CN114894917A - Detection and fingerprint spectrum construction method for volatile components of nardostachys chinensis bunge - Google Patents
Detection and fingerprint spectrum construction method for volatile components of nardostachys chinensis bunge Download PDFInfo
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Abstract
The invention relates to the technical field of traditional Chinese medicine analysis, in particular to a method for detecting volatile components of nardostachys chinensis bunge and constructing a fingerprint. The invention adopts GC-Q-exact Orbitrap MS technology, and 74 chemical components including monoterpene, sesquiterpene and non-terpenoid are searched and identified by a high-resolution mass spectrum library, and the obtained data has higher reliability and accuracy. Wherein, the calamene, the Ledene oxide- (II) the trumpet-shaped alkene oxide- (II) and the patchouli alcohol are the main components of the volatile components of the nardostachys chinensis bunge. In addition, a gas phase fingerprint analysis method is also established, 19 common peaks of the volatile component gas phase fingerprint of the nardostachys chinensis batal are determined, the method is high in repeatability and good in stability, and the established gas phase fingerprint can be used for overall quality control and evaluation of the nardostachys chinensis batal medicinal material.
Description
Technical Field
The invention relates to the technical field of traditional Chinese medicine analysis, in particular to a method for detecting volatile components of nardostachys chinensis bunge and constructing a fingerprint.
Background
The heart stabilizing granules are the core large variety of Shandong stepage pharmaceutical company, the traditional Chinese medicine is prepared from codonopsis pilosula, rhizoma polygonati, pseudo-ginseng, nardostachys chinensis and other medicinal materials, but the quality of the medicinal materials has obvious difference due to different production places of the nardostachys chinensis. In order to ensure the inherent quality of the nardostachys chinensis bunge medicinal material, the company develops related nardostachys chinensis bunge quality standard research.
Rhizoma Nardostachyos, a herb identified as dried root and rhizome of Nardostachys jatamansi DC of Valerianaceae. Also named as Duomi amara, Nardostachys japonicas, Panax ginseng, Musk fruit and Potentilla discolor, are indispensable perfume varieties in Tibet areas of China and are distributed in Gansu, Qinghai, Sichuan and other places. Has the effects of dispelling pathogenic wind, eliminating dampness, expelling pus, removing toxic substances, promoting granulation, relieving pain, regulating qi-flowing, tranquilizing mind, dispersing stagnated liver qi, and relieving qi stagnation, and can be used for treating qi stagnation, chest distress, abdominal distention, anorexia, emesis, neurasthenia, hysteria, insomnia, and convulsion, and is clinically used with other medicines for treating spleen and stomach diseases, cardiopalmus, chest and abdominal fullness, etc. The nardostachys chinensis bunge is an aromatic medicinal material rich in volatile components, and a large number of pharmacological experiments show that the nardostachys chinensis bunge has the effects of resisting arrhythmia, protecting cardiac muscle cells, relieving anxiety, regulating blood sugar metabolism and the like, and has increasingly wide clinical application. Due to the lack of large-scale resource planting bases, the nardostachys chinensis is mainly supplied to markets by wild resources, and the annual yield is higher in areas such as the Fuhuo county, the Yuan county, the Hongyuan county and the Pan county of the Qiang nationality of the Kangzi Tibetan province, the Fuhuo county, the Yuntang county and the Xueqin county of the Kangzi Tibetan province in Sichuan province. Due to the different growing environments, the volatile components of nard also have different contents.
At present, identification of nardostachys chinensis benth in 2020 edition Chinese pharmacopoeia comprises character identification and thin-layer chromatography, and the identification method is single. For content measurement of rhizoma Nardostachyos, volatile components content of the product should not be less than 2.0% (m/g) according to 2204 rule. The active ingredient of Nardostachys chinensis Benth, is measured by high performance liquid chromatography as described in general regulation 0512. However, the prior art is not strong in specificity and lacks of application of instruments with higher sensitivity due to the identification method of volatile components of nardostachys chinensis bunge. In addition, the fingerprint of volatile components of the nardostachys chinensis bunge is not constructed, and the quality of the traditional Chinese medicinal materials is difficult to control systematically and in many aspects. Therefore, a comprehensive detection method with high sensitivity and strong specificity is urgently needed for identifying the volatile components of the nardostachys chinensis bunge and constructing a fingerprint method of the volatile components of the nardostachys chinensis bunge to qualitatively and quantitatively determine the effective components of the volatile components of the nardostachys chinensis bunge, so that the quality of the volatile components of the nardostachys chinensis bunge is effectively controlled.
Disclosure of Invention
The invention provides a method for detecting volatile components of nardostachys chinensis and constructing a fingerprint, wherein GC-Orbitrap-MS is adopted, and an Orbitrap mass spectrometer is used, so that the detection method has the advantages of high resolution, high quality precision and high stability. The invention also establishes a fingerprint spectrum method, can realize higher separation degree in a short time, has the calibration quantity of 19 common peaks, and can carry out integral evaluation on the internal quality of the nardostachys chinensis bunge medicinal material.
In order to solve the technical problem, the invention provides a method for detecting volatile components of nardostachys chinensis bunge, which is characterized by comprising the following steps of:
preparing a test article solution: weighing rhizoma Nardostachyos, adding distilled water, heating and reflux-extracting with ethyl acetate as extraction solvent, collecting ethyl acetate layer, drying, metering volume, and filtering to obtain sample of test solution;
the method comprises the following steps: using woolA thin-tube column chromatographic column, wherein the injection port temperature is 250-270 ℃, the injection amount is 0.6-1.2 mu l, the split ratio is 30-50: 1, and the temperature is programmed: the initial temperature is 60-80 ℃, and the temperature is 3-7 ℃ per minute -1 The temperature is raised to 80-100 ℃ at a speed of 30-50 ℃ per minute -1 Heating to 130-140 ℃ at a speed, and keeping for 4-6 min; at a temperature of 8-12 ℃ per minute -1 Raising the temperature to 170-180 ℃ at a speed, and keeping the temperature for 8-10 min; at 6-8 ℃ per minute -1 Heating to 240-260 ℃ by a program, and keeping for 10-20 min;
the mass spectrum conditions are as follows: EI ion source, electron energy 60-80 eV, ion source temperature: 270-290 ℃, solvent delay time: 2-3 min, wherein the scanning mode is full scanning, the detection range is m/z 50-550, and a GC-Q-active Orbitrap MS total ion flow graph of volatile components of the nardostachys chinensis is obtained;
fourthly, ingredient identification: data acquisition and analysis were performed using X Calibur software, and the chemistry in the volatile components of Nardostachys chinensis was determined using first-order mass spectrometry EI-MS matched against the nominal mass library NIST MS Search 2, Mainlib, Chinese Pharma databases.
The heating reflux extraction time in the step (1) is 1-3 h, and preferably 2 h.
Preferably, the drying in the step (1) is performed by using anhydrous Na 2 SO 4 And (5) drying.
Preferably, the gas chromatography conditions of step (2) are: adopting a Thermo TG-WAXMS capillary column chromatographic column, wherein the injection inlet temperature is 260 ℃, the injection amount is 1 mul, the split ratio is 40:1, and the temperature is programmed: initial temperature 70 deg.C, at 5. min -1 Heating to 175 deg.C at a speed of 7 deg.C/min for 9min -1 The temperature was programmed to 250 ℃ and held for 15 min.
Preferably, the capillary column chromatography column in step (2) has a specification of 0.25mm × 30m × 0.25 μm.
A nardostachys chinensis volatile component fingerprint spectrum construction method comprises the following steps:
preparing a test article solution: weighing rhizoma Nardostachyos, adding distilled water, heating and reflux-extracting with ethyl acetate as extraction solvent, collecting ethyl acetate layer, drying, metering volume, and filtering to obtain sample of test solution;
the gas chromatography conditions are as follows: capillary column chromatographic column, temperature programming: the initial temperature is 105-115 ℃, the temperature is kept for 0.8-1.2 min, and the temperature is 23-27 ℃ min -1 Heating to 123-127 ℃, and keeping for 4-6 min; at 4-6 ℃ per minute -1 Heating to 125-135 ℃, and keeping for 2.5-3.5 min; at 28-32 ℃ per minute -1 Heating to 180-190 ℃, and keeping for 6.5-7.5 min; at 23-27 ℃ per minute -1 Heating to 205-215 ℃, and keeping for 1.5-2.5 min; at 13-17 ℃ min -1 Heating to 240-260 ℃, keeping for 4.5-5.5 min, controlling the temperature of a sample inlet to be 230-250 ℃ and the temperature of a detector to be 240-260 ℃; split-flow sample injection is carried out, wherein the split-flow ratio is 14-16: 1;
identification of the common peaks: introducing a gas chromatogram obtained after detecting a nardostachys chinensis volatile component test solution into Chempatern chemometrics software for analysis, calibrating a common peak by taking a chromatographic peak with a percentage peak area larger than 1.0 as a screening condition, and identifying the components of the common peak by retrieving GC-Q-active Orbitrap MS related mass spectrum data;
fourthly, establishing a fingerprint map: and (3) carrying out scaling pretreatment on the data of the common peak area, and generating a control fingerprint of the nardostachys chinensis volatile component common mode by adopting a curve simulation method, thereby establishing the fingerprint of the nardostachys chinensis volatile component.
Preferably, the gas chromatography conditions are as follows: thermo TG-WAXMS capillary column; temperature programming: the initial temperature is 110 ℃, the temperature is kept for 1min, the temperature is raised to 125 ℃ at 25 ℃ min-1, and the temperature is kept for 5 min; heating to 130 deg.C at 5 deg.C/min-1, and maintaining for 3 min; heating to 185 deg.C at 30 deg.C/min-1, and maintaining for 7 min; heating to 210 deg.C at 25 deg.C/min-1, and maintaining for 2 min; heating to 250 deg.C at 15 deg.C/min-1, maintaining for 5min, with the injection inlet temperature of 240 deg.C and the detector temperature of 250 deg.C; split-flow sample injection with a split-flow ratio of 15: 1.
Preferably, the Thermo TG-WAXMS capillary column in step (2) has a specification of 0.25mm × 30m × 0.25 μm.
Preferably, 74 compounds are identified from the volatile components of nardostachys chinensis bunge according to the method for detecting the volatile components of nardostachys chinensis bunge, wherein the compounds are sequentially: beta-Patchouline, beta-malarene, naphylalene, 1,2,4a,5,8,8a-hexahydro-4, 7-dimethylene-1- (1-methylethenyl) -, (1 alpha, 4a beta, 8a alpha) - (+ -) -aristolocene, alpha-guaiene, (+) -calarene, alpha-malarene, (-) -alpha-gulcene, (-) -alpha-patchoulene, 8, 9-dehydroneoisolongifolene, 1H-Cyclopropa [ a ] Naphthalene,1a,2,6,7,7a,7b-hexahydro-1,1,7,7 a-tetramethy-, [1a alpha, 7a,7 b) ], 4, 7-Cycloundecatriene, 1,5,9, 9-tetramethylene-, Z, Z-, alpha-buxene, 4a,5-Dimethyl-3- (prop-1-en-2-yl) -1,2,3,4,4a,5,6, 7-octahydroaphthalene-1-ol, 1H-Cyclopropa [ a ] naphthalene,1a,2,6,7,7a,7b-hexahydro-1,1,7,7 a-tetramethylene-, (3S,3aS,5R) -3, 8-dimethyle-5-prop-1-en-2-yl-1, 2,3,3a,4,5,6, 7-octalene, (-beta-cyclopentene, 1H-cyclopropene ] naphthalene,1,2,3, 3a,4,5, 7-octalene, 1, 7-octalene-1, 3,7, 7 a-trimethylene-, [1aS- (1a α,3a α,7a β,7b α) ] -, (-) -eudesma-3,4,11-triene, 1,3-Trimethyl-1H-indene, Naphtalene, 1,2,4a,5,8,8a-hexahydro-4, 7-dimethylene-1- (1-methylthio) -, (1S,4aR,8aS) -, Bicyclo [4.4.0] dec-1-ene, 2-isopropylene-5-methy-9-methyene-, (2S,4aR,8aR) -4a, 8-dimethylene-2- (prop-1-en-2-yl) -1,2,3,4,4a,5,6,8 a-thiolene, 5, 10-isophthylene-1, 2,3,4,4a,5,6,8 a-methyne-4, 5, 10 a-phenylene4, 5, 10 a-phenylene4, 4,5, 10, 5, 10 a-phenylene-, and the like, Beta-dihydroionone, 1- (3,6, 6-trimethy-1, 6,7,7a-tetrahydrocyclopenta [ c ] pyran-1-yl) ethane, 1H-Cyclopenta [1,3] cyclopropa [1,2] benzen-3-ol, octahydro-3,7-dimethyl-4- (1-methythynyl) -, (3R,3aR,3bR,4S,7R,7aR) -, isospathunol, 1-Oxaspiro [2.5] octane,5,5-dimethyl-4- (3-methyl-1,3-butadienyl) -, metagalol, beta-ionone, 3-buytene-2-4- (2, 6-Trimethyl-1, 2-1-methoxy-1, 7-1-yl), (1, 2-methoxy-1, 3-dimethyl-1-yl) acetol, 3aS,7S,7aS,7bR) -1,1,3a, 7-tetramethyldehydro-1H-cyclopropa [ a ] napthalene-7-ol, Selin-6-en-4 alpha-ol, Ledol trumpet tea terpene alcohol, epoxidized lupene II, (-) -eudesmol, (2R) -2,3,4,4a,5,6,7, 8-Octahydro-alpha, 4a beta, 8 beta-tetramethylethylene-2-napthalene methyl alcohol, eucalyptol, 5-azuemethylalcohol, 1,2,3,4,5,6,7,8-Octahydro-a, a,3, 8-tetramethylethylene-, 5-acetate, (3S,5R,8S) -, 6-isophytol-4, 8-isophytol-1, 8, 8-napthalene-2, 8, 8-isophytol-5, 5-acetyl, 3S, 8S, 6-5-isophytol, 8-5-isophytol, 8-2, 8-isophytol, 8, 2, 8-isophytol, 2, 8, 5-isophytol, 2, 8, 5, 2,5, 3, 2,3,4,5, 4,5, 4, 3, 2,3, 2,3,4, 2,3,4, 3, Patchoulolihol patchoulol, (-) -a-Cadinol (-) - α -dolol, (1aR,7R,7aR,7bS) - (+) -1a,2,3,5,6,7,7a,7b-Octahydro-1,1,7,7 a-tetramethyl1H-cyclopropa [ a ] naphthalene-3-one (E) -3- ((4S,7R,7aR) -3, 7-dimethylene-2, 4,5,6,7,7a-hexahydro-1H-inden-4-yl) -2-methoxyldide, a-Vetivol-enol, (-) -spathuol eucalyptol, (-) -guaiene, cyclohexadiol, 1, 3-dimethylene-6-enol, 2-naphthol, 2,3,4,4a,5,6,7,8-octahydro-4,4 a-dimethylene-6- (1-methylthioidene) -, (2R,4R,4aS) -, 1-naphthol, 1,2,3,4,4a,5,6,8a-octahydro-1,4 a-dimethylene-7- (1-methylthioyl) -, (1R,4aR,8aR) -, Acetic acid,3-hydroxy-6-isopropenyl-4,8 a-dimethylene-1, 2,3,5,6,7,8,8 a-octahydrophthalene-2-yler, 2,7, 7-tetracyclino [1, 6-octadecylen-25, 3-octadecylen-12-2-octadecylen-3, 4-octadecylen-12, 3-octadecylen-3-4-octadecylen-3, 4-1-4-2-1, 4-dimethylene-12, 5-octadecylen-2-enecarboxylic acid,3, 4,4 a-dimethylene-1, 4,4 a-dimethylene-1, 3,5,6, 5, 6-trimethylenecarboxylic acid, 2-octadecylen-2-octadecylen-2-1, 4, 4-octadecylen-1, 4-octadecylen-4, 4-dimethylene, 4, 3-dimethylene, 2-dimethylene, 4, 2-dimethylene, 2-dimethylene, 3-2-dimethylene, 2-one, 2,4, 2,4, 2,4, 3-one, 2, 3-dimethylene, 2,4, 2,3,4, 3,4, 3, 2,3, 2,3, 2,3, 2,3, 2,3, 2, ledene oxide- (II) allene oxide- (II), cis-Valerenyl acetate cis-Valerine ester, 2,7,7-Tetramethyltricyclo [6.2.1.0(1,6) ] undec-4-en-3-one, 2aS,3aR,5aS,9bR) -2a,5a, 9-trimethy-2 a,4,5,5a,6,7,8,9 b-octahydro-2H-naphto [1,2-b ] oxoiro [2,3-c ] furan, 2(3H) -naphtalenone, 4,4a,5,6,7, 8-xanthene-1-hydroxy-4 a, 5-dimethy-3- (1-methylene), (4, 5,6,7, 8-xanthene-1-hydroxy-4 a,5-dimethyl-3- (1-methyne) -, 4-methylene-4, 5-dimethyl-3- (3, 4, 3-butyl) -3-dimethyl-3-butyl-3-ethyl acetate cis-4-1-butyl-3-dimethyl-2 a, 5-3-dimethyl-2-3-4-dimethyl-2-b-2-methyl-2-4-dimethyl-2-4-one, 4-dimethyl-4-3-4-3-dimethyl-3-4-3-4-dimethyl-4-3-4-one, 4-3-one, 4-one, 4-dimethyl-4-dimethyl-4-one, 3-4-one, 3-4-one, 3-one, and-4-one, (E) -3- ((4S,7R,7aR) -3,7-Dimethyl-2,4,5,6,7,7a-hexahydro-1H-inden-4-yl) -2-methylalydene, α -Valerenol α -valerienol, aristolocone, methyl 6, 9-octadecadienoate, γ -Himachalene γ -cedrene, naphalene, 1,2,3,4-tetrahydro-1,6,8-trimethyl-, 4- (3, 3-Dimethyl-but-1-yl) -4-hydroxy-2,6,6-trimethylcyclohex-2-enone, 2-Propen-1-ol,3- [ (4S,7R,7aR) -2,4,5,6,7,7 a-hexahydro-2-enone, 7-dimethyl-1H-inden-4-yl ] -2-methyl-,1-acetate, (2E) -, (4aR,5S) -1-Hydroxy-4a,5-dimethyl-3- (propan-2-ylidine) -4,4a,5, 6-tetrahydronaphtalen-2 (3H) -one, (3S) -3,4,4a,5,6,7-Hexahydro-4a beta, 5 beta-dimethyl-3-isopenpenylphthalalen-1 (2H) -one, 2aS,3aR,5aS,9bR) -2a,5a, 9-methyl-2 a,4,5,5a,6,7,8,9 b-octahydro-2H-napthyl [1, 2-enol ] amino [1, 2-oxy ] furan [ 3, 3-oxy ] furan [ 2H-naphthalene [1, 2-oxy ] furan [ 3H ] -2, Narcinone.
According to the detection method of the nardostachys chinensis volatile components, the retention time of the compounds on a GC-Q-active Orbitrap MS total ion flow diagram is as follows in sequence: 6.79min, 7.3min, 7.48min, 7.84min, 8.08min, 8.17min, 8.3min, 8.57min, 8.89min, 8.99min, 9.27min, 9.43min, 9.89min, 9.96min, 10.15min, 10.28min, 10.42min, 10.51min, 10.74min, 10.87min, 11.1min, 11.17min, 11.27min, 11.74min, 12.5min, 13.24min, 13.4min, 13.72min, 13.96min, 14.08min, 14.23min, 14.36min, 15.11min, 15.19min, 15.33min, 15.74min, 15.98min, 16.6min, 17.25min, 17.63min, 18.2min, 18.52min, 18.96min, 19.17min, 19.33 min, 15.74min, 15.26 min, 15.98min, 16.6min, 17.25min, 27.25 min, 27.26 min, 27.26.26 min, 27.26.26.26 min, 27.26 min, 27.26.26.26 min, 27.26.26 min, 27.26 min, 27.26.26.26 min, 27.26 min, 27.26.26 min, 27.26 min, 27.26.26.26.26.26 min, 27.26.26 min, 27.26 min, 27.26.26 min, 7.26.26 min, 7.7.7.7.7.7.7.7.7.7.7.7.7.7.7.7.7 min, 7.7.7 min, 7.7.7.7.7.7.7 min, 7.7.7 min, 7min, 7.7.7.7.7.7.7.7.7 min, 7.7 min, 7.7.7.7.7.7 min, 7min, 7.7 min, 7min, 7.7.7.7.7.7.26 min, 27.7.7.26 min, 27min, 27.7.7.26 min, 27min, 27.26 min, 27min, 27.26 min, 27min, 27.26 min, 27min, 27.26 min, 27.26.26 min, 27.26 min, 27min, 27.26 min, 27..
The nardostachys chinensis volatile component detection method and the fingerprint construction method provided by the invention have the following beneficial technical effects:
the method disclosed by the invention uses GC-Orbitrap-MS for the first time, realizes a high-flux qualitative flow by using the Orbitrap mass spectrometer, and fully exerts the performance advantages of the high resolution, high quality precision and high stability of the Orbitrap mass spectrometer. The initial identification is carried out on the chemical components of the volatile components of the nardostachys chinensis bunge, and the obtained data has high reliability and accuracy. Finally, 74 chemical components, mainly sesquiterpene and monoterpene components, are identified in the volatile components of the nardostachys chinensis bunge. Wherein the sesquiterpene component accounts for 72.17%, and comprises aristolocidine type and guaiane type sesquiterpenes, and the monoterpene component accounts for 5.72%.
The fingerprint spectrum method constructed by the invention can realize higher separation degree in a short time, the nominal number of the common peaks is 19 common peaks, the specific components are (-) -aristolocene, calamene, alpha-malilene, (-) -alpha-gulene 8, 9-dehydroneolongifolene, beta-ionone, (-) -eudesmol, eucalyptol, patchouli alcohol and the like, and the similarity of the fingerprint spectrums of all batches of samples is calculated by a correlation coefficient method to be within the range of 0.9689-0.9994. The fingerprint detection method established by the invention is subjected to sample injection measurement according to set gas chromatography conditions, and the repeatability test result shows that the RSD of the relative retention time of each common peak is 0.01-0.03%, and the RSD of the relative peak area is 0.28-3.25%, thus the method has good repeatability. The stability test result shows that the RSD of the relative retention time of each common peak is 0.01-0.07%, the RSD of the relative peak area is 0.61-4.97%, and the stability of the test solution in 24h is good. The data also show that the established quality detection method can be used for overall evaluation of the quality of the nardostachys chinensis bunge medicinal material.
Drawings
The invention will be further described with reference to the accompanying drawings and examples, in which:
FIG. 1 is a GC-Q-active Orbitrap MS total ion flow diagram of a nardostachys test sample solution in example 1 of the present invention;
FIG. 2 is a graph showing the distribution of the content of each component in the Nardostachys jatamansi test solution in example 1 of the present invention;
FIG. 3 is the fingerprint of 12 batches of the spikenard test solution in example 2;
FIG. 4 is a control fingerprint of the consensus pattern of volatile components of Nardostachys chinensis in example 2 of the present invention;
FIG. 5 is a three-dimensional analysis chart of the principal components of volatile components of Nardostachys chinensis Batal in example 2 of the present invention;
FIG. 6 is the score of the contribution of 19 common peak areas to the grouping of volatile components of Nardostachys chinensis in example 2 of the present invention.
Detailed Description
In order to make the objects, technical solutions and advantages of the present invention more apparent, the present invention is described in further detail below with reference to the accompanying drawings and embodiments. It should be understood that the specific embodiments described herein are merely illustrative of the invention and are not intended to limit the invention.
The samples of 12 batches of the nardostachys chinensis bunge used in the following examples were identified by the food and drug inspection institute of Shandong province as dried roots and rhizomes of nardostachys chinensis bunge of Valerianaceae. Wherein, the No. 1 to No. 10 samples are wild medicinal materials collected in the Sichuan province in modern industrial gardens of Anguo city in Hebei province, and the No. 11 to No. 12 samples are Gansu stock medicinal materials provided by Huayu Chinese medicinal decoction piece Limited company in Bozhou province in Anhui province.
Example 1
The embodiment of the invention provides a method for detecting volatile components of nardostachys chinensis bunge, which is characterized by comprising the following steps:
(1) extraction of volatile components
Volatile components are extracted by referring to a method A of determining volatile components according to a general rule 2204 of pharmacopoeia of the people's republic of China (four parts) of 2020 edition. Pulverizing rhizoma Nardostachyos, and sieving with a second sieve to obtain coarse powder. Taking 5g of rhizoma Nardostachyos powder, placing in a 250mL round bottom flask, adding 100mL of distilled water and a little broken ceramic chip, shaking, mixing, adding 5mL of ethyl acetate at the upper end of a volatile component extractor to fully dissolve volatile components, connecting a volatile component detector and a reflux condenser, boiling and extracting for 2h, and standing to room temperature. Collecting ethyl acetate layer, precisely transferring 1mL anhydrous Na 2 SO 4 Diluting the dried upper layer solution with ethyl acetate, respectively determining the solution to be contained in 100mL volumetric flasks and 5mL volumetric flasks, and filtering the solution through a 0.22 mu m microporous filter membrane to sequentially obtain GC-Q-active Orbitrap MS analysis samples.
(2) GC-Q-Exactive Orbitrap MS analysis
The GC conditions were: a Thermo TG-WAXMS capillary column (0.25mm multiplied by 30m multiplied by 0.25 mu m), high-purity helium gas as a carrier gas, wherein the helium gas has a constant pressure of 70.0kPa, a sample inlet temperature of 260 ℃, a sample injection amount of 1 mu l, a split flow ratio of 40:1, and programmed heating (initial temperature of 70 ℃, temperature of 90 ℃ at a speed of 5 ℃ min < -1 >, temperature of 135 ℃ at a speed of 40 ℃ min < -1 >, holding for 5min, temperature of 175 ℃ at a speed of 10 ℃ min < -1 >, holding for 9min, and temperature of 250 ℃ at a speed of 7 ℃ min < -1 > and holding for 15 min).
The MS conditions are as follows: electron bombardment ion source (EI), electron energy 70eV, ion source temperature 280 ℃, solvent delay time 2.6min, scanning mode is full scanning, detection range m/z is 50-550, and resolution is 60000 FWHM. The MS transmission and auxiliary lines 1 and 2 are at 250 ℃. The GC-Q-active Orbitrap MS total ion flow diagram of volatile components of nardostachys chinensis is shown in figure 1.
Data acquisition and analysis were performed using X Calibur software, and 74 compounds were identified in total using first-order mass spectrometry EI-MS to match the nominal mass library NIST MS Search 2, Mainlib, Chinese Pharma databases, all with a threshold of match greater than 750, as shown in table 1. The total detection rate of chemical components of the volatile components is up to 96.87 percent by calculating according to percentage conversion of a peak area normalization method. In 12 batches of samples, the 3 highest-content components are calamene ((+) -Calarene, patchouli alcohol and Ledene oxide- (II) in sequence, the majority of volatile components of nardostachys chinensis are sesquiterpenes and oxidized derivatives thereof, and contain a small amount of monoterpene and ester components, and the overall components are classified according to the attribution, and the relative content distribution is shown in figure 2.
TABLE 1 volatile component chemical analysis of Nardostachys chinensis Franch
Example 2
The embodiment of the invention provides a method for constructing volatile component gas-phase fingerprint of nardostachys chinensis bunge, which comprises the following steps:
(1) preparation of test solution
Volatile components are extracted by referring to a method A of determining volatile components according to a general rule 2204 of pharmacopoeia of the people's republic of China (four parts) of 2020 edition. Pulverizing rhizoma Nardostachyos, and sieving with a second sieve to obtain coarse powder. Taking 5g of rhizoma Nardostachyos powder, placing in a 250mL round bottom flask, adding 100mL of distilled water and a little broken ceramic chip, shaking, mixing, adding 5mL of ethyl acetate at the upper end of a volatile component extractor to fully dissolve volatile components, connecting a volatile component detector and a reflux condenser, boiling and extracting for 2h, and standing to room temperature. Collecting ethyl acetate layer, precisely transferring 1mL anhydrous Na 2 SO 4 Diluting the dried upper layer solution with ethyl acetate, respectively determining the diluted upper layer solution in volumetric flasks of 100mL and 5mL, and filtering the diluted upper layer solution through a 0.22-micrometer microporous filter membrane to obtain gas-phase fingerprint samples in sequence.
(2) Chromatographic conditions
The GC conditions were: thermo TG-WAXMS capillary column (0.25 mm. times.30 m. times.0.25 μm); the temperature raising procedure is that the initial temperature is 110 ℃, the temperature is maintained for 1min, the temperature is raised to 125 ℃ at 25 ℃ and min-1, and the temperature is maintained for 5 min; heating to 130 ℃ at 5 ℃ min-1, and keeping for 3 min; heating to 185 deg.C at 30 deg.C/min-1, and maintaining for 7 min; heating to 210 deg.C at 25 deg.C/min-1, and maintaining for 2 min; the temperature is raised to 250 ℃ at 15 ℃ and min-1, and the temperature is kept for 5 min. The temperature of the sample inlet is 240 ℃, and the temperature of the detector is 250 ℃; split-flow sample injection is carried out, and the split-flow ratio is 15: 1.
(3) Methodology survey
Taking a 14 # patchouli alcohol chromatographic peak with a middle peak-out position and good resolution as a reference peak, taking the prepared nardostachys chinensis test sample solution, and continuously carrying out sample injection determination for 6 times according to set gas chromatography conditions to obtain the RSD of the relative retention time of each common peak of 0.01-0.03%, and the RSD of the relative peak area of 0.50-2.73%, which indicates that the instrument has good precision; taking 6 parts of prepared nardostachys chinensis test solution, carrying out sample injection measurement according to set gas chromatography conditions, and calculating to obtain the RSD of the relative retention time of each common peak of 0.01-0.03% and the RSD of the relative peak area of 0.28-3.25%, which indicates that the method has good repeatability; and taking the prepared nardostachys chinensis volatile component test solution, respectively carrying out sample injection measurement for 0 hour, 4 hours, 8 hours, 10 hours, 15 hours and 24 hours according to set gas chromatography conditions, and calculating to obtain the RSD of the relative retention time of each common peak of 0.01-0.07 percent and the RSD of the relative peak area of 0.61-4.97 percent, which indicates that the test solution has good stability in 24 hours.
(4) Establishment of fingerprint and identification of common peak
Taking 12 batches of nardostachys chinensis batal samples, preparing a sample solution according to the method under the item of (1) preparation of the sample solution, then carrying out sample injection measurement according to the item of (2) chromatographic condition, introducing an obtained GC (gas chromatography) chart into ChemPattern chemometrics software, analyzing, and superposing the samples to obtain a gas chromatography chart, which is shown in figure 3. And (4) calibrating 19 common peaks by taking the chromatographic peak with the percentage peak area larger than 1.0 as a screening condition.
All common peak components are identified by searching GC-Q-active Orbitrap MS related mass spectrum data and comparing related literature data, the matching degree is greater than 780 in mass spectrum analysis, and specific detection results can be shown in Table 2.
After Pareto scaling pretreatment is carried out on all the selected peak area data, a Gaussian curve simulation method is adopted to generate a control fingerprint spectrum of the nardostachys chinensis volatile component common mode, and the control fingerprint spectrum is shown in figure 4. And calculating the fingerprint similarity of each batch of samples within the range of 0.9689-0.9994 by using a correlation coefficient method.
TABLE 2 common peaks of volatile constituents of Nardostachys chinensis Franch by finger print
(5) Multivariate statistical analysis
1.1 principal component analysis
In chempatern software, selected consensus peak data were Pareto-scaled and preliminary evaluations were made using differences between principal component analysis samples. As can be seen from the principal component analysis three-dimensional graph in fig. 5, the first principal component contribution rate is 84.49%, the second principal component contribution rate is 6.72%, the third principal component contribution rate is 3.60%, and the cumulative contribution rate of the first 3 principal components is 94.81%. The established model has better discrimination. Fig. 5 shows that samples 11 to 12 of the nardostachys chinensis batal et al do not have a great difference from wild herbs, and the sample 2 has a lower similarity and a longer distance compared with other samples, which indicates that the content of the nardostachys chinensis batal in different batches is different.
2.2 Quadrature partial least squares discriminant analysis
To further look for differences in the chemical composition of volatile components of Nardostachys chinensis, a supervised OPLS-DA pattern was selected using SIMCA-P14.1 software. OPLS-DA combines orthogonal signals with PLS-DA analysis methods and is more sensitive to less correlated variables. Grouping the classification results displayed by PCA, performing Pareto scaling treatment on the common peak-to-peak area before multivariate data analysis, and calculating R by OPLS-DA 2 X,R 2 Y scores of 0.999, 0.996, Q 2 Is 0.942, and is greater than 0.5, and after 200 times replacement test, the score chart shows Q 2 The intercept of the fitted straight line on the Y coordinate axis is-2.61, which shows that the established model is reliable and has better stability and prediction capability. Ranking the contribution of 19 consensus peak areas to the grouping (VIP) size, selecting the metabolism with higher discrimination potential in the predictive modelAnimal (VIP score)>1) The total 6 chromatographic peaks meet the conditions, and the peak 3, the peak 15, the peak 14, the peak 10, the peak 12, the peak 19 and the VIP score chart are respectively shown in FIG. 6.
The above description is only for the purpose of illustrating the preferred embodiments of the present invention and is not to be construed as limiting the invention, and any modifications, equivalents and improvements made within the spirit and principle of the present invention are intended to be included within the scope of the present invention.
Claims (9)
1. A detection method for volatile components of nardostachys chinensis benth is characterized by comprising the following steps:
preparing a test article solution: weighing rhizoma Nardostachyos, adding distilled water, heating and reflux-extracting with ethyl acetate as extraction solvent, collecting ethyl acetate layer, drying, metering volume, and filtering to obtain sample of test solution;
the method comprises the following steps: adopting a capillary column chromatographic column, wherein the injection inlet temperature is 250-270 ℃, the injection amount is 0.6-1.2 mu l, the split ratio is 30-50: 1, and the temperature is programmed: the initial temperature is 60-80 ℃, and the temperature is 3-7 ℃ per minute -1 The temperature is raised to 80-100 ℃ at a speed of 30-50 ℃ per minute -1 Heating to 130-140 ℃ at a speed, and keeping for 4-6 min; at a temperature of 8-12 ℃ per minute -1 Raising the temperature to 170-180 ℃ at a speed, and keeping the temperature for 8-10 min; at 6-8 ℃ per minute -1 Heating to 240-260 ℃ by a program, and keeping for 10-20 min;
the mass spectrum conditions are as follows: EI ion source, electron energy 60-80 eV, ion source temperature: 270-290 ℃, solvent delay time: 2-3 min, wherein the scanning mode is full scanning, the detection range is m/z 50-550, and a GC-Q-active Orbitrap MS total ion flow graph of volatile components of the nardostachys chinensis is obtained;
fourthly, ingredient identification: data acquisition and analysis were performed using X Calibur software, and the chemistry in the volatile components of Nardostachys chinensis was determined using first-order mass spectrometry EI-MS matched against the nominal mass library NIST MS Search 2, Mainlib, Chinese Pharma databases.
2. The detection method according to claim 1, wherein the heating reflux extraction time in the step (1) is 1-3 h.
3. The detection method according to claim 2, wherein the heating reflux extraction time in the step (1) is 2 h.
4. The detection method according to claim 1, wherein the drying in step (1) is carried out using anhydrous Na 2 SO 4 And (5) drying.
5. The detection method according to claim 1, wherein the gas chromatography conditions in step (2) are: adopting a Thermo TG-WAXMS capillary column chromatographic column, wherein the injection inlet temperature is 260 ℃, the injection amount is 1 mul, the split ratio is 40:1, and the temperature is programmed: initial temperature 70 deg.C, at 5. min -1 Heating to 175 deg.C at a speed of 7 deg.C/min for 9min -1 The temperature is programmed to 250 ℃ and kept for 15 min.
6. The detection method according to claim 5, wherein the capillary column chromatography column in the step (2) has a size of 0.25mm x 30m x 0.25 μm.
7. A nardostachys chinensis volatile component fingerprint construction method is characterized by comprising the following steps:
preparing a test article solution: weighing rhizoma Nardostachyos, adding distilled water, heating and reflux-extracting with ethyl acetate as extraction solvent, collecting ethyl acetate layer, drying, metering volume, and filtering to obtain sample of test solution;
the gas chromatography conditions are as follows: capillary column chromatography, temperature programming: the initial temperature is 105-115 ℃, the temperature is kept for 0.8-1.2 min, and the temperature is 23-27 ℃ per min -1 Heating to 123-127 ℃, and keeping for 4-6 min; at 4-6 ℃ per minute -1 Heating to 125-135 ℃, and keeping for 2.5-3.5 min; at 28-32 ℃ per minute -1 Heating to 180-190 ℃, and keeping for 6.5-7.5 min; at 23-27 ℃ per minute -1 Heating to 205-215 ℃, and keeping for 1.5-2.5 min; at 13-17 ℃ min -1 Temperature riseKeeping the temperature to 240-260 ℃ for 4.5-5.5 min, wherein the temperature of a sample inlet is 230-250 ℃, and the temperature of a detector is 240-260 ℃; split-flow sample injection is carried out, wherein the split-flow ratio is 14-16: 1;
identification of the common peaks: introducing a gas chromatogram obtained after detecting a nardostachys chinensis volatile component test solution into Chempatern chemometrics software for analysis, calibrating a common peak by taking a chromatographic peak with a percentage peak area larger than 1.0 as a screening condition, and identifying the components of the common peak by retrieving GC-Q-active Orbitrap MS related mass spectrum data;
fourthly, establishing a fingerprint map: and (3) carrying out scaling pretreatment on the common peak area data, and generating a control fingerprint of the common mode of the volatile components of the nardostachys chinensis bunge by adopting a curve simulation method, thereby establishing the fingerprint of the volatile components of the nardostachys chinensis bunge.
8. The fingerprint construction method according to claim 7, characterized in that the steps are as follows: thermo TG-WAXMS capillary column; temperature programming: the initial temperature is 110 ℃, the temperature is kept for 1min, the temperature is raised to 125 ℃ at 25 ℃ min-1, and the temperature is kept for 5 min; heating to 130 deg.C at 5 deg.C/min-1, and maintaining for 3 min; heating to 185 deg.C at 30 deg.C/min-1, and maintaining for 7 min; heating to 210 deg.C at 25 deg.C/min-1, and maintaining for 2 min; heating to 250 deg.C at 15 deg.C/min-1, maintaining for 5min, with the injection inlet temperature of 240 deg.C and the detector temperature of 250 deg.C; split-flow sample injection with a split-flow ratio of 15: 1.
9. The fingerprint construction method according to claim 8, wherein the Thermo TG-WAXMS capillary column in step (2) has a specification of 0.25mm x 30m x 0.25 μm.
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