Supercritical carbon dioxide combined with high power ultrasound: An effective method for the pasteurization of coconut water

Industrially, thermal treatments are extensively used to inactivate microorganisms in foods. However, the demand for new pasteurization methods with reduced impact on the nutritional content and overall food quality is increasing. In this context, this study investigated and compared the effect of supercritical carbon dioxide (SC-CO₂) alone or in combination with high power ultrasound (HPU) on both the natural microbial flora (mesophilic, lactic acid bacteria and yeast and molds) of coconut water and the pathogenic Gram-negative bacteria Salmonella enterica inoculated in the product. Inactivation kinetics were obtained at 12 MPa, by means of batch apparatuses, at different times (from 1 up to 60 min) and temperature conditions (from 25 up to 45 °C). The synergistic effect of SC-CO₂ + HPU was evident and a higher microbial reduction was achieved compared to SC-CO₂ alone: at 12 MPa and 40 °C about 5 log reductions were achieved for natural microbial flora in about 15 min while about 30 min were needed for SC-CO₂ treatment. The storage study highlighted that SC-CO₂ treated coconut water resulted microbiologically unstable and showed heavy regrowth phenomena during the storage, while, a full shelf life of 4 weeks was assured for SC-CO₂ + HPU treated samples.     

Modeling the inactivation of Staphylococcus aureus and Serratia marcescens in clinical solid waste using supercritical fluid carbon dioxide

The aim of the present study was to determine an effective sterilization method for safe handling and recycle-reuse of clinical solid waste materials. Supercritical fluid carbon dioxide (SC-CO₂) was applied in the inactivation of gram positive Staphylococcus aureus (S. aureus) and gram negative Serratia marcencens (S. marcescens) in clinical solid waste. The colony forming activity of the bacteria was completely lost at pressures 10–40 MPa, temperatures 35–80 °C and treatment period between 5 and 120 min. An increase in pressure at constant temperature and vice versa with the increasing treatment time enhanced the SC-CO₂ inactivation efficiency. The inactivation process was illustrated by the modified Gompertz equation. The SC-CO₂ inactivation of bacteria was compared with the steam autoclaved bacteria. Regrowth of the bacteria was observed in the autoclaved sample while no re-growth was detected in the SC-CO₂ treated clinical solid waste. Results from SEM image analysis, cellular protein and enzymatic activity of untreated, autoclaved and SC-CO₂ treated S. marcescens and S. aureus cells confirmed that SC-CO₂ is an effective sterilization method.     

Supercritical carbon dioxide extraction of microalgae lipid: Process optimization and laboratory scale-up

Supercritical carbon dioxide (SC-CO₂) extraction of lipid from Scenedesmus sp. for biodiesel production was investigated and compared to conventional extraction methods. The effect of biomass pre-treatment prior to extraction and extracting conditions, namely pressure in the range of 200–500 bar, temperatures in the range of 35–65 °C and CO₂ flow rate in the range of 1.38–4.02 g min⁻¹, on SC-CO₂ extraction yield and quality of lipid were investigated. Three levels full factorial design of experiments and response surface methodology was used to model the system. A second order polynomial model was developed and used to predict the optimum conditions. Scaling up to a laboratory larger scale was also tested. The results indicated that SC-CO₂ extraction was superior to other extraction techniques, but exhibited significant variations in yield with changes in operating parameters. In the developed model, it was found that the linear and quadratic terms of the temperature, as well as the interaction with pressure had a significant effect on lipid yield; whereas, their effect on lipid quality was insignificant. The best operating conditions, in the tested range, were 53 °C, 500 bar and 1.9 g min⁻¹, in which lipid extraction yield of 7.41% (dry weight basis) was obtained. Negligible differences were observed when the fatty acid composition of SC-CO₂ extracted lipid was compared to that extracted by the conventional methods. At the optimum conditions, SC-CO₂ extraction was successfully scaled-up by eight-folds and the extracted lipid yield dropped by 16%.     

Water and ethanol as co-solvent in supercritical fluid extraction of proanthocyanidins from grape marc: A comparison and a proposal

Supercritical carbon dioxide (SC-CO₂) extraction of grape marc was studied using water (W) and ethanol (EtOH) as co-solvent at 15% (w/w), 100 and 200 MPa, and 313.15, 323.15 and 333.15 K to analyze their influence upon total phenols of the extracts. The overall extraction curves were determined and suggested 10 MPa and 313.15 K as the best operating conditions for SC-CO₂ + 15%W extraction, and 10 MPa and 333.15 K for SC-CO₂ + 15% EtOH. The phenolic yields obtained were 63.4 g/kg of extract for SC-CO₂ + 15% W and 38.8 g/kg of extract for SC-CO₂ + 15% EtOH. An alternative method combining Sc-CO₂ + 15% W extraction, followed by SC-CO₂ + 15% EtOH was tested. This procedure provided the best results allowing to obtain the highest phenolic yield (68.0 g/kg of extract), phenol content (733.6 mg GAE/100 g DM), proanthocyanidins concentration (572.8 mg catechin/100 g DM) and antioxidant activity (2649.6 mg α-tocopherol/100 g DM). SC-CO₂ methods were compared with methanol extraction.     

Combined high hydrostatic pressure and carbon dioxide inactivation of pectin methylesterase,polyphenol oxidase and peroxidase in feijoa puree

A combined treatment of high hydrostatic pressure (HHP) and dense phase carbon dioxide (DPCD) was investigated to inactivate pectin methylesterase (PME), peroxidase (POD) and polyphenol oxidase (PPO) in feijoa (Acca sellowiana) puree. The treatments were HHP (HHP); carbonation and HHP (HHPcarb); carbonation + addition of 8.5 mL CO₂/g puree into the headspace of the package and HHP (HHPcarb + CO₂). The different samples were treated at 300, 450 and 600 MPa, for 5 min.The residual POD and PPO activity decreased in the order HHP > HHPcarb > HHPcarb + CO₂ at all pressures used. Treatments with HHP at 300 MPa increased POD activity to 140%. The residual PME activity of HHPcarb and HHPcarb + CO₂ samples at 600 MPa (45–50%) was significantly (p < 0.05) lower than for HHP treatment (65%).The simultaneous application of HHP and DPCD seems to synergistically enhance the inactivation of the enzymes studied, the CO₂ concentration being a key process factor.     

Inactivation of microbes using compressed carbon dioxide—An environmentally sound disinfection process for medical fabrics

High-pressure (HP) CO₂ treatment was applied to disinfect a fabric which is frequently used in hospitals. The physical properties of the treated textile were evaluated and found not to be negatively influenced. Subsequently, the significance of the main parameters influencing the disinfection process were determined using multi-factor analysis of variance. Efficacy of the developed technique was demonstrated and optimised for Gram-negative Escherichia coli and Gram-positive Micrococcus luteus. Water addition was found to be crucial for the reduction of both bacteria species. Complete inactivation was achieved at temperatures as low as 20 °C for E. coli and 65 °C for M. luteus, respectively. The effective pressure required for the disinfection was only 50 bar. Finally, based on the experimentally revealed results, an empirical non-linear model was developed describing the inactivation of E. coli and M. luteus in the low-temperature process using highly compressed liquid, gaseous or supercritical CO₂.     

Validation of a mathematical model for predicting high pressure carbon dioxide inactivation kinetics of Escherichia coli spiked on fresh cut carrot

Inactivation kinetics of Escherichia coli spiked on fresh cut carrot and exposed to high pressure carbon dioxide (HPCD) treatment at several conditions of pressure (6, 8, 10, and 12 MPa) and two conditions of temperature (26 and 35 °C) were obtained as a function of the treatment time (up to 30 min).The Weibull model was applied to fit the inactivation kinetics and calculate δ and n model parameters for each pressure and temperature. The results demonstrated that the model was able to fit with good agreement the inactivation curves (high R² and low RMSE values). In a second attempt, the model parameters were correlated with CO₂ density resulting in a linear relationship. Validation of the proposed model was also performed at 6.6 and 10 MPa, 26 °C and at 8 MPa, 35 °C providing log reduction residual values (observed value–predicted value) lower than 0.50 and showing a good agreement between the experimental and the predicted inactivation data.The model proved to be a powerful tool to fit and predict, in the proposed operative range, the inactivation kinetics of E. coli spiked on fresh cut carrot treated by HPCD. The results demonstrated the potential of a relative simple correlative model for the interpretation of the inactivation data and for HPCD process design and optimization.     

Effects of supercritical CO2 extracts of Melia azedarach L. on the control of fall armyworm (Spodoptera frugiperda)

This work reports the use of Melia azedarach L. extracts obtained from supercritical carbon dioxide extraction (SC-CO₂) as an insecticidal agent against fall armyworm (Spodoptera frugiperda). For this purpose, SC-CO₂ extractions were performed, varying the pressure (150–250 bar), temperature (313–333 K), sample particle size and extraction time. Secondary metabolites from the classes of coumarins, sterols and terpenes were identified in the extracts, with the triterpene melianone being the major constituent. For the biological activity tests, diets were prepared with different SC-CO₂ extract concentrations (100, 500, 1000 and 5000 mg/kg) and offered to S. frugiperda (Lepidoptera: Noctuidae). The results indicated that mortality increased with increasing extract concentrations with 50% mortality (LC₅₀) at a concentration of 376.74 mg/kg and reaching 100% mortality at 5000 mg/kg. The inhibition of insect growth was observed at higher concentrations due to the antifeedant action of the extract. At the lowest extract concentration (100 mg/kg), ingestion caused low pupal viability and adults presenting morphological deformities, which thus indicated a chronic toxicity effect.     

Digestive enzymes characterization of krill (Euphausia superba) residues deoiled by supercritical carbon dioxide and organic solvents

In this study, Enzyme activities of krill were characterized before and after lipid extraction by supercritical carbon dioxide (SC-CO₂) and organic solvent, n-hexane and acetone. Krill SC-CO₂ extraction was performed under the conditions of temperature range from 35 to 45 °C and pressure, 150–250 bar for 2.5 h with a constant flow rate of 22 g/min. Extraction yields of lipids increased with pressure and temperature. The digestive enzyme activities of protease, lipase and amylase of SC-CO₂ treated krill residues were slightly decreased comparing to organic solvent, n-hexane and acetone treated residues. In SC-CO₂ treated samples, all of the digestive enzymes showed slightly higher temperature stability. In the other hand the crude extracts of SC-CO₂ and n-hexane treated krill samples showed almost same optimum pH and pH stability for each of the digestive enzymes. It was also found in SDS-PAGE that there are no significant differences in protein patterns of the crude extracts of untreated, SC-CO₂, n-hexane and acetone treated krill indicating no denaturation of proteins.     

Supercritical CO2 extraction of omega-3 rich oil from Sacha inchi (Plukenetia volubilis L.) seeds

Supercritical carbon dioxide (SC-CO₂) was employed to extract omega-3 rich oil from Sacha inchi (Plukenetia volubilis L.) seeds and partially defatted cake. For ground seeds, the supercritical extraction was carried out at temperatures of 40, 50 and 60 °C and pressures of 300 and 400 bar, and for the cold pressed partially defatted cake, the extraction was carried out with 300 bar at 40 °C and with 400 bar at 60 °C. The global extraction yields (X₀), oil solubility, fatty acid composition of the oil and tocopherol content were determined. The seed samples used in this work contained 54.3% oil, of which 50.5% was linoleinc acid (ω-3). The maximum extraction recovery for the seeds as 92% at 400 bar and 60 °C, but on one occasion a recovery of 99.1% oil was obtained when cold pressed extraction was employed, followed by supercritical extraction at 400 bar and 60 °C. A high tocopherol content of about 2–3 g/kg of oil was obtained.     

Ethanol modified supercritical carbon dioxide extraction of flavonoids from Momordica charantia L. and its antioxidant activity

Ethanol modified supercritical carbon dioxide (SC-CO₂) extraction of flavonoids from Momordica charantia L. fruits and its antioxidant activity were performed. The influences of parameters such as temperature, extraction time and pressure on the yield of flavonoids were investigated. The antioxidant activities of flavonoids were assessed by means of 2,2-diphenyl-1-picrylhydrazyl (DPPH) radical-scavenging assay and β-carotene bleaching test. The experimental data obtained indicated that pressure, temperature and time had significant effect on the extraction yield. The optimum extraction conditions, determined by the 3D response surface and contour plots derived from the mathematical models, were as follows: extraction temperature 46 °C, pressure 33.4 MPa, and extraction time 53.2 min. Under these conditions, the experimental value was 15.47 mg/g, which was well matched with value predicted by the model. The antioxidant activity of flavonoids obtained by ethanol modified SC-CO₂ extraction method had higher antioxidant activity than the flavonoids extracted by conventional solvent extraction (CSE) method. The DPPH radical-scavenging ability of flavonoids obtained by ethanol modified SC-CO₂ extraction method reached to 96.14 ± 1.02%, equivalent to the clearance rate of ascorbic acid at 1.2 mg/mL. Results indicated that ethanol modified SC-CO₂ extraction was a suitable approach for the selective extraction of flavonoids from M. charantia L.     

Characterization of wheat bran oil obtained by supercritical carbon dioxide and hexane extraction

Supercritical carbon dioxide (SC-CO₂) and soxhlet extraction using was carried out to extract oil from wheat bran oil. For SC-CO₂, the pressure and temperature were ranging from 10 to 30 MPa and 313.15–333.15 K. The extraction was performed in a semi batch process with a CO₂ flow rate of 26.81 g/min for 2 h. Wheat bran oil was characterized to investigate the quality. Acid value (AV) and peroxide value (POV) were higher in hexane extracted oil compared to SC-CO₂ extracted oil. Induction period was measured by rancimat test. The oil obtained by SC-CO₂ extraction had higher capability to delay the oxidation by surrounding environment. The DPPH radical scavenging activity was also measured. The SC-CO₂ extracted oil showed higher radical scavenging activity compared to hexane extracted oil.     

High pressure phase behavior of poly[isopropyl acrylate] and poly[isopropyl methacrylate] in supercritical fluid (SCF) solvent and SCF solvent + cosolvent mixtures

Cloud-point data are reported for poly(isopropyl acrylate) [P(IPA)] in CO₂, propane, propylene, butane, 1-butene, and dimethyl ether (DME) and for poly(isopropyl methacrylate) [P(IPMA)] in CO₂. P(IPA) + alkene cloud-point curves are ∼100 °C lower than the P(IPA) + alkane curves, which are close to the P(IPA) + CO₂ curve located at temperatures greater than 130 °C and pressures of 2500 bar. P(IPA) dissolves in pure DME at conditions as mild as 50 °C and 200 bar. Since IPA and IPMA monomers are used as cosolvents with CO₂, binary IPA + CO₂ and IPMA + CO₂ data are reported to complement the ternary cloud-point data. Both monomer + CO₂ mixtures exhibit type-I behavior and both are adequately modeled with the Peng–Robinson equation of state. IPMA is a more effective cosolvent than IPA. The polymer + CO₂ + monomer phase behavior suggests that it is viable to polymerize IPA or IPMA in CO₂ at moderate operating conditions.     

Supercritical extraction of carob kibbles (Ceratonia siliqua L.)

Carob pulp kibbles, a by-product of carob been gum production, was studied as a source of bioactive agents. Firstly, the carob kibbles were submitted to an aqueous extraction to extract sugars, and supercritical fluid extraction (SFE) was applied to the solid residue of that aqueous extraction, by using compressed carbon dioxide (SC-CO₂) as the solvent and a mixture of ethanol and water (80:20, v/v) as a co-solvent. Pressure and temperature were studied in the ranges 15–22 MPa, and 40–70 °C. Particle diameter, and co-solvent percentage in ranges of 0.27–1.07 mm, and 0–12.4%, respectively, were also studied, as well as the flow rate of SC-CO₂ between 0.28 and 0.85 kg h⁻¹, corresponding, respectively, to 0.0062 and 0.0210 cm s⁻¹ of superficial velocity. The extracts were characterised in terms of antioxidant capacity by DPPH method, and total phenolics content by the Folin–Ciocalteu method. The central composite non-factorial design was used to optimise the extraction conditions, using the Statistica, version 6 software (Statsoft). The best results, in terms of yield and antioxidant capacity, were found at 22 MPa, 40 °C, 0.27 mm particle size, about 12.4% of co-solvent and a flow rate of 0.29 kg h⁻¹ of SC-CO₂. The phenolics profile of the extracts obtained at these conditions was qualitatively evaluated by HPLC-DAD. The solid residue of the supercritical extraction was also studied showing to be a dietary fiber, which can be compared to Caromax™, a carob fiber commercialised by Nutrinova Inc.     

Response surface optimization of supercritical CO2 extraction of α-tocopherol from gel and skin of Aloe vera and almond leaves

Supercritical fluid extraction (SFE) was studied as an alternative technology in the pharmaceutical industry for the separation of α-tocopherol from gel and skin of Aloe vera and almond leaves. The influence of operating conditions was investigated on the recovery of supercritical carbon dioxide (SC-CO₂) extraction of α-tocopherol from three-year old Aloe vera (Aloe barbadensis Miller) leaf gel. The obtained results were compared with the conventional Soxhlet extraction. Response surface methodology (RSM) was applied to optimize effective variables on the extracted recovery of α-tocopherol. The maximum α-tocopherol recovery of 53.41% from Aloe vera gel was obtained with employing RSM predicted optimal operating conditions of 32 MPa, 45.91 °C, 0.84 ml SC-CO₂/min and 140 min for extraction. The α-tocopherol extraction yield for gel and skin of Aloe vera and almond leaves at these optimal operating conditions were obtained 1.53, 16.29 and 2.61 mg/100 g dry sample, respectively.     

Supercritical carbon dioxide extraction of bioactive flavonoid from Strobilanthes crispus (Pecah Kaca)

The bioactive flavonoid compounds of Strobilanthes crispus (Pecah Kaca) leaves obtained by using supercritical carbon dioxide (SC-CO₂) extraction were investigated and the obtained crude extract yields were compared in order to select the best operation parameters. Since carbon dioxide is a non-polar solvent, ethanol was used as co-solvent to increase the polarity of the fluid. The studied parameters were pressure (100, 150 and 200 bar), temperature (40, 50 and 60 °C) and dynamic extraction time (40, 60 and 80 min). The optimum extraction condition occurred at 200 bar, 50 °C and 60 min. Based on the mean value, pressure had dominant effect on the extraction yield. Apart from the optimum SFE conditions two other conditions namely at minimum (100 bar, 40 °C, 40 min) and maximum (200 bar, 60 °C, 80 min) levels of each studied parameters as control runs were analyzed by HPLC to determine the major bioactive flavonoid compounds from S. crispus. Under the optimum conditions eight flavonoid compounds were identified; they were (+)-catechin, (?)-epicatechin, rutin, myricetin, luteolin, apigenin, naringenin and kaempferol.     

Antibacterial activity of organomontmorillonites and organovermiculites prepared using chlorhexidine diacetate

Organoclays with antibacterial activity were prepared from cation exchanged Ag⁺, Cu^2 + and Zn^2 + forms of montmorillonite and vermiculite using five concentrations of chlorhexidine diacetate. The samples were characterized by X-ray diffraction (XRD) and Fourier transform infrared spectroscopy (FTIR). The antibacterial activity against Enterococcus faecalis, Escherichia coli and Pseudomonas aeruginosa was evaluated by finding the minimum inhibitory concentration (MIC). All prepared organomontmorillonites and organovermiculites showed the best antibacterial activity against an E. coli bacterial strain.     

Preparation of superhard BxCy fibers by microvortex-flow hyperbaric laser chemical vapor deposition

A novel class of freestanding B_xC_y fibers was prepared by hyperbaric-pressure laser chemical vapor deposition. Utilizing mixtures of diborane and helium with hydrocarbons, such as methane, ethene, and pentane, B_xC_y-alloy fibers were prepared at axial rates of up to 12.2 μm/s. Regions of kinetically-limited and transport-limited growth were identified, and the activation energy for deposition from B₂H₆ + C₅H₂₀ + He mixtures (at relative concentrations of 1:25:10) was found to be 197 ± 27 kJ/mol, while the rate constant was approximately 1810 μm/s. Compositions ranged from B_0.4C_0.6 to B_0.03C_0.97 depending on the gas mixture and laser powers employed; axial and radial fiber compositions/microstructure were explored using Auger spectroscopy and electron microscopy. Glassy B_xC_y fibers with Vickers hardnesses of 42–45 GPa were grown at laser powers below 150 mW. The growth kinetics of pure boron fibers was also investigated from BCl₃ + H₂, BF₃ + H₂, and B₂H₆ + H₂ gas mixtures, producing fine-grained α-boron and large single-crystals of β-boron. Micro-scale vortices in the gas flow emanating from the reaction zone were observed using particle image velocimetry; such vortices enhance axial fiber growth rates through rapid gas mixing. Arrays of fibers were also grown in-parallel using diffractive optical elements.     

Response surface optimization of Smyrnium cordifolium Boiss (SCB) oil extraction via supercritical carbon dioxide

In this study, the essential oil of aerial parts of a species of a plant called Smyrnium cordifolium Boiss (SCB) was extracted by supercritical CO₂. The essence was analyzed by the method of GC/MS. Design of experiments was carried out with response surface methodology by Minitab 16 software to optimize four operating variables of supercritical carbon dioxide (SC-CO₂) extraction (pressure, temperature, CO₂ flow rate and extraction dynamic time). This is the first report announcing optimization of the operation of supercritical extraction of SCB in laboratorial conditions. Optimizing process was done to achieve maximum yield extraction. Independent variables were dynamic time (t_d), pressure (P), temperature (T) and flow rate of SC-CO₂ (Q) in the range of 30–150 min, 10–30 MPa, 40–60 °C and 0.5–1.7 ml/min, respectively. The experimental optimal recovery of essential oil (0.8431, w/w%) was obtained at 13.43 MPa, 40 °C, 150 min (dynamic) and 1.7 ml/min (CO₂ flow rate).     

Effect of supercritical CO2 flux,temperature and processing time on physicochemical and morphological properties of commercial reverse osmosis membranes

Coupling supercritical CO₂ (SC-CO₂) extraction with membrane separation leads to energy savings by recycling CO₂ at supercritical state while separating extract components. However, high pressure operating conditions may cause physicochemical and morphological changes in polymer membranes, which in turn can adversely affect membrane performance. In this study, the effect of different flux (50 and 200 kg/m² h), temperature (40 and 80 °C) and time (0–8 h) levels were investigated at 120 bar on two commercial reverse osmosis membranes, AK and SG using contact angle, ATR-FTIR and FE-SEM measurements. Contact angle of AK increased substantially with high flux and high temperature processing unlike SG. The peaks assigned to N–H and carbonyl groups at 1541, 1609 and 1663 cm⁻¹ showed the highest decrease in absorbance with high flux processing while high temperature was more effective on O–H groups between 2700 and 3700 cm⁻¹. AK membrane exhibited the formation of bead-like structures at different processing times and conditions. The effect of SC-CO₂ processing on the membranes varied depending on their chemical structure, which is important to understand for further process development.