Fractionation of fish oil with supercritical carbon dioxide

In order to verify the possibility of using supercritical CO₂ (SC-CO₂) to concentrate polyunsaturated ω−3 fatty acids in the form of natural fish oil, experimental phase equilibrium data were measured for a CO₂ – fish oil system. Phase equilibrium was measured at temperatures from 301 to 323 K and pressures from 7.8 to 29.4 MPa, using the dynamic method. The oil solubility and fatty acid composition of the extracts were measured and these data used to verify CO₂ selectivity. The best operational conditions to fractionate the oil were 7.8 MPa and 301.15 K, although in all the conditions analyzed, eicosapentaenoic acid (EPA) could not be fractionalized. The equilibrium for a mixture of 50% fish oil and 50% babassu (Attalea funifera) fat was measured in order to understand how the fatty acid composition influenced the fractionation. It was observed that the solubility of the mixture was an average of the individual solubility values, and the composition of the extracts could be calculated from the individual solubility of each component.     

大蒜超临界CO2萃取物成分分析

对大蒜超临界CO2萃取物进行了GC-MS分析，借助NTST98.L数据库的质谱图数据，参考文献和人工解析对其中的20多种组分进行，定性鉴定，并利用峰面积归一化法进行了初步定量。大蒜风味物的GC-MS分析表明：大蒜超临界CO2萃取物中含有许多水蒸汽蒸馏蒜油中没有检测到的风味成分，其中最显蔷的是蒜素色谱分析中脱水衍生的3-乙烯基-l，2-二硫杂-4-环已烯(3．96％)及3-乙烯基-1．2-二硫杂-5-环己烯(17．88％)，此外还含有少量的亚油酸及油酸。     

Impact of ethanol addition on the solubility of various soybean isoflavones in supercritical carbon dioxide and the effect of glycoside chain in isoflavones

Solubilities of glycoside isoflavones (daidzin, genistin and glycitin) and their aglycons (daidzein, genistein and glycitein) in supercritical carbon dioxide (SCCO₂) were measured. In the SCCO₂-only system, the solubility of glycoside isoflavones was very low. Adding over 0.1 molar fraction of ethanol to SCCO₂ increased the solubility of glycoside isoflavones. The solubility was almost proportional to the third power of the molar fraction of ethanol. Adding ethanol significantly affected the solubility of glycoside isoflavones. In particular, the solubility of daidzin was remarkably increased by ethanol addition. The solubility of six tested isoflavones in SCCO₂ with ethanol was correlated with the second virial coefficient. The solubility depended on seventh power of the molar fraction of ethanol in SCCO₂. This suggested that the addition of ethanol facilitated cluster formation of CO₂ molecules in the supercritical phase, enhancing the solubility of isoflavones. A SCCO₂ and ethanol binary system was especially effective in extracting glycoside isoflavones.     

Fractionation of buffalo butter oil by supercritical carbon dioxide

Buffalo butter oil was fractionated by supercritical carbon dioxide into four fractions (F₁-F₄). Fractionation was performed at 50 and 70 °C over a pressure range of 10.9-40.1 MPa. Short chain fatty acids (C₄-C₈), medium chain fatty acids (C₁₀-C₁₄) and saturated fatty acids were decreased from F₁ to F₄, while long chain fatty acids (C₁₆-C_18:3) and unsaturated fatty acids were increased. Triacylglycerol molecular species exhibited a similar trend as fatty acids. Cholesterol was concentrated in F₁, and with increasing the fluid density, it decreased by more than 50% in F₄. Substantial changes occurred in the chemical composition of the fractions led to distinctive differences in their thermal profile and solid fat content. Fractions obtained in the initial stages of the fractionation exhibited lower melting behavior that obtained in the late stages.     

Extraction of lipids from cherry seed oil using supercritical carbon dioxide

 Cherry seeds (Prunus avium L.) were extracted with compressed carbon dioxide at 313 K and 333 K in the pressure range 18–22 MPa. The influence of superficial velocity was also analysed using values of 0.02, 0.06 and 0.08 cm/s. The extraction yield was increased by a reduction in particle size. The physical and chemical characteristics of the oil were determined. The results, in terms of free fatty acids and sterol compositions, were compared with those obtained when hexane was used as solvent. Other physical and chemical characteristics were also compared with refined hexane-extracted oil. Received: 29 February 2000 / Revised version: 19 April 2999     

Mathematical modelling of soybean oil solubility in supercritical carbon dioxide

The solubility of soybean oil in supercritical carbon dioxide has been determined in the pressure range of 100–300 bar and in the temperature range of 313–323 K. The obtained values (from 0.0005 to 0.02055 g L^?1) have been correlated using four different empirical equations proposed correspondingly by Chrastil, del Valle and Aquilera, Adachi and Lu and Sparks et al. Since the Sparks et al. equation provided the lowest average absolute relative deviation (AARD) (10.25%) than other models in the examined experimental range, a modified equation of Sparks et al. model was developed for predicting the solubility of soybean oil in supercritical carbon dioxide as a function of temperature and density. An improved equation showed the lowest deviation (2.15%) between experimental data than the other empirical equations considered in this study. The proposed equation was also applied for correlating the solubility of linoleic acid (AARD was 2.40%).     

Response surfaces of hazelnut oil yield in supercritical carbon dioxide

Response Surface Methodology was used to determine the effects of solvent flow rate (1, 3 and 5 g/min), pressure (300, 375 and 450 bar) and temperature (40, 50 and 60 °C) on hazelnut oil yield in supercritical carbon dioxide (SC-CO₂). Oil yield was represented by a second order response surface equation (R²=0.997) using Box-Bhenken design of experiments. Oil yield increased with increasing SC-CO₂ flow rate, pressure and temperature. The maximum oil yield was predicted from the response surface equation as 0.19 g oil/g hazelnut (34% of initial oil) when 4 g hazelnut particles (particle diameter<0.85 mm) were extracted with 5 g/min SC-CO₂ flow rate at 450 bar, and 60 °C for 10 min. Total extraction time at these conditions was predicted to be 35 min.     

Effect of supercritical carbon dioxide treatment on the Maillard reaction in model food systems

The effect of supercritical carbon dioxide treatment on the development of the Maillard reaction in powdered model systems of lactose/ovine caseinmacropeptide and lactose/β-lactoglobulin at different pH values was studied. Supercritical carbon dioxide treatments in static conditions at 30 MPa and 50 °C for up to 5 h were applied to model systems. Control experiments at 50 °C were also performed. All assayed model systems treated with carbon dioxide under supercritical conditions showed lower extent of the Maillard reaction than control treated samples. Differences between supercritical carbon dioxide treated and control samples increased with pH. These results indicate that supercritical carbon dioxide treatment of food samples does not favour the Maillard reaction and thus can be applied in foods that may require special care to avoid excessive loss of available lysine.     

Effects of cosolvents on the decaffeination of green tea by supercritical carbon dioxide

Due to the adverse effects of the caffeine in a variety of plant products, many methods have been explored for decaffeination, in efforts to remove or reduce the caffeine contained in plant materials. In this study, in order to remove caffeine from green tea (Camellia sinensis) leaves, we have employed supercritical carbon dioxide (SC–CO₂), which is known to be an ideal solvent, coupled with a cosolvent, such as ethanol or water. By varying the extraction conditions, changes not only in the amount of caffeine, but also in the quantities of the principal bioactive components of green tea, including catechins, such as epigallocatechin gallate (EGCG), epigallocatechin (EGC), epicatechin gallate (ECG) and epicatechin (EC), were determined. The extraction conditions, including temperature, pressure and the cosolvent used, were determined to affect the efficacy of caffeine and catechin extraction. In particular, the type and concentration of a cosolvent used constituted critical factors for the caffeine removal, combined with minimal loss of catechins, especially EGCG. When the dry green tea leaves were extracted with SC–CO₂ modified with 95% (v/v) ethanol at 7.0 g per 100 g of CO₂ at 300 bar and 70 °C for 120 min, the caffeine content in the decaffeinated green tea leaves was reduced to 2.6% of the initial content. However, after the SC–CO₂ extraction, a substantial loss of EGCG, as much as 37.8% of original content, proved unavoidable.     

Deacidification of olive oil by countercurrent supercritical carbon dioxide extraction: Experimental and thermodynamic modeling

Supercritical carbon dioxide was used as an extractive solvent to remove free fatty acids from cold-pressed olive oil. Crude oil of different acidity content (from 0.5 to 4.0 wt%) was extracted in a packed column at 313 K and pressures of 180, 234 and 250 bar. The group contribution equation of state was employed to simulate the separation process, representing the oil as a simple pseudo-binary oleic acid + triolein mixture. Despite the simple representation of oil composition to simulate the deacidification process, a satisfactory agreement between the experimental and calculated yields and acidity of raffinates was obtained. The thermodynamic model was employed to study a continuous countercurrent multistage extraction process which yielded a raffinate having acidity lower than 0.7 wt%, when crude olive oil with different FFA content was processed.     

Extraction and fractionation of alkylresorcinols from triticale bran by two-step supercritical carbon dioxide

Bran from triticale cultivars Ultima and Pronghorn and Canadian Prairie Spring (CPS) wheat were fractionated using a two-step sequential supercritical carbon dioxide (SC-CO₂) extraction technique with and without ethanol to selectively extract and enrich high-value alkylresorcinols (ARs). Pure SC-CO₂ (70 °C; flow rate 25 g/min; pressure 35 MPa), was used for the first extraction step. The non-polar lipids yield ranged from 3.08 to 3.26 g/100 g and they were composed mainly of C18:2 (33-41 g/100 g), C18:1 (15-21 g/100 g), C16:0 (15-19 g/100 g), and C18:3 (4-5 g/100 g) fatty acids. The second extraction step, performed on the bran remaining after the first extraction, was carried out with SC-CO₂ plus 0.5 mL/min ethanol (70 °C; flow rate 5 g/min; pressure 35 MPa). The resulting total polar lipid yield of bran samples ranged between 0.62 and 0.86 g/100 g and the main compounds present in the polar lipids were ARs. The total AR contents of triticale cv Ultima, wheat, and triticale cv Pronghorn were 70, 68 and 36 mg/100 g, respectively. Saturated and unsaturated AR homologues of C15:0, C17:0, C19:0, C19:1, C21:0, C21:1, C23:0 and C25:0 were detected in all samples. Over 98% of the triticale ARs and over 95% of the wheat ARs were extracted under the SC-CO₂ conditions used.     

Drying of foods using supercritical carbon dioxide — Investigations with carrot

The use of supercritical carbon dioxide (scCO₂) for the removal of moisture from cylindrical pieces of carrot has been investigated. The experiments were carried out at 20 MPa pressure and the effects of temperature and co-solvent (ethanol) addition were examined. At the investigated conditions, comparisons with air-drying indicated that drying kinetics and the associated drying mechanisms differed between the techniques. The microstructural characteristics of carrot pieces that had been dried using the different techniques were compared using X-ray microtomography and light microscopy. Carrots dried in the supercritical fluid environment were seen to retain their shape much better than air-dried carrots which underwent shrinkage. Samples dried in ethanol-modified scCO₂ possessed less dense structures and consequently displayed more favourable rehydrated textural properties than the air-dried equivalents.

Industrial relevance

Drying is a common unit operation in food processing, but the rehydrated product is often of very poor quality. Comparatively little work has been done on optimising drying for quality of the final, rehydrated product. Supercritical drying is a possible way of maintaining product microstructure, and this paper describes experiments in which the supercritical drying of carrot is studied and compared with conventional processes.     

Inactivation and structural change of horseradish peroxidase treated with supercritical carbon dioxide

The influence of supercritical carbon dioxide (SCCO₂) at 55 °C on inactivation of horseradish peroxidase (HRP) in buffer solution, pH 5.6, was studied while its structural change was analyzed by far UV-circular dichroism (CD) and tryptophan fluorescence spectroscopy. SCCO₂ treatment had significant effects on the residual activity of HRP, the least residual activity was only 12% at 30 MPa. HRP’s secondary and tertiary structures were changed. The α-helix relative content in the secondary structure decreased and the intrinsic relative fluorescence intensity (RFI) increased as the pressure of SCCO₂ treatment was elevated. The HRP’s inactivation closely corresponded to the loss of α-helix relative content and the increase of RFI. After a 7-day storage at 4 °C, the restoration of residual activity and the reversion of the α-helix relative content were observed while RFI resumed with exception of the 30 MPa treatment.     

Extraction of coffee diterpenes and coffee oil using supercritical carbon dioxide

Commercial green and roasted coffee beans were used to maximize oil extraction and conditions were studied to obtain the highest and lowest diterpene levels on green and roasted coffee oil, respectively. Thus, operational temperatures (60–90 °C) and pressure (235–380 bar) were optimized for coffee oil extraction. Oil content levels and diterpene oil concentration were compared to the results obtained with the extraction with Soxhlet apparatus, using hexane as solvent. In general, an inverse correlation was observed between the amount of extracted oil and diterpene concentration levels. As a result, different oil contents with different diterpene concentrations could be obtained. The HPLC analysis of cafestol and kahweol in the oil extracted from green coffee beans at 70 °C/253 bar resulted in the highest concentration (453.3 mg 100 g⁻¹), which was 48% lower than in the oil extracted with hexane while in the oil extracted from roasted coffee beans at 70 °C/371 bar, resulted in 71.2% reduction of diterpenes.     

Inactivation of polyphenol oxidases in cloudy apple juice exposed to supercritical carbon dioxide

The inactivation of polyphenol oxidase (PPO) in cloudy apple juice exposed to supercritical carbon dioxide (SCCO₂) treatment was investigated. Higher pressure, higher temperature, and longer treatment time caused more inactivation of PPO. The maximum reduction of PPO activity reached more than 60% at 30 MPa and 55 °C for 60 min. The experimental data followed first-order reaction kinetics; the kinetic rate constant k and the decimal reduction time D were closely related to the pressure and temperature of SCCO₂ treatment. Higher pressures or higher temperatures resulted in lower D values (higher k), the D value of PPO was minimized to 145 min treated by the combination of 30 MPa and 55 °C. Activation energy of 18.00 kJ /mol, was significantly reduced by SCCO₂ treatment at 30 MPa, as compared to activation energy of 72.0 kJ/mol for identical treatment at atmospheric pressure. Pressure and temperature sensitivity of kinetic parameters were studied. Z_P at 55 °C was 66.7 MPa and Z_T at 30 MPa was 108 °C.     

Effects of supercritical carbon dioxide treatment for sterilization purpose on meat quality of porcine longissimus dorsi muscle

The objective of this study was to investigate the effect of supercritical carbon dioxide (SC-CO₂) treatment for the sterilization purpose on meat quality and protein denaturation of the porcine longissimus dorsi muscle. The conditions of SC-CO₂ treatment were 7.4 and 15.2 MPa at 31.1 °C for 10 min. SC-CO₂ treatment had no effect on muscle pH, tenderness, and water-holding capacity (WHC). However, the samples treated at 7.4 MPa had a higher lightness value (52.97 vs. 46.94, P<0.001) and a more pronounced extent of sarcoplasmic protein denaturation (73.80 vs. 80.73, P<0.01) than the control samples. These results suggest that the paler color of samples treated with SC-CO₂ was associated with the sarcoplasmic protein denaturation, and the major denaturated proteins were determined to be phosphorylase b (PH), creatine kinase (CK), triosephophate isomerase (TPI), and one unknown protein. On the other hand, other quality traits were generally unaffected by the SC-CO₂ treatments at 7.4 or 15.2 MPa.     

Addition of ethanol to supercritical carbon dioxide enhances the inactivation of bacterial spores in the biofilm of Bacillus cereus

Supercritical carbon dioxide (SC-CO₂) was used to inactivate Bacillus cereus spores inside biofilms, which were grown on stainless steel. SC-CO₂ treatment was tested using various conditions, such as pressure treatment (10–30 MPa), temperature (35–60 °C), and time (10–120 min). B. cereus vegetative cells in the biofilm were completely inactivated by treatment with SC-CO₂ at 10 MPa and at 35 °C for 5 min. However, SC-CO₂ alone did not inactivate spores in biofilm even after the treatment time was extended to 120 min. When ethanol was used as a cosolvent with SC-CO₂ in the SC-CO₂ treatment using only 2–10 ml of ethanol in 100 ml of SC-CO₂ vessel for 60–90 min of treatment time at 10 MPa and 60 °C, B. cereus spores in the biofilm were found to be completely inactivated in the colony-forming test. We also assessed the viability of SC-CO₂-treated bacterial spores and vegetative cells in the biofilm by staining with SYTO 9 and propidium iodide. The membrane integrity of the vegetative cells was completely lost, while the integrity of the membrane was still maintained in most spores. However, when SC-CO₂ along with ethanol was used, both vegetative cells and spores lost their membrane integrity, indicating that the use of ethanol as a cosolvent with SC-CO₂ is efficient in inactivating the bacterial spores in the biofilm.     

Extraction of soybean isoflavones from soybean meal with aqueous methanol modified supercritical carbon dioxide

The effects of modifier composition in terms of methanol content in water, modifier concentration, meal particle size and extraction conditions (temperature, pressure and CO₂ flow rate) on isoflavones recovery from soybean meal by supercritical carbon dioxide (SC–CO₂) extraction were investigated. The highest isoflavones recovery attained was 87.3%, at 40 °C and 50 MPa, using CO₂ flow rate of 9.80 kg/h containing a modifier 7.8 mass% of 80% (v/v) aqueous methanol. Using different modifier concentrations (60–100% methanol) at 50 MPa and 40 °C, it was shown that 80% methanol was optimum for isoflavones extraction. In addition, isoflavones recovery increased with the modifier content in SC–CO₂ up to 10.2%. The optimal particle size was 20–30 mesh with bigger and smaller particles resulting in lower isoflavones recovery. The results showed that increasing the temperature from 40 to 70 °C drastically reduced isoflavones recovery at 50 MPa. The higher the extraction pressure, the higher was the isoflavones recovery. The extraction rate increased with CO₂ flow rate but the percentage recovery was more or less the same.     

Extraction yield of isoflavones from soybean cake as affected by solvent and supercritical carbon dioxide

Soybean cake has been shown to be a rich source of isoflavone and can be produced during processing of soybean oil as byproduct. The objectives of this study were to compare the extraction yield of isoflavone from soybean cake by solvent and supercritical carbon dioxide, and study the conversion of isoflavone glucosides to the biologically active aglycone by employing β-glucosidase. Results showed that with supercritical carbon dioxide extraction, a maximum yield of malonylglucoside and glucoside was generated at 60 °C and 350 bar, while a high level of acetylglucoside and aglycone was produced at 80 °C and 350 bar. Supercritical carbon dioxide extraction resulted in a lower yield of total isoflavone than solvent extraction, but the former was more applicable to extraction of acetylglucoside and aglycone, and the latter to malonylglucoside and glucoside. A peak level of aglycone was attained from conversion of isoflavone glucoside by β-glucosidase at 55 °C, pH 5, concentration 50 U/ml and incubation time of 2 h.     

超临界CO2下酶催化脂质水解反应

近年来以超临界CO_2流体作为反应介质已成为化学和生物化学反应研究一个热点,以超临界CO_2流体为介质进行酶催化脂质水解反应,与其它非水相酶催化介质相比,有其独特优越性。该文介绍超临界CO_2流体特性及在超临界CO_2流体中影响酶催化脂质水解因素。