultra microcellular supercritical CO₂ foaming of amorphous polymers.     

Development of molecularly imprinted co-polymeric devices for controlled delivery of flufenamic acid using supercritical fluid technology

This work reports the development of a novel class of affinity co-polymeric materials using supercritical fluid technology. Polymeric materials with molecular recognition to flufenamic acid, were first synthesized in supercritical carbon dioxide (scCO₂) using the drug as template. Molecularly imprinted co-polymers of methacrylic acid (MAA) or N-isopropyl acrylamide (NIPAAm) crosslinked with ethylene glycol dimethacrylate (EGDMA) were synthesized using different crosslinking degrees and template:monomer ratios, at 65 °C and 21 MPa. High-pressure NMR experiments confirmed that the nature of the interactions between the drug and the functional monomers during the polymerization step are mainly hydrogen bonds. scCO₂-assisted impregnation revealed that the imprinted matrices were able to uptake higher amounts of flufenamic acid. This effect was particularly evidenced in the more crosslinked matrices, with P(MAA-EGDMA) imprinted copolymers binding up to 101.5 mg drug/g polymer against only 50.5 mg/g in the non-imprinted copolymer. In vitro drug delivery experiments showed that imprinted co-polymers release the drug in a more sustained way than the corresponding non-imprinted matrices. Overall it was shown that supercritical fluid technology is a viable approach for the development of self-assembly molecular recognition polymers with potential application in controlled drug delivery systems.     

Synthesis of cross-linked poly(4-vinylpyridine) and its copolymer microgels using supercritical carbon dioxide: Application in the adsorption of copper(II)

Compared with conventional precipitation polymerization method, cross-linked poly(4-vinylpyridine) (P4VP) and its microgels copolymerized with α-methacrylic acid (MAA) were synthesized through a new route of stabilizer-free polymerization in supercritical fluids. The yellow, dry, fine powders were directly obtained from precipitation polymerization of 4-vinylpyridine in supercritical carbon dioxide (scCO₂) at pressures ranging from 70.0 to 230 bar, using N,N′-methylenebisacrylamide as cross-linker. The effects of the reaction pressure, cross-linker ratio, initiator concentration, and reaction time were investigated. The capacity of this microgel for adsorption of copper(II) was also studied. At higher cross-linker concentrations, a high yield of the cross-linked P4VP microgel was generated in scCO₂, and its particle size was less than 300 nm. Polymerization of cross-linked P4VP in scCO₂ was extremely sensitive to the density of the continuous phase. The adsorption followed the Langmuir isotherm. The adsorption capacities of cross-linked P(4VP-co-MAA) and cross-linked P4VP were 47.2 and 26.9 mg g⁻¹, respectively.     

Regeneration of Pd/TiO2 catalyst deactivated in reductive CCl4 transformations by the treatment with supercritical CO2, ozone in supercritical CO2 or oxygen plasma

Carbonaceous deposits formation was established as the primary reason of Pd/TiO₂ catalyst deactivation during reductive processing of CCl₄ to form hydrodechlorination and oligomerization products. Three methods of carbonaceous deposits elimination were tested: (1) extraction by supercritical CO₂, (2) oxidation by ozone in supercritical CO₂, and (3) low-temperature glow-discharge oxygen plasma treatment. Synchronic thermal analysis confirms effective carbonaceous deposits removal during regeneration by ozone or low temperature glow-discharge oxygen plasma; by XPS deep oxidation of surface Pd after oxidative treatment (by ozone or oxygen plasma) was found. Thus H₂ reduction was proposed as the second step making possible full regeneration of initial catalytic activity of Pd/TiO₂.     

A green separation process for recovery of healthy oil from pumpkin seed

In this study, pumpkin seeds, called as “Ürgüp Sivrisi” and grown in Cappadocia region, were used as plant materials because of high aroma contents. In the supercritical fluid extraction of pumpkin seed oil, the effect of main process parameters as the particle size (250-2360 μm), the volumetric flow rate of supercritical solvent (0.06-0.30 L/h), the operating pressure (20-50 MPa), the operating temperature (40-70 °C), the type of entrainer (ethanol and n-hexane) and those concentrations (0-10 vol.%) on the extraction yield, the oil solubility and the initial extraction rate were investigated. A cross-over effect for the extraction of pumpkin seed oil using supercritical CO₂ was determined at the operating pressure of 20-30 MPa. The maximum extraction yield obtained with entrainer free was reached 0.50 g oil/g dry seed at 600-1180 μm, 0.12 L/h, 50 MPa and 70 °C for the operation time of 5 h. The maximum extraction yield obtained with ethanol as an entrainer in the experiments was reached 0.54 g oil/g dry seed at the conditions of 600-1180 μm, 0.12 L/h, 30 MPa, 40 °C and 8 vol.% for the operating time of 2 h. The oil compositions were determined by gas chromatography analysis and the results showed that the compositions of pumpkin seed oil which were obtained by means of organic solvent extraction and supercritical fluid extraction were similar. The average oil compositions determined as 9.3 (±0.43)% palmitic acid, 7.5 (±0.6)% stearic acid, 32.3 (±0.6)% oleic acid, 48.1 (±0.6)% linoleic acid and 0.7 (±0.3)% linolenic acid. The morphological changes in the seeds were determined by the scanning electron microscopy analysis.     

Chitosan—A versatile semi-synthetic polymer in biomedical applications

This review outlines the new developments on chitosan-based bioapplications. Over the last decade, functional biomaterials research has developed new drug delivery systems and improved scaffolds for regenerative medicine that is currently one of the most rapidly growing fields in the life sciences. The aim is to restore or replace damaged body parts or lost organs by transplanting supportive scaffolds with appropriate cells that in combination with biomolecules generate new tissue. This is a highly interdisciplinary field that encompasses polymer synthesis and modification, cell culturing, gene therapy, stem cell research, therapeutic cloning and tissue engineering. In this regard, chitosan, as a biopolymer derived macromolecular compound, has a major involvement. Chitosan is a polyelectrolyte with reactive functional groups, gel-forming capability, high adsorption capacity and biodegradability. In addition, it is innately biocompatible and non-toxic to living tissues as well as having antibacterial, antifungal and antitumor activity. These features highlight the suitability and extensive applications that chitosan has in medicine. Micro/nanoparticles and hydrogels are widely used in the design of chitosan-based therapeuticsystems. The chemical structure and relevant biological properties of chitosan for regenerative medicine have been summarized as well as the methods for the preparation of controlled drug release devices and their applications.     

Fractional factorial design for the optimization of supercritical carbon dioxide extraction of La, Ce and Sm ions from a solid matrix using bis(2,4,4-trimethylpentyl)dithiophosphinic acid + tributylphosphate

In this study, La³⁺, Ce³⁺ and Sm³⁺ were removed from a solid matrix using supercritical CO₂ which contained bis(2,4,4-trimethylpentyl)dithiophosphinic acid (Cyanex 301) as a chelating agent and tributylphosphate (TBP) as a co-extractant. The fractional factorial design, 2⁵⁻¹, was employed to optimize the SFE of these ions from spiked filter paper matrices. Effect of five experimental factors: amount of Cyanex 301, flow rate, temperature, pressure and amount of TBP and each factor at two levels on the SFE of these ions were studied and optimized. The results showed that these ions could be quantitatively extracted from the solid matrix at amount of Cyanex 301 of 0.14 g, flow rate of 4 ml min⁻¹, 313 K, 250 bar and amount of TBP of 30 μl. Finally, by employing a regression analysis a model was proposed. Results showed that obtained recoveries are similar to those predicted by the model.     

Modelling the supercritical fluid extraction of edible oils and analysis of the effect of enzymatic pre-treatments of seed upon model parameters

In this work the supercritical fluid extraction of grape seed oil in a semi-continuous unit has been modelled and discussed in detail. The model embodies the concept of broken plus intact cells, and assumes series mass transfer from intact to broken cells, and then to the fluid phase. The numerical solution has been accomplished by the method of lines using finite differences with upwind flow correction. Experimental extraction curves for both untreated seed and enzymatically pre-treated seed have been modelled in order to evaluate the performance of the model in terms of correlation capability and physical meaning of the parameters. The extraction curves for untreated and treated seed have been accurately represented with average deviations between 2.30 and 7.25%. The model parameters that are intimately related with the internal structure of the seed are the grinding efficiency (or fraction of broken cells) and the internal mass transfer coefficient. Both parameters have been optimised and attained physically sound values, in view of the fact they increased after the enzymatic pre-treatment, and obeyed simple restrictions imposed. The model has been able to generate coherent concentration profiles in the bed and elution curves as well.     

致密气藏压裂液水锁抑制剂筛选及性能评价

为缓解压裂过程造成的水锁伤害,需在压裂液中添加水锁抑制剂。以吸液量、表面张力、接触角、岩心渗透率伤害程度及液锁量等为考察指标,对水锁抑制剂进行了筛选。结果表明,药剂SDY具有良好的防水锁性能,添加SDY的破胶液对岩心渗透率伤害程度较低,液锁量也较小。