WO2012169443A1 - 精製された植物性スクアレンの製造方法及び精製された植物性スクアレン - Google Patents

精製された植物性スクアレンの製造方法及び精製された植物性スクアレン Download PDF

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WO2012169443A1
WO2012169443A1 PCT/JP2012/064286 JP2012064286W WO2012169443A1 WO 2012169443 A1 WO2012169443 A1 WO 2012169443A1 JP 2012064286 W JP2012064286 W JP 2012064286W WO 2012169443 A1 WO2012169443 A1 WO 2012169443A1
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squalene
purified
impurity
peak
vegetable
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PCT/JP2012/064286
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English (en)
French (fr)
Japanese (ja)
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季之 高橋
秀忠 永井
光利 東
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Ｊｘ日鉱日石エネルギー株式会社
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Priority to KR1020137030907A priority Critical patent/KR20130143139A/ko
Publication of WO2012169443A1 publication Critical patent/WO2012169443A1/ja

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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C7/00—Purification; Separation; Use of additives
    • C07C7/12—Purification; Separation; Use of additives by adsorption, i.e. purification or separation of hydrocarbons with the aid of solids, e.g. with ion-exchangers
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C11/00—Aliphatic unsaturated hydrocarbons
    • C07C11/21—Alkatrienes; Alkatetraenes; Other alkapolyenes
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C7/00—Purification; Separation; Use of additives
    • C07C7/10—Purification; Separation; Use of additives by extraction, i.e. purification or separation of liquid hydrocarbons with the aid of liquids

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  • the present invention relates to a method for producing highly purified plant squalene and a highly purified plant squalene.
  • Squalene is a fat that belongs to terpenoids, is a colorless, odorless, tasteless, low-volatile oily liquid, has a relatively light oily feel, has excellent skin permeability and lubricity, and has very good elongation. In addition, since it has characteristics such as easy emulsification, it is widely used today as an oily base for various cosmetics and pharmaceuticals.
  • the natural squalene that has been used heretofore has been mainly animal squalene starting from deep-sea bream typified by sharks.
  • the catch of deep-sea bream has declined, making it difficult to supply natural squalene.
  • plant squalene is attracting attention as a new natural squalene to replace animal squalene.
  • plant squalene is mainly contained in plant oils and fats obtained from plant fruits and seeds, even if the content is high, it is about several thousand ppm. Therefore, in order to obtain the target plant squalene, a concentration treatment for increasing the content of squalene in the vegetable oil is required at a high magnification. In addition, the above-mentioned concentration treatment also concentrates other small / trace components, such as normal paraffin or various polar substances, that are similar in physical properties such as squalene and boiling point, contained in the vegetable oil and fat. In order to increase the purity of squalene, a purification process for separating and removing small / trace components other than these squalene from squalene is also necessary.
  • the present invention aims to provide a new purified plant squalene production method capable of easily obtaining highly purified plant squalene, and a highly purified plant squalene.
  • the present inventors have purified the vegetable oil containing concentrated squalene by chromatography using a silica column, thereby purifying it with high purity. It has been found that plant squalene can be obtained, and the present invention has been completed.
  • the present invention includes the following.
  • Purified vegetable squalene comprising at least a chromatography step of supplying vegetable oil containing concentrated squalene to a silica column as a hexane and / or heptane solution to obtain purified squalene as a flow-through fraction Manufacturing method.
  • Acetone is added to the flow-through fraction obtained from the chromatography step to obtain a homogeneous solution, then water is further added to the mixture, and the two layers are separated by allowing to stand, and the layer containing acetone and water is removed.
  • the purified vegetable squalene comprises impurity 1, wherein the gas chromatogram of the purified vegetable squalene, the ratio RT of the retention time RT S of the main peak at a retention time of RT 1 and squalene peak of the impurity 1 1 / RT s is in the range of 1.01 to 1.07, and the ratio of the peak area of the impurity 1 with the retention time RT 1 to the total peak area is 0.0005 to 0.0020, [1] to [8] The production method according to any one of [8].
  • Purified plant squalene according to [10] comprising the following impurity 1:
  • the retention time RT 1 of the impurity 1 peak and the main peak of squalene The ratio RT 1 / RT s to the retention time RT S is in the range of 1.01 to 1.07, and the ratio of the peak area of the impurity 1 of the retention time RT 1 to the area of all the peaks is 0.0005 to 0
  • the peak of impurity 1 with retention time RT 1 in the gas chromatography analysis gives peaks with mass numbers 392, 253 and 199.
  • a method for producing purified plant squalene and a highly purified plant squalene which can easily obtain plant squalene purified to a high purity.
  • highly purified vegetable squalene can be manufactured and supplied on an industrial scale.
  • FIG. 1 shows a gas chromatogram of the acetone-treated product (5) obtained in the example.
  • FIG. 2-1 shows a gas chromatogram of olive squalene (before thin film centrifugal distillation treatment and urea treatment).
  • FIG. 2-2 shows a gas chromatogram of olive squalene (before thin film centrifugal distillation treatment and urea treatment).
  • FIG. 3-1 shows a gas chromatogram of purified squalene derived from a commercially available deep-sea shark.
  • FIG. 3-2 shows a gas chromatogram of purified squalene derived from a commercially available deep-sea shark.
  • FIG. 4-1 shows the results of GC analysis of the acetone-treated product (5) obtained in the example.
  • FIG. 4-2 shows the result of GC / MS analysis of impurity 1. Peaks estimated as molecular ions, m / z 253, 199, 69, and other peaks can be seen at mass number (m / z) 392.
  • FIG. 5-1 shows the result of GC analysis of purified squalene derived from commercially available deep-sea bream.
  • the first aspect of the present invention includes at least a chromatography step of supplying vegetable oil containing concentrated squalene to a silica column as a hexane and / or heptane solution to obtain purified squalene as a flow-through fraction.
  • the present invention relates to a method for producing purified plant squalene.
  • the production method of the present invention it is possible to easily obtain highly purified vegetable squalene from vegetable oil containing concentrated squalene.
  • the “vegetable fats and oils containing concentrated squalene” used in the method for producing purified vegetable squalene of the present embodiment can be obtained from vegetable fats and oils containing squalene as a starting material.
  • the vegetable oil containing squalene is not particularly limited as long as it contains squalene, and examples thereof include olive oil, corn oil, soybean oil, safflower oil, rice bran oil, wheat germ oil, and palm oil. Even if the squalene content in these vegetable fats and oils is high, it is about several thousand ppm.
  • the vegetable oil containing concentrated squalene used in the production method of the present embodiment is a vegetable oil with an increased squalene content obtained by concentrating the vegetable oil containing squalene.
  • the method for obtaining vegetable oil containing squalene concentrated by subjecting vegetable oil containing squalene to concentration treatment or rough purification treatment in addition to concentration treatment is not limited, and known methods can be used. These methods include, for example, simple distillation method, thin film centrifugal distillation method, thin film multistage centrifugal distillation method, short process distillation method, and conversion of fatty acid glycerides or free fatty acids contained in vegetable oils and fats to methyl ester or ethyl ester. The method of performing the distillation can be used.
  • this deacidification and deodorization treatment can also be regarded as a concentration treatment of squalene or a concentration and crude purification treatment, and the deacidified and deodorized distillate is used as a vegetable oil containing the preferred concentrated squalene.
  • squalene is contained in the non-saponified fraction in the saponification treatment of vegetable oil containing squalene, this non-saponified product fraction is recovered and used as vegetable oil containing concentrated squalene. You can also
  • vegetable oil containing vegetable squalene is mixed with an organic solvent containing urea or thiourea, heated to 40 to 120 ° C., and then 2 to 15 at 0 to 35 ° C.
  • the cooling can be carried out slowly over time, and after cooling, the urea or thiourea crystals and the organic solvent can be removed.
  • Examples of the organic solvent used for the urea or thiourea treatment include lower alcohols having about 2 to 4 carbon atoms. Examples of such lower alcohol include isopropanol and ethanol (not particularly limited).
  • a solvent such as methanol, which is a concern for safety due to mixing into the product.
  • the amount of the organic solvent used in the urea or thiourea treatment is suitably 0.2 to 100 times the weight of the vegetable oil containing vegetable squalene, and particularly about 0.3 to 10 times. Is preferred.
  • urea or thiourea commercially available industrial urea and industrial thiourea conforming to JIS standards can be used.
  • the amount used is preferably about 0.2 to 20 times, particularly about 0.3 to 5 times the weight of the raw material.
  • the squalene concentration treatment and rough purification treatment may be performed using any one of the above methods, including the case where the concentration treatment and the rough purification treatment are performed simultaneously, or may be used in combination of two or more.
  • the vegetable oil containing concentrated squalene contains impurities such as normal paraffin derived from vegetable oil and polar substances in addition to squalene, even when the above-described rough purification treatment is performed. It is preferable that the purity measured by the gas chromatography internal standard method in the vegetable oil containing concentrated squalene used in the present embodiment is at least 90%.
  • the vegetable oil containing concentrated squalene is subjected to a rough purification treatment, and the content of normal paraffin thereof is preferably 2% by mass or less, more preferably less than 1% by mass, and Even more preferably, it is less than 9% by weight.
  • the vegetable oil containing concentrated squalene contains 2% by mass or more of normal paraffin, the fluidity deteriorates at room temperature, and when the content is further increased, it solidifies at room temperature and is difficult to use as a raw material. There is also a problem.
  • vegetable oil containing concentrated squalene is dissolved in an oleophilic organic solvent, and the resulting solution is subjected to a chromatography step using a silica column.
  • impurities (especially polar substances) other than squalene contained in vegetable oil containing concentrated squalene can be removed by adsorption to silica, and squalene can be purified efficiently. it can.
  • lipophilic organic solvent various lipophilic organic solvents can be used, but it is considered that the purified plant squalene as the target product is used for various cosmetics, foods, medicines, etc. Then, it is preferable to select from hexane and / or heptane.
  • the amount of the oleophilic organic solvent used is suitably 0.25 to 3.00 times the mass of the vegetable oil containing concentrated squalene, and is particularly suitable for the vegetable property containing concentrated squalene. It is preferable to use the same amount as oil.
  • the apparatus used in the chromatography step can be performed using an apparatus for performing general column chromatography, and the equilibration and flow rate of the column are determined by the vegetable oil and fat containing the column size and concentrated squalene. It can be set as appropriate depending on the amount of processing.
  • the silica to be packed in the silica column is not particularly limited as long as polar impurities can be removed by adsorption, and crushed silica or spherical silica can be used.
  • silica gel PSQ-100B (trade name) manufactured by Fuji Silysia Chemical Co., Ltd.
  • Daiso Gel (trade name) manufactured by Daiso Corporation
  • Wakogel (trade name) manufactured by Wako Pure Chemical Industries, Ltd. (50- 200 ⁇ m spherical shape).
  • purified with high purity can be obtained by collect
  • the purity of squalene in purified vegetable squalene or vegetable oil containing concentrated squalene is determined by gas chromatography using a capillary column (hereinafter also referred to as “GC”). it can.
  • gas chromatography relative purity of squalene refers to all of the samples derived from the sample detected by GC of the sample containing the target squalene.
  • the peak attributed to squalene refers to a peak attributed to all squalene isomers.
  • purity measured by gas chromatography internal standard method of squalene refers to the purity obtained by the following method.
  • a standard squalene a reagent dodecane as an internal standard substance is added to a reagent squalene (indicated purity: 99.5% or more) at a predetermined mass ratio, and this is further diluted to a predetermined concentration with normal hexane.
  • a reagent squalene indicated purity: 99.5% or more
  • the resulting calculates a ratio A s between the relative purity RP s and squalene area of the peak of the peak area and from dodecane attributed to (including all isomers) standard squalene from the chromatogram.
  • the sample containing squalene to be measured is added with dodecane at the same mass ratio and diluted with normal hexane, and then GC analysis is performed. From the obtained chromatogram, the ratio A between the area of the peak attributed to squalene and the area of the peak derived from dodecane is calculated. Then, the internal standard method purity of squalene in the sample is calculated by the following formula.
  • the gas chromatograph is GC-2010 (OCI specification) manufactured by Shimadzu Corporation, the detector is FID, the analytical column is J & W Scientific DB-5 manufactured by Agilent Technologies, the column equilibration time is 0 minutes, the sample injection amount is 1 ⁇ L, Injection mode is full volume injection, carrier gas is He, control mode is flow rate 15.0 mL / min, purge dose is 1.5 mL / min, total analysis time is 35 minutes, detector temperature is 280 ° C., makeup flow rate is 20 mL / min Min, the hydrogen flow rate is 40 mL / min, the air flow rate is 400 mL / min, the temperature program for the vaporization chamber and the temperature program for the column oven are as shown in Tables 1 and 2, respectively. Peak separation in the resulting chromatogram is performed by splitting from the baseline.
  • the chromatography step impurities that are polar substances are mainly removed by adsorption onto silica, but impurities that are nonpolar substances typified by normal paraffin are difficult to remove by adsorption onto silica.
  • the solution containing the flow-through fraction (flowing solution in the chromatography step) is cooled to make normal paraffin as a solid.
  • the normal paraffin content in the refined vegetable squalene can be further reduced by precipitating and subjecting it to a step of removing solid content by filtration (cooling / separation step).
  • the peak area is increased by the cooling / separation step.
  • the ratio can be 0.002 or less.
  • the temperature in the cooling / separation step is preferably ⁇ 10 to 15 ° C.
  • the chromatography step and the cooling / separation step can be performed in one step. That is, by cooling a solution in which vegetable oil containing concentrated squalene is dissolved in a lipophilic organic solvent, and / or subjecting the solution to a chromatography step using a silica column under cooling, At the same time, the normal impurities that are precipitated as a solid in the solution can be removed by filtration using a silica column as a filter medium. In this case, it is not necessary to provide the cooling / separation process as a separate process, and the process can be simplified.
  • the cooling temperature of the solution and / or the treatment temperature in the chromatography step is preferably ⁇ 10 to 15 ° C.
  • the “hydrophilic organic solvent” includes various hydrophilic organic solvents. In consideration of using the obtained purified plant squalene for various cosmetics, foods, medical uses, etc., acetone is preferable. .
  • the washing step can be performed by the following procedure.
  • a hydrophilic organic solvent is added to and mixed with a passing solution comprising a purified vegetable squalene and a lipophilic solvent obtained by the chromatography step (including the cooling / separation step in some cases) A good solution.
  • a small amount of water is added to the solution, mixed and allowed to stand to separate into a layer of a mixture containing a hydrophilic organic solvent and water and a layer of a mixture containing squalene and a lipophilic organic solvent. Let me. And the refined vegetable squalene can be obtained by fractionating the layer of the mixture containing a squalene and a lipophilic organic solvent, and collect
  • water-soluble impurities contained in the flow-through liquid are transferred to the layer of the mixture containing the hydrophilic organic solvent and water and removed from the mixture containing squalene and the lipophilic organic solvent.
  • plant squalene purified to a high purity can be obtained. That is, a purified plant squalene having a relative purity of 97% or more, preferably 98% or more, and an internal standard method purity of 95% or more, preferably 96% or more can be obtained.
  • the amount of the hydrophilic organic solvent used in the washing step is 0.1 to 3 times, preferably 0.1 to 2 times, more preferably the amount of the passing liquid obtained by the chromatography step. Is 0.5 to 1 times the amount.
  • the amount of a small amount of water to be added later varies depending on the amount of the hydrophilic organic solvent used, but is 0.01 to 0.5 times the amount of the hydrophilic organic solvent, preferably 0.1. Double amount to 0.3 times amount.
  • a purified vegetable squalene can be obtained by removing the lipophilic organic solvent from the flow-through obtained from the chromatography step (optionally including the cooling / separation step and / or the washing step). .
  • the method for removing the solvent is not particularly limited, and a known method such as steam distillation or spraying under reduced pressure can be used.
  • the squalene has a property of being easily oxidized, and when it is oxidized, it generates a specific odor. Therefore, the squalene contains the concentrated squalene as a raw material, the chromatography step, the cooling / separation step, the washing step. Concentration treatment, crude refining treatment for obtaining vegetable oil and fat, and possibility of contact of squalene with air, including storage and transfer of vegetable oil and fat containing purified squalene or refined vegetable squalene It is preferable to perform a certain process, process, etc. in inert gas atmosphere, such as nitrogen.
  • the purified plant squalene obtained through the chromatography step or the washing step contains at least a specific impurity (hereinafter referred to as “impurity 1”).
  • Impurity 1 wherein the chromatography step or in the gas chromatogram of vegetable squalene purified obtained through the washing step, the ratio of the retention times RT S of the main peak of a retention time impurities 1 RT 1 and squalene RT 1 / RT s is in the range of 1.01 to 1.07, and the peak area of impurity 1, it is preferable the ratio of the area of all peaks is 0.0005 to 0.0020.
  • the ratio of the peak area of the impurity 1 to the total peak area is 0.0020 or less, so that it can be used for bases and foods of pharmaceuticals and cosmetics, especially for pharmaceuticals. Can also be used.
  • the ratio of the area of the peak of impurity 1 to the area of all peaks is less than 0.0005, for example, it is necessary to extremely increase the contact time with the silica column in the production method of the present embodiment. Thus, it becomes difficult to produce the purified plant squalene with economic rationality.
  • plant squalene is obtained in a high purity of 98% or more as relative purity and 96% or more as internal standard method purity from vegetable oil containing concentrated squalene. Plant squalene that can be applied to various uses as a base for pharmaceuticals and cosmetics and foods can be produced.
  • the refined plant squalene can be obtained by hydrogenating the refined plant squalene obtained by the production method of the present embodiment according to a conventional method.
  • the purified plant squalene thus obtained has a high purity as with the purified plant squalene obtained by the production method of the present embodiment.
  • the second aspect of the present invention relates to a purified plant squalene having a purity of at least 96% as measured by a gas chromatography internal standard method.
  • the purified plant squalene of the present embodiment can be produced by the above-described method for producing purified plant squalene of the present invention.
  • High-purity squalene is manufactured and supplied for animal squalene derived from deep sea bream.
  • the squalene content in the vegetable oil containing squalene, which is the starting material is extremely low, and the fats and oils contain many impurities that approximate physical properties to squalene. It was difficult to obtain a highly pure product by concentration and purification. Therefore, the refined vegetable squalene of this embodiment is a highly pure vegetable squalene which is not conventionally known.
  • the refined plant squalene of this embodiment is compared with the conventionally known refined animal squalene, not only the starting material is different but also the composition itself is different. That is, first, purified plant squalene and purified animal squalene are different from each other in the composition of the squalene isomers constituting each. Although many isomers exist in squalene, the composition of isomers constituting squalene differs depending on whether the starting material is plant or animal. Moreover, the refined plant squalene and the refined animal squalene have different impurity compositions.
  • Purified plant squalene and purified animal squalene inevitably contain trace amounts of impurities, but the composition of these impurities depends on whether the starting material is plant or animal. is there. Thus, the refined plant squalene is different from those of the refined animal squalene in the chemical composition of the main component and the chemical composition as a composition including impurities.
  • the purified plant squalene of this embodiment contains at least an impurity 1.
  • Impurity 1 in a gas chromatography analysis of the purified vegetable squalene in this embodiment, the ratio RT 1 / RT s and the retention time RT S of the main peak of a retention time impurities 1 RT 1 and squalene 1.01 Is characterized by a ratio of the area of the peak of impurity 1 to the area of all peaks being 0.0005 to 0.0020. Further, in the GC / MS analysis, the peak of the impurity 1 having the retention time RT 1 in the gas chromatography analysis gives peaks of mass numbers 392, 253, and 199.
  • the impurity 1 specified by GC analysis and GC / MS analysis contained in the purified plant squalene of the present embodiment is a terpene-like compound whose structure is not specified as described above. And it was confirmed that this impurity 1 is not contained in the refined animal squalene.
  • the purified animal squalene contains a plurality of impurities that give a peak having a retention time ratio close to that of the impurity 1 in the GC analysis. From the results of GC / MS analysis, all of the impurities are the impurities. It has been confirmed that the substance is different from 1.
  • the impurity 1 gives a large peak to mass numbers (m / z) 392, 253, and 199 in the GC / MS analysis, but the plurality of impurities in the purified animal squalene are all GC / In the MS analysis, the three mass number peaks are not given together.
  • the purified squalene contains the impurity 1, it is determined that the purified squalene is vegetable.
  • the refined plant squalene of the present embodiment has the above-mentioned properties, and can be used for pharmaceuticals and cosmetic bases and foods, which are difficult with conventional plant squalene, especially for pharmaceuticals.
  • 0LSQE olive squalene
  • the raw material (57.7 g) was dissolved in an equal amount (57.7 g) of hexane (HPLC grade: the same applies to hexane described below), and then a silica column Sep-Pak VAX PS-2 (registered trademark) (Waters Impurity adsorption treatment was carried out.
  • the adsorption treatment was carried out at a flow rate of 2 mL / min using a Shimadzu HPLC pump AV-10.
  • the column treatment was performed at 15 ° C.
  • the recovered material (squalene amount: 32.5 g) until the raw material / hexane solution did not flow out from the lower part of the column was designated as “silica filtered product (1)”.
  • a part of the silica filter product (1) is taken out, treated with an evaporator at 40 ° C. for 2 hours, and then the solvent is distilled off by vacuum drying (40 ° C.) for 3 hours. The amount of purified plant squalene recovered And the purity was confirmed.
  • hexane-cleaned product (2) (squalene amount: 15.6 g) was dissolved in hexane (57.7 g) in an amount equivalent to that of the raw material, an impurity adsorption treatment was performed on the silica column in the same manner as described above. A part of the hexane-cleaned product (2) was taken out and the recovered amount and purity were confirmed in the same manner as in the above method.
  • the hexane-cleaned product (2) After completion of feeding the hexane-cleaned product (2), the hexane-cleaned product (2) / the product collected until the hexane solution no longer comes out from the bottom of the column (squalene amount: 6.3 g) was designated as “silica filtered product (3)”. A part of the silica filtered product (3) was taken out, and the recovered amount and purity were confirmed in the same manner as in the above method.
  • hexane-cleaned product (4) A part of the hexane-cleaned product (4) was taken out and the recovered amount and purity were confirmed in the same manner as in the above method.
  • Table 3 shows the purity (relative purity and internal standard method purity) and step recovery in each step.
  • FIG. 1 shows a GC chromatogram of a typical acetone-treated product (5).
  • Figures 2-1 and 2-2 show gas chromatograms of olive squalene used (before thin film centrifugal distillation and urea treatment) for reference.
  • Figures 3-1 and 3-2 show gas chromatograms of purified squalene derived from commercially available deep-sea bream as a reference.
  • the peak with a retention time of 43.567 minutes corresponds to “Impurity 1” contained in the purified plant squalene.
  • the mass spectrum of impurity 1 is shown in FIG. In the mass spectrum, a peak estimated as a molecular ion at a mass number (m / z) 392, m / z 253, 199, 69, and other peaks are seen.
  • the peak of impurities having a retention time ratio approximate to the peak attributed to impurity 1 contained in the purified plant squalene is the main. Five things are observed. Each mass spectrum of these peaks is different from the mass spectrum of impurity 1 contained in the purified plant squalene, and does not show both m / z 392, 253, and 199 peaks. It belongs to a substance different from the impurity 1.
  • the peak of each impurity in the GC chromatogram of the purified animal squalene is attributed as shown in Table 4 from the comparison between the mass spectrum and the library. Among these, a mass spectrum of an impurity (assigned to coprostan) that gives a peak at a retention time of 42.181 minutes in the GC chromatogram is shown as an example in FIG.
  • the purified plant squalene obtained has an isomer composition and an impurity composition of squalene different from the purified animal squalene.
  • a method for producing a purified plant squalene that can easily obtain a highly purified plant squalene, and a highly purified plant squalene. This is expected to contribute greatly to the production of various cosmetics, pharmaceuticals, foods and the like.

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PCT/JP2012/064286 2011-06-06 2012-06-01 精製された植物性スクアレンの製造方法及び精製された植物性スクアレン WO2012169443A1 (ja)

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CN105367370A (zh) * 2014-08-27 2016-03-02 浙江医药股份有限公司新昌制药厂 一种从提取天然维生素e后的脚料中提取角鲨烯的方法
WO2024126194A1 (en) * 2022-12-12 2024-06-20 Evonik Operations Gmbh Process for obtaining plant-based squalene

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CN105699561A (zh) * 2016-02-29 2016-06-22 中国烟草总公司广东省公司 一种烟叶中角鲨烯的检测方法
CN111307981B (zh) * 2020-03-17 2022-05-10 广西科技大学 一种快速测定角鲨烯的方法

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