Composition Analysis of Black Pepper Oil Resin by Supercritical Fluid Extraction
The optimum conditions for supercritical CO2 extraction of Black Pepper Oil were as follows:
Pulverization degree: 60 mesh
Extraction pressure: 30 Mpa
Extraction temperature: 50°C
Extraction time: 3h
Under the static conditions of supercritical CO2 extraction pressure of 30 Mpa, extraction time of 3 h and extraction temperature of 50 °C, the black pepper raw materials without any treatment, absolute ethanol treatment and ethyl acetate treatment were extracted. The oleoresin was analyzed by gas chromatography-mass spectrometry coupled with GCMS for the component analysis of the extracted black pepper oleoresin, and the material was qualitatively analyzed by retention index and MS. The results showed that under supercritical extraction conditions, there were 22 aroma components of black pepper oleoresin without pretreatment, and 17 kinds of aroma components of black pepper oleoresin pretreated with absolute ethanol. There are 41 aroma components of the pre-treated black pepper oleoresin.
Most of the extraction of black pepper oleoresin is based on solvent extraction, supplemented by ultrasound and microwave. Among them, although the solvent extraction method has a large amount of treatment, it has disadvantages such as a large amount of solvent, a long extraction time, destruction of an active ingredient, and residual organic solvent. Supercritical CO2 extraction is usually carried out at low temperature, which can effectively prevent oxidation and escape of heat-sensitive components. CO2 is a gas under normal conditions, non-toxic, easy to remove after separation of extract components, and completely solvent-free, effectively solving the traditional extraction method. Solvent residue problems and low product aroma quality issues. Supercritical CO2 has gradually become an effective and widely used technology for extracting essential oils and oleoresins from natural products. Supercriticality has been seen as an alternative to traditional solvent extraction and molecular distillation techniques. The extraction process of black pepper oleoresin was studied by supercritical CO2, and the extraction process was optimized with oleoresin yield and piperine recovery. Enzyme-assisted supercritical extraction of black pepper oleoresin was used to investigate the effects of temperature, pressure, time and enzyme dosage on oleoresin yield, piperine content and resin oxidation resistance. Pepper oleoresin was obtained by Soxhlet extraction and its composition was analyzed by GCMS. The black pepper extract of the supercritical extraction was subjected to GCMS analysis, and the identified components contained piperine.
Most of the chemical composition analysis of pepper is focused on the analysis of pepper essential oil. The volatile components of white pepper were analyzed by GCMS using steam distillation and headspace sampling method. GCMS analysis of the volatile oil components of white pepper was carried out. Most of the research on black pepper oleoresin focuses on the extraction process of oleoresin, and there are few studies on the analysis of oleoin components. In addition, for the supercritical CO2 extraction, the entrainer dynamic extraction method is used. The pretreatment of the sample is first studied, and the research on the extraction of black pepper oleoresin by supercritical static method is less. Therefore, this study chose to extract black pepper oleoresin by supercritical CO2 static method, pre-treat the sample by solvent soaking, determine the oleoresin yield and the content of piperine in the resin, and pass GCMS to the black pepper oleoresin. Analysis of aroma components provides a reference for further development of black pepper oleoresin.
1 Materials and methods
a.1 Black pepper raw material
Analytical pure ethanol
Ethyl acetate analysis
Analytical pure sodium sulfate
a.3 Instruments and equipment
Vacuum drying oven
Supercritical CO2 extraction equipment
b.1 Preparation of black pepper oleoresin
Black pepper granules were crushed, passed through a 60 mesh sieve, accurately weighed 100.0 g, and charged into an extraction vessel with a supercritical CO2 extraction apparatus. The extraction pressure was 30 Mpa, the time was 3 h, and the temperature was 50 °C. The black pepper oleoresin S1 was pulverized with black pepper, passed through a 60 mesh sieve, accurately weighed 100.0 g, soaked in 10 mL of absolute ethanol for 24 h, and charged into an extraction vessel with a supercritical CO2 extraction apparatus at an extraction pressure of Black pepper oleoresin S2 was prepared at 30 Mpa for 3 h at a temperature of 50 °C. 100.0 g of black pepper powder was accurately weighed and soaked in 10 mL of ethyl acetate for 24 h. Pepper oleoresin S3.
b.2 Determination of piperine content
The content of piperine in black pepper oleoresin was determined by the method of GBT 175282016 with minor modifications. High performance liquid chromatography was used to detect the column as reverse phase C18 column 2504.6 mm5 m, mobile phase was 77:23 volume methanol and aqueous solution, flow rate was 1.0 mL/min, column temperature was 30 °C, detection wavelength was 343 nm. The injection volume was 10 L, and the external standard method was used for quantitative analysis.
b.3 temperament analysis method
Gas chromatographic conditions: column BR5ms 30meter, 0.25 mm/ID, 0.25 m df carrier gas is high purity helium carrier gas flow rate is 1.0 mL/min, inlet temperature is 230 °C, injection volume is 1 L, split ratio It is 1:30. The temperature rise program was maintained at 60 °C for 0 min, at 3 °C/min to 300 °C, for 3 min, and the solvent was delayed for 5 min.
Mass spectrometry conditions: ion source EI, ionization energy of 70 eV, ion source temperature of 280 °C, and transmission line temperature of 250 °C. Full scan Mass-to-charge ratio 40~400. The normal paraffin injection method is the same as the sample injection method.
2 Results and analysis
a. Comparison of black pepper oleoresin yield and piperine content
The yields of the three kinds of black pepper oleoresin obtained under supercritical extraction conditions were as follows: S1 was 0.46%, S2 was 0.61%, and S3 was 0.78%. The contents of piperine in the three kinds of black pepper oleoresin were as follows: S1 was 22.60%, S2 was 53.00%, and S3 was 25.73%. The yield of black pepper oleoresin extracted by supercritical static method is about 0.7%, which is close to the results obtained in this study, but the yield of continuous extraction below the entrainer may be due to the entrainer during the extraction process. Continue to add to dissolve the substance more into the fluid.
b. Analysis of black pepper oleoresin composition
Among the three kinds of black pepper oleoresin extracted by supercriticality, 48 kinds of aroma substances were identified. Among them, 22 kinds of aroma components were identified in the black pepper oleoresin S1 obtained by supercritical extraction. The main compounds were 3.89% of citrus limene, 6.53% of decene, 3.15% of decene, and 53.70% of caryophyllene. In the supercritical fluid extraction of oleoresin S2, a total of 17 kinds of aroma components were identified in the supercritical fluid extraction of oleoresin S2, the main compounds were 8.45% citrus limene and 2.19% linalool. A total of 41 compounds were identified in 47.80% sesquiterpene, 1.75% hydrazine, and 26.34% oleine. The main compounds were terpenes 4.81%, elemene 11.00%, and elemene 1.48. %, elemene 57.70%, cis-farnesene 3.26%, sweet myrrhene 2.20%, decyl enol 1.61%, and piperine 11.09%.
The oleoresin is a viscous, slightly darker, essential oil-containing resinous product extracted from the pulverized spices by an appropriate method. Almost all of the aroma and taste components in the spice can be extracted, and in addition to the essential oil, the oleoresin is also contained. Non-volatile spicy ingredients, fats, pigments and other substances that can be dissolved in solvents. These substances represent the active ingredients in spices, and their aroma and taste are balanced, intact and full. Black pepper oleoresin contains pyrrolidine amide alkaloid piperine in addition to aroma substances.
24 components were isolated and identified from the pepper extract obtained by supercritical CO2 fluid extraction. In this study, three kinds of black pepper oleoresins S1, S2 and S3 were obtained by different pretreatment of pepper raw materials, 48 compounds were isolated and identified from the Chinese Communist Party, and the characteristic substance piperine in black pepper oleoresin was identified. The oleoresin of Hainan black and white pepper was extracted by different methods. The main aroma components obtained by GCMS analysis were caryophyllene, caryophyllene, D limonene, 6,6 dimethyl 2 methylene bicycloheptane and the like. The supercritical CO2 extraction method can retain the active ingredients in the pepper to the utmost extent, and the extracted black pepper oleoresin not only contains the aroma components in the pepper essential oil, but also contains the characteristic spicy ingredient piperine in pepper. Therefore, the black pepper oleoresin obtained by supercritical CO2 extraction method has rich aroma and complete flavor, which can replace the traditional extraction method for the extraction of black pepper oleoresin, and provide a theoretical basis for the utilization of black pepper oleoresin.