Preparation of micro particles of functional pigments by gas-saturated solution process using supercritical carbon dioxide and polyethylene glycol

Particle design is presently a major development of supercritical fluids applications, mainly in the paint, cosmetic, pharmaceutical, and specialty chemical industries. The particles from the gas-saturated solutions (PGSS) process were used to micronize the functional compounds, fucoxanthin and astaxanthin. Fucoxanthin was extracted from brown seaweed using supercritical carbon dioxide (SC-CO₂) at 20 MPa and 45 °C. The particle formation of functional pigments with biodegradable polymer, polyethelene glycol (PEG) was performed by PGSS using SC-CO₂ in a thermostatted stirred vessel. Different temperatures (40 and 50 °C) and pressures (10–30MPa) were applied to optimize the conditions for the formation of functional pigment particles. Two nozzles of different diameter (250 and 300 μm) were used for PGSS and the reaction time was 1 hr. The average diameter of the particles obtained by PGSS at different conditions was about 0.78–1.42 μm.     

Supercritical anti-solvent micronization of marigold-derived lutein dissolved in dichloromethane and ethanol

This work aims to study supercritical anti-solvent (SAS) micronization of lutein derived from marigold flowers. Lutein solution in dichloromethane (DCM) or ethanol was atomized into the stream of supercritical carbon dioxide (SC-CO₂) through a concentric nozzle in a pressurized vessel. The effects of pressure and SC-CO₂ flow rate on morphology, mean particle size (MPS) and particle size distribution (PSD) were investigated. The reduction in lutein MPS from 202.3 μm of unprocessed lutein to 1.58 μm and 902 nm could be achieved by SAS micronization using DCM and ethanol, respectively. In both solvent systems, no significant effects of pressure and SC-CO₂ flow rate on particle morphology were observed. However, pressure was found to have a significant effect on MPS and PSDs of lutein particles.     

Extraction of bioactive components from Centella asiatica using subcritical water

Bioactive components, asiatic acid and asiaticoside, were extracted from Centella asiatica using subcritical water as an extraction solvent. Extraction yields of asiatic acid and asiaticoside were measured using high-performance liquid chromatography (HPLC) at temperatures from 100 to 250 °C and pressures from 10 to 40 MPa. As temperature or pressure increased, the extraction yield of asiatic acid and asiaticoside increased. At the optimal extraction conditions of 40 MPa and 250 °C, the extraction yield of asiatic acid was 7.8 mg/g and the extraction yield of asiaticoside was 10.0 mg/g. Extracted asiatic acid and asiaticoside could be collected from water as particles with a simple filtering process. Dynamic light scattering (DLS) was used to characterize particle size. Particles containing asiatic acid were larger (1.21 μm) than particles containing asiaticoside (0.76 μm). The extraction yields of asiatic acid and asiaticoside using subcritical water at 40 MPa and 250 °C were higher than extraction yields using conventional liquid solvent extraction with methanol or ethanol at room temperature while the subcritical water extraction yields were lower than extraction yields with methanol or ethanol at its boiling point temperature.     

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.     

Flexural strength and fracture behavior of ZrB2–SiC ultra-high temperature ceramic composites at 1800 °C

ZrB₂–15 vol.%SiC and ZrB₂–30 vol.%SiC composites with smaller starting particle sizes in which the particle sizes of ZrB₂ and SiC are 2 μm and 0.5 μm, respectively, demonstrated marked plasticity and significant reduction in the flexural strength at 1800 °C. The flexural strengths of these two composites are 112 ± 12 MPa and 48 ± 10 MPa, respectively, and their corresponding strength retentions are 13% and 7%, respectively. Large ZrB₂ grains were commonly observed in the samples containing 15 vol.%SiC, which are always the sites for the crack initiation. Cavities were found in the samples containing 30 vol.%SiC and the grain boundaries are the main sites for the crack and cavity nucleation. To improve ultra-high temperature strength, larger starting particle sizes (ZrB₂ and SiC are 5 μm and 2 μm, respectively) were used for the preparation of ZrB₂–15 vol.%SiC. This sample fractured in an elastic manner up to 1800 °C and showed a very high strength with a value of 217 ± 16 MPa.     

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.     

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.     

Influence of silicon carbide particle size on the microstructure and mechanical properties of zirconium diboride–silicon carbide ceramics

The influence of silicon carbide (SiC) particle size on the microstructure and mechanical properties of zirconium diboride–silicon carbide (ZrB₂–SiC) ceramics was investigated. ZrB₂-based ceramics containing 30 vol.% SiC particles were prepared from four different α-SiC precursor powders with average particle sizes ranging from 0.45 to 10 μm. Examination of the dense ceramics showed that smaller starting SiC particle sizes led to improved densification, finer grain sizes, and higher strength. For example, ceramics prepared from SiC with the particle size of 10 μm had a strength of 389 MPa, but the strength increased to 909 MPa for ceramics prepared from SiC with a starting particle size of 0.45 μm. Analysis indicates that SiC particle size controls the strength of ZrB₂–SiC.     

Enzymatic conversion of corn oil into biodiesel in a batch supercritical carbon dioxide reactor and kinetic modeling

Synthesis of fatty acid methyl esters (FAME) as biodiesel from corn oil was studied in a batch supercritical carbon dioxide (SC-CO₂) bioreactor using immobilized lipase (Novozym 435) as catalyst. Effects of reaction conditions on the contents of FAME, monoacylglycerols (MAG), diacylglycerols (DAG), and triacyglycerols (TAG) were investigated at various enzyme loads (5–15%), temperatures (40–60 °C), substrate mole ratios (corn oil:methanol; 1:3–1:9), pressures (10–30 MPa), and times (1–8 h). The highest FAME content (81.3%) was obtained at 15% enzyme load, 60 °C, 1:6 substrate mole ratio, and 10 MPa in 4 h. A reaction kinetic model was used to describe the system, and the activation energy of the system was calculated as 72.9 kJ/mol. Elimination of the use of organic solvents, chemical catalysts and wastewater as well as reasonably high yields make the enzymatic synthesis of biodiesel in SC-CO₂ a promising green alternative to conventional biodiesel process.     

Supercritical anti-solvent micronization of chromatography purified marigold lutein using hexane and ethyl acetate solvent mixture

This work aims to study supercritical anti-solvent micronization of marigold derived purified lutein that was dissolved in the mixture of hexane and ethyl acetate (70:30 v/v), the solvent used as the mobile phase for chromatographic purification. The results show significant effect of pressure on the morphology of micronized lutein particles. The increase in lutein initial concentration from 1.5 mg/ml to 3.2 mg/ml and the increase in SC-CO₂ flow rate from 15 ml/min to 25 ml/min show no significant effects on the morphology of lutein particles. However, the reduction of mean particle size from about 2 μm to 0.8 μm was observed by increasing SC-CO₂ flow rate. The X-ray diffraction patterns of the micronized lutein particles show apparent amorphous nature, while the Fourier transform infrared spectroscopy results show that no chemical structural changes occurred. Moreover, the solubility of the micronized lutein particles in aqueous solution was found to increase significantly from being almost insoluble to having approximately 20% solubility     

Ball milling assisted hydrothermal synthesis of ZrO2 nanopowders

The formation of ZrO₂ nanopowders under various hydrothermal conditions such as temperature, time, autoclave rotation speed, heating rate and particularly assistance of ball milling during reaction was investigated. Full ZrO₂ formation (with monoclinic phase) from zirconium solution was completed at shorter times with increasing temperature such as after 4 h at 150 °C, 2 h at 175 °C and less than 2 h at 200 °C. Crystallite size increased from 2.9 to 4 nm with increasing reaction temperature from 125 °C to 200 °C, respectively. Ball milling assisted hydrothermal runs were performed to understand the effect of mechanical force on phase formation, crystallinity and particle size distribution. Monoclinic ZrO₂ was formed in both milled and non-milled runs when zirconium solution was used. Mean particle size for the 2 M solution was measured to be 94 nm for the milled and 117 nm for the non-milled powders. However, when amorphous aqueous zirconia gels (precipitated at pH 5.8) were used, tetragonal phase was also formed in addition to monoclinic phase. Mean particle size was measured to be 0.7 μm (d₉₀≅1.3 μm) for the milled and 7.9 μm (d₉₀≅13 μm) for the non-milled powders. Ball milling during hydrothermal reactions of both zirconium solution and aqueous zirconium gel resulted in smaller crystallite size and mean particle size and, at the same time, effectively controlled particle size distribution (or agglomeration) of nanopowders.     

Micronization of salicylic acid and taxol (paclitaxel) by rapid expansion of supercritical fluids (RESS)

The particle sizes of the pharmaceutical substances are important for their bioavailability. The bioavailability can be improved by reducing the particle size of the drug. In this study, salicylic acid and taxol were micronized by the rapid expansion of supercritical fluids (RESS). Supercritical CO₂ and CO₂ + ethanol mixture were used as solvent. Experiments were carried out to investigate the effect of extraction temperature (318–333 K) and pressure (15–25 MPa), pre-expansion temperature (353–413 K), expansion chamber temperature (273–293 K), spray distance (6–13 cm), co-solvent concentration (ethanol, 1, 2, 3, v/v, %) and nozzle configuration (capillary and orifice nozzle) on the size and morphology of the precipitated salicylic acid particles. For taxol, the effects of extraction pressure (25, 30, 35 MPa) and co-solvent concentration (ethanol, 2, 5, 7, v/v, %) were investigated. The characterization of the particles was determined by scanning electron microscopy (SEM), optical microscopy, and LC–MS analysis.The particle size of the original salicylic acid particles was L/D: 171/29–34/14 μm/μm. Depending upon the different experimental conditions, smaller particles (L/D: 15.73/4.06 μm/μm) were obtained. The particle size of taxol like white crystal powders was reduced from 0.6–17 μm to 0.3–1.7 μm The results showed that the size of the precipitated salicylic acid and taxol particles were smaller than that of original particles and RESS parameters affect the particle size.     

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.     

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.     

Mathematical modeling of Salmonella typhimurium inactivation under high hydrostatic pressure at different temperatures

Inactivation curves of Salmonella typhimurium under high-hydrostatic pressures (HHPs) (200, 250, 300 and 350 MPa) at different temperatures (15, 25, 35 and 45 °C) in tryptone soy broth were analyzed using the modified Gompertz model. The phase of disappearance (time for inactivation of all cells, λ) and the inactivation rate (μ) of S. typhimurium were inversely related. Inactivation rates of S. typhimurium were higher (P < 0.05) at 45 °C than 15, 25 and 35 °C under HHPs from 200 to 350 MPa. The μ values were ?2.66, ?6.06, ?7.67 and ?7.99 min^?1 at 200, 250, 300 and 350 MPa HHP treatments, respectively, at 45 °C. A negative μ value (always negative) indicates that an increase (become more negative) in μ with increasing pressure or temperature is related to the S. typhimurium inactivation process. The μ values were also increased with increasing temperature from 15 to 45 °C at same treated pressures. Increased pressure and temperature had significant effects on the survival of S. typhimurium. The temperature dependence of the inactivation rate constant was analyzed based on the Arrhenius, linear and square-root models. The pressure sensitivity (low E_μ) determined based on the Arrhenius model was lower at high pressure. E_μ (activation energy) value was 1.94 kJ/mol at 350 Mpa, and 42.88, 12.99 and 3.73 kJ/mol at 200, 250 and 300 MPa, respectively. Results of this study enable the prediction of microbial inactivation exposed to HHPs at different temperatures.     

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).     

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.     

Effect of spinel content on hot strength of alumina-spinel castables in the temperature range 1000–1500°C

Hot modulus of rupture of Al₂O₃-spinel castables containing 5–15 wt% alumina-rich magnesia alumina spinel and 1·7 wt% CaO generally increases with increase in spinel content and temperature from 1000 to 1500°C. The magnitudes of hot modulus of rupture of castables containing 15 wt% spinel and 1·7 wt% CaO are 14·3 MPa at 1400°C and 15·6 MPa at 1500°C, while those of castables containing 20 wt% spinel and 1·7 wt% CaO are 12·5 MPa at 1400°C and 14·7 MPa at 1500°C. The former castables contained 15 wt% spinel of −75 μm size, while the latter contained 10 wt% spinel of +75 μm size and another 10 wt% spinel of −75 μm size. The bond linkage between the CA₆ and spinel grains in the matrix is believed to cause both the spinel content and temperature dependence of hot strength of Al₂O₃-spinel castables, as well as fine grain spinel even in amount less than coarser grain spinel to be more effective for enhancing hot strength. The trend of the magnitude of thermal expansion under load (0·2 MPa) above 1500°C of the castables is not necessarily indicative of the magnitude of hot modulus of rupture at 1400 or 1500°C. ©     

Modelling of the inactivation kinetics of Escherichia coli,Saccharomyces cerevisiae and pectin methylesterase in orange juice treated with ultrasonic-assisted supercritical carbon dioxide

The combined effect of supercritical carbon dioxide (SC-CO₂) and high power ultrasound (HPU) on the inactivation kinetics of Escherichia coli, Saccharomyces cerevisiae and pectin-methyl esterase (PME) in orange juice was studied in order to select models that can predict their inactivation behaviour based on process parameters. Experiments were performed at different temperatures (31–41 °C, 225 bar) and pressures (100–350 bar, 36 °C). The inactivation rate of E. coli, S. cerevisiae and PME increased with pressure and temperature during SC-CO₂ + HPU treatments. The SC-CO₂ + HPU inactivation kinetics of E. coli, S. cerevisiae and PME were represented by models that included temperature, pressure and treatment time as variables, based on the Biphasic, the Peleg Type B, and the fractional models, respectively. The HPU-assisted SC-CO₂ batch system permits the use of mild process conditions and treatment times that can be even shorter than those of continuous SC-CO₂ systems.     

Supercritical CO2 extraction of lutein esters from marigold (Tagetes erecta L.) enhanced by ultrasound

As a novel technique, supercritical CO₂ (SC-CO₂) extraction enhanced by ultrasound was applied to the extraction of lutein esters from marigold and the extraction curves were described by Sovová model. The mass transfer coefficient in the solid phase (k_s) increased from 3.1 × 10⁻⁹ to 4.3 × 10⁻⁹ m/s due to ultrasound. The effect of extraction parameters including particle size of matrix, temperature, pressure, flow rate of CO₂, and ultrasonic conditions consisting of power, frequency and irradiation time/interval on the yield of lutein esters were investigated with single factor experiments. The results showed that the yield of lutein esters increased significantly with the presence of ultrasound (p < 0.05). The maximal yield of lutein esters (690 mg/100 g) was obtained for a particle size fraction of 0.245–0.350 mm, extraction pressure of 32.5 MPa, temperature of 55 °C and CO₂ flow rate of 10 kg/h with ultrasonic power of 400 W, ultrasonic frequency of 25 kHz and ultrasonic irradiation time/interval of 6/9 s.