CN115792012A - Method for detecting fragrance components of rose dew and method for measuring fragrance component content of rose dew - Google Patents
Method for detecting fragrance components of rose dew and method for measuring fragrance component content of rose dew Download PDFInfo
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Abstract
The invention provides a method for detecting fragrance components of rose dew and a method for measuring the content of the fragrance components of the rose dew, and belongs to the technical field of analysis and detection. The method adopts ultrasonic-assisted dispersion liquid-liquid microextraction and gas chromatography-mass spectrometry technology to measure the fragrance components of the rose dew, can identify 80 fragrance components from the rose dew, can measure the content of 10 fragrance components in the rose dew, establishes a simple, rapid and high-sensitivity method for measuring the fragrance components of the rose dew, and can be used for measuring and analyzing mass rose dew samples.
Description
Technical Field
The invention relates to the technical field of analysis and detection, in particular to a method for detecting fragrance components of rose dew and a method for measuring the content of the fragrance components of the rose dew.
Background
The rose water is a byproduct generated in the distillation and extraction process of the rose essential oil, is a pure natural product, is not doped with any essence and preservative, contains trace rose essential oil components and other water-soluble components, has light and pleasant fragrance, and has the effects of resisting allergy, diminishing inflammation, resisting bacteria, supplementing skin moisture, relieving skin aging, enhancing skin vitality and the like. The cellular fluid of the fresh rose flower is liquid formed by condensing volatile substances in cells of the fresh rose flower at low temperature, and has the natural fragrance of the fresh rose flower. The rose water and rose cell sap are collectively called as "rose dew". The rose flower water is an important raw material for developing rose series foods, cosmetics, fresheners and the like, and has higher development and utilization values. The fragrance of the rose dew is an important focused index in product development and utilization, is positively correlated with the quality and economic benefit, and is a main basis for determining the quality of the rose dew. Therefore, the control of the characteristic aroma components and the content of the rose dew has important guiding significance for the reasonable processing and utilization of the rose dew. At present, methods for enriching the fragrance of rose dew include a solid phase microextraction method (SPME), a purging and trapping method (P & T), a liquid-liquid extraction method (LLE), an activated carbon adsorption method and the like, but all of the methods have certain limitations. For example, the solid-phase microextraction method and the sweeping and trapping method need special equipment, so that the equipment cost is high, and the wide application is not facilitated; the liquid-liquid extraction method usually consumes a large amount of organic solvent, is harmful to human health and causes environmental pollution; the activated carbon adsorption method is long in time consumption and complicated in steps, and is not beneficial to batch detection.
Disclosure of Invention
The invention aims to provide a method for detecting fragrance components of rose flower syrup and a method for measuring the content of the fragrance components of the rose flower syrup, wherein 80 fragrance components of the rose flower syrup can be simultaneously detected, and 10 fragrance components can be quantitatively and accurately measured.
In order to achieve the above object, the present invention provides the following technical solutions:
the invention provides a method for detecting fragrance components of rose dew, which comprises the following steps:
mixing the rose dew and the dispersed micro-extraction solution, and extracting under an ultrasonic condition to obtain an extract liquid; the dispersed micro-extraction solution is a mixed solution of an extracting agent and a dispersing agent;
performing gas chromatography-mass spectrometry detection on the extract, and performing qualitative detection on aroma components by using an NIST11 standard library to retrieve the obtained GC-MS spectrogram to obtain the aroma components of the rose dew;
the gas chromatography conditions in the gas chromatography-mass spectrometry detection comprise: a chromatographic column: HP-INNOWAX; temperature programming: the initial temperature is 60 ℃, the temperature is kept for 1min, the temperature is increased to 245 ℃/min at the speed of 2 ℃/min, and the temperature is kept for 5min; carrier gas: high purity helium gas; sample inlet temperature: 250 ℃; no shunt sampling;
the conditions of the mass spectrum in the gas chromatography-mass spectrometry detection comprise: electron bombardment ion source; electron energy: 70eV; mass spectrum voltage: 0.4kv; the transmission line temperature is 250 ℃; ion source temperature: 230 ℃; mass spectrum voltage: 0.4kv; scanning mode: a scan mode; mass scan range: m/z is 35-500u;
the fragrance component of the rose flower dew comprises 2-heptanone, n-dodecane, isoamyl alcohol, 2,6,11-trimethyldodecane, 3-methyl-1,5-pentanediol, 2-ethyl-2-hexenal, cyclohexanone, 2-heptanol, methylheptenone, n-hexanol, rose ether A, rose ether B, folyl alcohol, tetradecane, benzyl methyl ether, (S) -linalool oxide, n-heptanol, 6-methyl-5-hepten-2-ol, (E) -linalool oxide, benzaldehyde, linalool, dihydrocarveol, n-heneicosane, 4-terpenol, myrcenol, (-) -trans-rosinol, furfuryl alcohol, L-menthol, (Z) -3,7-dimethyl-2,6-octadienal, 2- (4-methyl-3-cyclohexenyl) propionaldehyde, 2-methyl-3-cyclohexenyl) propionaldehyde alpha-terpineol, verbenol, benzyl acetate, citral, 3,7-dimethyl-7-octenol, citronellol, lavandiol, (-) -myrtenol, nerol, isogeraniol, caryophyllene oxide, phenylethyl acetate, verbenol, geraniol, guaiacol, benzyl alcohol, ocimene, isopulegol, phenethyl alcohol, 3- (2,6,6-trimethyl-1-cyclohexene-1-yl) acrolein, 2,6-dimethyloct-7-ene-2,6-diol, perillyl alcohol, methyl eugenol, heptanoic acid, 4-tert-butyl phenyl acetone, 3-phenylpropanol, 4,8-dimethyl-3,7-nonadien-2-yl acetate, methyl eugenol, heptanoic acid, 4-tert-butyl phenyl acetone, 3-phenylpropanol, 4,8-3525-zxft 3525-nonadien-2-yl acetate, P-menthane-1,8-diol, 2,7-dimethyl-2,7-octanediol, 1-cyclohexyl-1-butanone, eucalyptol, bisabolol oxide B, eugenol, hydroxycitronelrol, elemene, dec-7-en-2-one, isopulegol, cinnamyl alcohol, 2,4-di-tert-butylphenol, (R) - (+) -citronellac acid, farnesol, farnesic acid, neryl acetate, (2E) -3,7-dimethyl-2,6-octadienoic acid, 4- (2,2,6-trimethylcyclohexyl) -2-butanone, 3-ethoxy-3,7-dimethyloctyl-1,6-diene, geraniol, cedrene, bisabolol, and benzoic acid.
Preferably, the volume ratio of the rose flower water to the dispersed micro-extraction solution is (5.0-7.0) mL (600-800) mu L.
Preferably, the extractant comprises dichloromethane; the dispersant comprises acetonitrile.
Preferably, the volume ratio of the extracting agent to the dispersing agent is 1 (2-3).
Preferably, the extraction time is 1-3 min.
Preferably, the volume ratio of the rose dew to the dispersed micro-extraction solution is 7.0 mL; the volume ratio of the extracting agent to the dispersing agent is 1:2; the extraction time is 3min.
The invention provides a method for measuring the content of fragrance components of rose dew, which comprises the following steps:
preparing standard series of 10 rose dew aroma components mixed standard working solutions with different mass concentrations, performing gas chromatography-mass spectrometry detection to obtain a standard substance total ion flow graph of the 10 rose dew aroma components, and establishing a standard curve by taking peak areas as vertical coordinates and mass concentrations as horizontal coordinates;
mixing the rose dew and the dispersed micro-extraction solution, and extracting under an ultrasonic condition to obtain an extract liquid; the dispersed micro-extraction solution is a mixed solution of an extracting agent and a dispersing agent;
performing gas chromatography-mass spectrometry detection on the extract, and comparing the obtained GC-MS spectrogram with a standard substance spectrogram to determine 10 aroma components of the rose dew;
the gas chromatography conditions in the gas chromatography-mass spectrometry detection comprise: a chromatographic column: HP-INNOWAX; temperature programming: the initial temperature is 60 ℃, the temperature is kept for 1min, the temperature is raised to 245 ℃/min at the speed of 2 ℃/min, and the temperature is kept for 5min; carrier gas: high purity helium gas; sample inlet temperature: 250 ℃; the split ratio is as follows: 50;
the conditions of the mass spectrum in the gas chromatography-mass spectrometry detection comprise: electron bombardment ion source; electron energy: 70eV; mass spectrum voltage: 0.4kv; the transmission line temperature is 250 ℃; ion source temperature: 230 ℃; mass spectrum voltage: 0.4kv; scanning mode: a scan mode; mass scan range: m/z is 35-500u;
comparing the peak areas of the spectrograms of the 10 fragrance components of the rose dew with the standard curve to obtain the content of the fragrance components of the rose dew;
the 10 rose flower dew aroma components comprise citronellol, linalool, citronellyl acetate, methyl eugenol, phenethyl alcohol, geraniol acetate, nerol, eugenol, geraniol and benzyl alcohol.
The invention provides a method for detecting fragrance components of rose dew, which is used for detecting the fragrance components of the rose dew by combining ultrasonic-assisted dispersion liquid-liquid microextraction with a gas chromatography-mass spectrometry technology, wherein the dispersion liquid-liquid microextraction utilizes an extracting agent to form dispersed fine liquid drops in a sample solution under the action of a dispersing agent to form an extracting agent-dispersing agent-sample solution three-phase emulsion system, so that the contact area of the extracting agent and an analyte can be increased, and the analyte can be rapidly distributed and balanced between the sample solution and the extracting agent to complete extraction.
The method can identify 80 aroma components from the rose dew, wherein the rose cell sap identifies 61 aroma components, 55 aroma components of rose water, 53 aroma components of rose flower water and 55 aroma components of rose pickling flower water, and the aroma components with higher relative content comprise citronellol, hydroxy citronellol, eugenol, linalool, alpha-terpineol, phenethyl alcohol, nerol, geraniol, methyl eugenol and the like. The results of the examples show that the relative contents and the component compositions of the cell sap of the fresh rose flowers, the rose water, the rose dew obtained by different processing techniques and the fragrance component analysis of the rose dew of different manufacturers are different, and a certain theoretical basis is provided for the fragrance characteristics and the development and the utilization of the fragrance characteristics of the rose dew.
The invention provides a method for measuring the fragrance component content of rose dew, which adopts an ultrasonic-assisted dispersion liquid-liquid microextraction-gas chromatography/mass spectrometry combined technology to quickly quantify the fragrance components of the rose dew, can measure the content of 10 fragrance components in the rose dew and establish a simple, quick and high-sensitivity method for measuring the fragrance components of the rose dew, wherein the linear relation of the 10 fragrance components in the rose dew in a certain mass concentration range is good, the correlation coefficients are all larger than 0.9991, the detection limit of the method is 0.050-0.078 mg/L, the lower limit of quantification is 0.166-0.261 mg/L, the average recovery rate is 79.806-113.780%, and the relative standard deviation is 2.016-9.576%. The method is accurate and reliable, has the advantages of simple operation, small organic solvent consumption, rapidness, sensitivity and the like, and can be used for measuring and analyzing mass rose syrup samples.
Drawings
FIG. 1 is a graph showing the effect of different sample amounts on the aroma enrichment efficiency;
FIG. 2 is a graph showing the effect of different ultrasonic extraction times on the aroma component enrichment efficiency;
FIG. 3 is a graph of the effect of different extractant types (a) and extractant volumes (b) on aroma enrichment efficiency;
FIG. 4 is a graph of the effect of dispersant type and extractant and dispersant volume ratio on aroma enrichment efficiency;
FIG. 5 is a total ion flow diagram of the fragrance component of rose water of example 1; a is a total ion flow diagram of cell fluid of fresh flowers of the roses, b is a total ion flow diagram of water of the roses, c is a total ion flow diagram of water of the fresh flowers, and d is a total ion flow diagram of water of pickled flowers;
FIG. 6 is a diagram showing the classification analysis of cell sap of fresh rose flowers and aroma components of rose water;
FIG. 7 is a diagram of the classification analysis of the aroma components of the rose dew according to different processing techniques;
FIG. 8 is a classification chart of the fragrance components of rose dew from different manufacturers;
FIG. 9 is a total ion flow graph of 10 characteristic aroma component standards;
fig. 10 is a total ion flow diagram of the fragrance component of the rose dew in example 10, a is a total ion flow diagram of fresh flower cell sap (split ratio: 50: 1), b is a total ion flow diagram of rose water (split ratio: 50: 1), c is a total ion flow diagram of fresh flower water (split ratio: 50: 1), and d is a total ion flow diagram of pickled flower water (split ratio: 50.
Detailed Description
The invention provides a method for detecting fragrance components of rose dew, which comprises the following steps:
mixing the rose dew and the dispersed micro-extraction solution, and extracting under an ultrasonic condition to obtain an extract liquid; the dispersed micro-extraction solution is a mixed solution of an extracting agent and a dispersing agent;
performing gas chromatography-mass spectrometry detection on the extract, and performing qualitative detection on aroma components by using an NIST11 standard library to retrieve the obtained GC-MS spectrogram to obtain the aroma components of the rose dew;
the gas chromatography conditions in the gas chromatography-mass spectrometry detection comprise: a chromatographic column: HP-INNOWAX; temperature programming: the initial temperature is 60 ℃, the temperature is kept for 1min, the temperature is increased to 245 ℃/min at the speed of 2 ℃/min, and the temperature is kept for 5min; carrier gas: high purity helium gas; sample inlet temperature: 250 ℃; no-shunt sample introduction;
the conditions of the mass spectrum in the gas chromatography-mass spectrometry detection comprise: electron bombardment ion source; electron energy: 70eV; mass spectrum voltage: 0.4kv; the transmission line temperature is 250 ℃; ion source temperature: 230 ℃; mass spectrum voltage: 0.4kv; scanning mode: a scan mode; mass scan range: m/z is 35-500u;
the fragrance component of the rose flower dew comprises 2-heptanone, n-dodecane, isoamyl alcohol, 2,6,11-trimethyldodecane, 3-methyl-1,5-pentanediol, 2-ethyl-2-hexenal, cyclohexanone, 2-heptanol, methylheptenone, n-hexanol, rose ether A, rose ether B, folyl alcohol, tetradecane, benzyl methyl ether, (S) -linalool oxide, n-heptanol, 6-methyl-5-hepten-2-ol, (E) -linalool oxide, benzaldehyde, linalool, dihydrocarveol, n-heneicosane, 4-terpenol, myrcenol, (-) -trans-rosinol, furfuryl alcohol, L-menthol, (Z) -3,7-dimethyl-2,6-octadienal, 2- (4-methyl-3-cyclohexenyl) propionaldehyde, 2-methyl-3-cyclohexenyl) propionaldehyde alpha-terpineol, verbenol, benzyl acetate, citral, 3,7-dimethyl-7-octenol, citronellol, lavandiol, (-) -myrtenol, nerol, isogeraniol, caryophyllene oxide, phenylethyl acetate, verbenol, geraniol, guaiacol, benzyl alcohol, ocimene, isopulegol, phenethyl alcohol, 3- (2,6,6-trimethyl-1-cyclohexene-1-yl) acrolein, 2,6-dimethyloct-7-ene-2,6-diol, perillyl alcohol, methyl eugenol, heptanoic acid, 4-tert-butyl phenyl acetone, 3-phenylpropanol, 4,8-dimethyl-3,7-nonadien-2-yl acetate, methyl eugenol, heptanoic acid, 4-tert-butyl phenyl acetone, 3-phenylpropanol, 4,8-3525-zxft 3525-nonadien-2-yl acetate, P-menthane-1,8-diol, 2,7-dimethyl-2,7-octanediol, 1-cyclohexyl-1-butanone, eucalyptol, bisabolol oxide B, eugenol, hydroxycitronelrol, elemene, dec-7-en-2-one, isopulegol, cinnamyl alcohol, 2,4-di-tert-butylphenol, (R) - (+) -citronellac acid, farnesol, farnesic acid, neryl acetate, (2E) -3,7-dimethyl-2,6-octadienoic acid, 4- (2,2,6-trimethylcyclohexyl) -2-butanone, 3-ethoxy-3,7-dimethyloctyl-1,6-diene, geraniol, cedrene, bisabolol, and benzoic acid.
In the present invention, unless otherwise specified, all reagents or instruments required are commercially available products well known to those skilled in the art.
In the invention, the rose flower water preferably comprises one or more of fresh rose flower cell sap, rose flower water, fresh rose flower water and rose-pickled flower water. The source of the rose dew is not specially limited, and the rose dew is commercially available and well known in the field; in the examples of the present invention, samples of fresh rose flower water and rose-pickled flower water were provided by Tianrun rose industries, gansu, oriental, gansu; the cell sap samples of the rose water and the rose flowers are provided by Gansu Changsheng rose development Co.
In the invention, the dispersed micro-extraction solution is a mixed solution of an extracting agent and a dispersing agent; the extractant preferably comprises dichloromethane; the dispersant preferably comprises acetonitrile; the volume ratio of the extracting agent to the dispersing agent is preferably 1 (2-3), and more preferably 1:2; the volume ratio of the rose water to the dispersed micro-extraction solution is preferably (5.0-7.0) mL (600-800) μ L, more preferably 7.0 mL.
The rose dew and the dispersed micro-extraction solution are not particularly limited in the invention, and the materials are uniformly mixed according to the well-known process in the field.
The present invention is not particularly limited in the manner of providing the ultrasonic conditions, and any ultrasonic apparatus known in the art may be used; the extraction time is preferably 1 to 3min, more preferably 3min.
After the extraction is finished, the mixture is preferably centrifuged for 3min at the rotating speed of 3000r/min, the obtained extract phase is deposited at the bottom of the tube and is obviously separated from the water phase, and the extract phase is completely sucked out by using a micro-injector to obtain the extract liquid.
After the extract liquid is obtained, the extract liquid is subjected to gas chromatography-mass spectrometry detection, and the obtained GC-MS spectrogram is subjected to NIST11 standard library retrieval to determine the aroma components, so that the rose dew aroma components are obtained.
In the invention, the gas chromatography-mass spectrometry detection conditions comprise: a chromatographic column: HP-INNOWAX (60 m.times.0.250 mm. Times.0.5 μm); temperature programming: the initial temperature is 60 ℃, the temperature is kept for 1min, the temperature is increased to 245 ℃/min at the speed of 2 ℃/min, and the temperature is kept for 5min; carrier gas: high-purity helium (the purity is more than or equal to 99.999%); sample inlet temperature: 250 ℃; no split-flow sample introduction.
In the present invention, the conditions of mass spectrometry in the gas chromatography-mass spectrometry detection include: electron bombardment ion source; electron energy: 70eV; mass spectrum voltage: 0.4kv; the transmission line temperature is 250 ℃; ion source temperature: 230 ℃; mass spectrum voltage: 0.4kv; scanning mode: a scan mode; mass scan range: m/z is 35-500 u.
In the present invention, the gas chromatography-mass spectrometry detection is preferably performed by a GCMS-QP2010Ultra gas chromatography/mass spectrometer (Shimadzu corporation, japan).
In the present invention, the aroma components of the rose flower water in the GC-MS spectrogram are preferably searched by using a NIST17 standard library, and the identified components with the matching degree of more than 85 (the maximum value is 100) are reported and confirmed by combining with standard substances.
In the present invention, in the case of the present invention, the fragrance components of the rose water comprise 2-heptanone, n-dodecane, isoamyl alcohol, 2,6,11-trimethyldodecane, 3-methyl-1,5-pentanediol, 2-ethyl-2-hexenal, cyclohexanone, 2-heptanol, methyl heptenone, n-hexanol, rose ether A, rose ether B, folyl alcohol, tetradecane, benzyl methyl ether, (S) -linalool oxide, n-heptanol, 6-methyl-5-hepten-2-ol, (E) -linalool oxide, benzaldehyde, linalool, dihydrocarveol, n-heneicosane, 4-terpenol, myrcenol, (-) - -trans-rosinol, furfuryl alcohol, L-menthol, (Z) -3,7-dimethyl-2,6-octadienal 2- (4-methyl-3-cyclohexenyl) propanal, α -terpineol, verbenol, phenylmethyl acetate, citral, 3,7-dimethyl-7-octenol, citronellol, lavandil, (-) -myrtenol, nerol, isogeraniol, caryophyllene oxide, phenylethyl acetate, verbenol, geraniol, guaiacol, benzyl alcohol, ocimene, isopulegol, phenylethyl alcohol, 3- (2,6,6-trimethyl-1-cyclohexen-1-yl) acrolein, 2,6-dimethyloct-7-ene-2,6-diol, perillyl alcohol, methyl eugenol, heptanoic acid, 4-tert-butyl phenyl acetone, 3-phenylpropanol, 4,8-dimethyl-3,7-nonadien-2-yl acetate, p-menthane-1,8-diol, 2,7-dimethyl-2,7-octanediol, 1-cyclohexyl-1-butanone, eucalyptol, bisabolol oxide B, eugenol, hydroxycitronelrol, elemene, dec-7-en-2-one, isopulegol, cinnamyl alcohol, 2,4-di-tert-butylphenol, (R) - (+) -citronellac acid, farnesol, farnesic acid, neryl acetate, (2E) -3,7-dimethyl-3735 zxft 3535-octadienoic acid, 4- (2,2,6-trimethylcyclohexyl) -2-butanone, 3-ethoxy-3,7-dimethyloctyl-1,6-dienol, elemenol, bisabole, bisabolol, and benzoic acid.
The invention provides a method for measuring the fragrance component content of rose dew, which comprises the following steps:
preparing standard series of 10 rose dew aroma components mixed standard working solutions with different mass concentrations, performing gas chromatography-mass spectrometry detection to obtain a standard substance total ion flow graph of the 10 rose dew aroma components, and establishing a standard curve by taking peak areas as vertical coordinates and mass concentrations as horizontal coordinates;
mixing the rose dew and the dispersed micro-extraction solution, and extracting under an ultrasonic condition to obtain an extract liquid; the dispersed micro-extraction solution is a mixed solution of an extracting agent and a dispersing agent;
performing gas chromatography-mass spectrometry detection on the extract, and comparing the obtained GC-MS spectrogram with a standard substance spectrogram to determine 10 aroma components of the rose dew;
the gas chromatography conditions in the gas chromatography-mass spectrometry detection comprise: and (3) chromatographic column: HP-INNOWAX; temperature programming: the initial temperature is 60 ℃, the temperature is kept for 1min, the temperature is raised to 245 ℃/min at the speed of 2 ℃/min, and the temperature is kept for 5min; carrier gas: high purity helium gas; sample inlet temperature: 250 ℃; the split ratio is as follows: 50;
the conditions of the mass spectrum in the gas chromatography-mass spectrometry detection comprise: electron bombardment ion source; electron energy: 70eV; mass spectrum voltage: 0.4kv; the transmission line temperature is 250 ℃; ion source temperature: 230 ℃; mass spectrum voltage: 0.4kv; scanning mode: a scan mode; mass scan range: m/z is 35-500u;
comparing the peak areas of the spectrograms of the 10 fragrance components of the rose dew with the standard curve to obtain the content of the fragrance components of the rose dew;
the 10 kinds of fragrance components of the rose flower water comprise citronellol, linalool, citronellyl acetate, methyl eugenol, phenethyl alcohol, geraniol acetate, nerol, eugenol, geraniol and benzyl alcohol.
In the invention, the process of preparing the standard series of 10 mixed standard working solutions of rose dew aroma components with different mass concentrations is preferably as follows:
1) Standard mixed stock solution I and standard series mixed working solution
Taking dichloromethane as a solvent, accurately weighing a proper amount of linalool, citronellyl acetate, geranyl acetate, citronellol, nerol, geraniol, benzyl alcohol, phenethyl alcohol, methyl eugenol and eugenol standard substances (the accuracy is 0.1 mg), respectively using dichloromethane to fix the volume to 25mL, preparing single-standard solutions with mass concentrations of 2000mg/L, 4340mg/L, 4788mg/L, 3632mg/L, 2572mg/L, 4536mg/L, 4120mg/L, 4496mg/L, 4864mg/L and 5720mg/L, accurately measuring 750 mu L, 400 mu L and 400 mu L of the single-standard solutions in a 5mL volumetric flask to fix the volume, and preparing a standard mixed stock solution I, wherein the mass concentration of the standard mixed stock solution I is shown in a table 2.
2) Taking dichloromethane as a solvent, and taking the standard mixed stock solution I to dilute step by step.
Taking 700 mu L of standard mixed stock solution I, and preparing standard mixed working solution 1 after constant volume is 1.0 mL; taking 500 mu L of standard mixed stock solution I, and preparing standard mixed working solution 2 after the constant volume is 1.0 mL; taking 350 mu L of standard mixed stock solution I, and preparing standard mixed working solution 3 after the constant volume is 1.0 mL; taking 170 mu L of standard mixed stock solution I, and preparing standard mixed working solution 4 after the constant volume is 1.0 mL; taking 70 mu L of standard mixed stock solution I, and preparing standard mixed working solution 5 after the constant volume is 1.0 mL; taking 20 mu L of standard mixed stock solution I, and preparing a standard mixed working solution 6 after the constant volume is 1.0 mL; taking 10 mu L of the standard mixed stock solution I, and fixing the volume to 1.0mL to prepare a standard mixed working solution 6.
In the present invention, the conditions of gas chromatography in the gas chromatography-mass spectrometry detection preferably include: and (3) chromatographic column: HP-INNOWAX; temperature programming: the initial temperature is 60 ℃, the temperature is kept for 1min, the temperature is increased to 245 ℃/min at the speed of 2 ℃/min, and the temperature is kept for 5min; carrier gas: high purity helium gas; sample inlet temperature: 250 ℃; the split ratio is as follows: 50:1.
In the present invention, the conditions of mass spectrometry in the gas chromatography-mass spectrometry detection preferably include: electron bombardment ion source; electron energy: 70eV; mass spectrum voltage: 0.4kv; the transmission line temperature is 250 ℃; ion source temperature: 230 ℃; mass spectrum voltage: 0.4kv; scanning mode: a scan mode; mass scan range: m/z is 35-500 u.
The process of establishing the standard curve is not specially limited, and the standard curve can be established by adopting standard mixed working solution with different concentrations according to the process known in the art and taking the peak area as the ordinate and the mass concentration as the abscissa.
The process of measuring the content of the fragrance component of the rose dew by comparing the peak area of the spectrogram obtained by the technical scheme with the standard curve is not specially limited and can be carried out according to the process known in the field.
The technical solution of the present invention will be clearly and completely described below with reference to the embodiments of the present invention. It is to be understood that the described embodiments are merely exemplary of the invention, and not restrictive of the full scope of the invention. All other embodiments, which can be obtained by a person skilled in the art without making any creative effort based on the embodiments in the present invention, belong to the protection scope of the present invention.
In the following examples, the samples used: fresh rose flower cell sap, rose flower water, fresh rose flower water and rose pickling flower water;
the rose-pickled flower water is obtained by extracting rose essential oil from fresh flowers through salting, the rose-fresh flower water is obtained by extracting the rose essential oil from the fresh flowers without salting, and the rose-pickled flower water and the rose-fresh flower water samples are provided by Tianrun rose industry company of Gansu Orientia; the rose water is obtained by salting fresh flowers to extract essential oil of rose, and a sample is provided by Gansu Changsheng rose development Co., ltd; the fresh rose flower cell sap is liquid formed by condensing volatile substances in fresh rose flower cells at low temperature, and a fresh rose flower cell sap sample is provided by Gansu Changsheng rose development Co.
Example 1
Transferring 7.0mL of a rose sample (fresh rose cell sap, rose water, fresh rose flower water and rose pickled flower water) into a 15mL pointed-bottom centrifuge tube with a plug, adding 600 μ L of a dispersive microextraction solution (the volume ratio of dichloromethane (an extracting agent) to acetonitrile (a dispersing agent) is 1:2), extracting in an ultrasonic instrument for 3min, centrifuging the obtained mixture at 3000r/min for 3min, depositing the obtained extraction phase at the bottom of the centrifuge tube, and sucking out all the enriched extraction phase deposited at the bottom of the tube by using a micro-syringe to obtain an extraction solution;
and (3) carrying out gas chromatography-mass spectrometry detection on the extract liquor in a GCMS-QP2010Ultra gas chromatography/mass spectrometer:
gas chromatography conditions: and (3) chromatographic column: HP-INNOWAX (60 m.times.0.250 mm.times.0.5 μm); temperature programming: the initial temperature is 60 ℃, the temperature is kept for 1 minute, the temperature is increased to 245 ℃/min at the speed of 2 ℃/min, and the temperature is kept for 5min; carrier gas: high-purity helium (the purity is more than or equal to 99.999%); sample inlet temperature: 250 ℃; no shunt sampling;
mass spectrum conditions: electron bombardment ion source; electron energy: 70eV; mass spectrum voltage: 0.4kv; the transmission line temperature is 250 ℃; ion source temperature: 230 ℃; mass spectrum voltage: 0.4kv; scanning mode: a scan mode; mass scan range: m/z is 35-500u;
the resulting spectra were retrieved using the NIST17 standard library and identified components with a degree of match greater than 85 (100 max) were reported and confirmed in combination with standard substances.
Example 2
The only difference from example 1 is: the sample amounts were 1.0mL, 3.0mL, 5.0mL, 9.0mL, and 11.0mL, respectively.
Example 3
The only difference from example 1 is: the extraction time is 0min, 1min, 5min, 7min, and 9min.
Example 4
The only difference from example 1 is: the extracting agents are respectively trichloromethane, chlorobenzene, carbon tetrachloride and toluene.
Example 5
The only difference from example 1 is: the extractant volumes were 50. Mu.L, 100. Mu.L, 150. Mu.L, and 250. Mu.L, respectively.
Example 6
The only difference from example 1 is: the dispersant is methanol or acetone respectively.
Example 7
The only difference from example 1 is: the volume ratio of the extractant to the dispersant is 1:3, 1:4, 1:5, 1:6, 1:7, or 1:8.
Example 8
The only difference from example 1 is: the column was HP-5MS (30 m.times.0.250 mm. Times.0.25 μm) or DB-FFAP (60 m.times.0.250 mm. Times.0.5 μm), respectively.
Example 9
The only difference from example 1 is: the mass spectrometer voltages were 0.3kv, 0.5kv and 0.6kv, respectively.
Example 10
The only difference from example 1 is: the chromatographic detection adopts split sample injection, and the split ratio is 50.
1. Test results
1) FIG. 1 is a graph showing the effect of different sample amounts on the enrichment efficiency of the fragrance components of rose water; as can be seen from FIG. 1, when the sample amount is 1.0mL and 3.0mL, the rose water sample and the supernatant (acetonitrile) have obvious layering phenomenon, but dichloromethane and the sample solution are not layered, and the supernatant is taken for analysis, only citronellol is detected, and other main aroma components are not detected; when the sample amount is 5mL, 7mL, 9mL or 11mL, the dichloromethane and the rose water sample form a stable two-phase system, the layered interface is clear, but the dichloromethane volume of the precipitation layer is inversely proportional to the sample amount, and the larger the sample amount is, the smaller the volume of the lower-layer precipitator is; when the sample volume is 9.0mL, the volume of the precipitating agent is less than 20 muL, when the sample volume is 11.0mL, the volume of the precipitating agent is less, the volume of the precipitating agent cannot reach the minimum volume required by automatic sample injection of a gas chromatography-mass spectrometer, manual sample injection analysis is required, and the method is not suitable for high-throughput sample determination. As shown in FIG. 1, the peak area and the number of peaks both increased as the amount of the sample increased, and were the highest when the amount of the sample was 11 mL. However, when the sample amount is 9.0mL and 11.0mL, the mass spectrograms of the characteristic components of the rose water, namely linalool, citronellol, nerol, geraniol and eugenol, are saturated, so that the quantitative accuracy is influenced.
Fig. 2 shows the influence of different ultrasonic extraction times on the enrichment efficiency of the fragrance components in the rose water, and as can be seen from fig. 2, the total peak area and the peak number tend to increase first and then decrease, and when the ultrasonic time is 3min, the total peak area and the peak number are both the highest, so that 3min is selected as the optimal ultrasonic time.
FIG. 3 shows the effect of different types of extractants on the enrichment efficiency of the fragrance components of the rose water, as shown in FIG. 3, when dichloromethane is used as the extractant, the sum of the peak areas and the number of peaks of the fragrance components are the highest, and the enrichment efficiency of the fragrance components of the rose water is higher; when toluene is used as an extracting agent, the toluene and the rose water sample cannot form a two-phase system; therefore, dichloromethane was chosen as the extractant.
The influence of the volume of the extracting agent on the aroma component enrichment efficiency is researched, and the result shows that when the extracting agent is respectively 50 mu L, 100 mu L and 150 mu L, the dichloromethane and the rose water sample cannot form a stable two-phase system; when the extractant is 200 mu L and 250 mu L, the layering interface of dichloromethane and rose water samples is clear after centrifugation, and the dichloromethane dosage of 200 mu L is selected in the test in consideration of the enrichment times and the reagent dosage.
FIG. 4 is a graph showing the effect of the type of dispersant and the volume ratio of the extractant and dispersant on the efficiency of the enrichment of the fragrance component of rose water; as can be seen from a in fig. 4, the extraction efficiency of acetonitrile as a dispersant was higher than that of acetone or methanol, and the sum of the peak areas and the number of peaks of the aroma components were high. As can be seen from b in FIG. 4, the total peak area and the peak number of the fragrance components of the rose water are the highest when the volume ratio of the peak area to the peak number is 1:2, and the extraction capability is strong, so that the volume ratio of dichloromethane to acetonitrile selected in the experiment is 1:2.
The comparison of the results of the example 8 and the example 1 shows that the HP-5MS separation effect is poor, and the chromatographic peaks of citronellol and nerol which are main aroma components of rose water are completely overlapped through the verification of a standard substance; both HP-INNOWAX and DB-FFAP gave good separation, but both DB-FFAP peak area and peak number were lower than HP-INNOWAX at the same integration event. The main fragrance component content of the rose water is different, in order to detect trace fragrance components as far as possible and improve the equipment sensitivity, a non-shunting sample injection mode is adopted,
comparison of the results of example 9 with those of example 1 shows that at 0.3kv, the main aroma component has a lower chromatographic peak response, with linalool and citronellol being detected only, and no other components being detected; the main fragrance components can be detected at 0.4kv, 0.5kv and 0.6 kv; under the conditions of 0.5kv and 0.6kv, the chromatographic peak of the main aroma component is over saturated, the peak shape of each peak is not sharp, especially the chromatographic peak of citronellol is wide and asymmetric, which is not beneficial to quantitative analysis, and in addition, the baseline is also unstable, and the interference of miscellaneous peaks is large, so the analysis is selected to be carried out under 0.4 kv.
2. Qualitative testing
1) In example 1, after the fragrance component of the rose flower liquid is subjected to GC-MS separation, the total ion flow diagram of the fragrance component of the rose flower liquid is shown in FIG. 5, wherein a is the total ion flow diagram of cell fluid of fresh flowers of roses, b is the total ion flow diagram of water of the roses, c is the total ion flow diagram of water of the fresh flowers, and d is the total ion flow diagram of water of pickled flowers. Searching the spectrogram by using an NIST17 standard spectral library, reporting the identified components with the matching degree of more than 85 (the maximum value is 100), confirming by combining standard substances, obtaining the qualitative result of the fragrance components of the rose water, and relatively quantifying by adopting a peak area normalization method, wherein the qualitative result and the relative content are shown in a table 1.
TABLE 1 identification results and relative content of fragrance components of rose water
Note: nd was not detected.
As can be seen from Table 1, 80 aroma components are identified from different rose lotions, wherein 61 types of rose cell sap, 55 types of rose water, 53 types of rose flower water and 55 types of rose pickling flower water are identified, and the aroma components with relatively high content comprise citronellol (10.22-30.09%), hydroxycitronelol (2.14-10.23%), eugenol (6.75-9.76%), linalool (4.96-14.29%), alpha-terpineol (2.38-10.97%), phenethyl alcohol (3.84-5.96%), nerol (0.25-6.73%), geraniol (1.27-14.68%), methyl eugenol (2.30-5.93%) and the like. The functional groups can be divided into 8 categories, which are respectively: alcohols, phenols, ethers, ketones, esters, aldehydes, acids, and others.
2) Analysis of cellular fluid of fresh rose flower and fragrance component of rose water
The rose flower cell sap is a liquid obtained by condensing volatile substances in the cells of the rose flowers at low temperature, has the natural fragrance of the rose flowers, is a byproduct generated in the distillation and extraction process of rose essential oil, detects the fragrance components of the rose flower cell sap according to the method in the example 1, and is shown in a classification chart of the fragrance components of the rose cell sap and the rose flower water in figure 6.
FIG. 6 is a diagram of classification analysis of cell sap of fresh rose flowers and aroma components of rose water. As can be seen from FIG. 6, 70 aroma components are identified from the cellular fluid of fresh roses and the rose water, wherein 61 fragrance components are identified from the cellular fluid of fresh roses and 55 fragrance components are identified from the rose water, the cellular fluid of fresh roses and the rose water share 45 fragrance components such as citronellol, nerol, geraniol and phenethyl alcohol, and the sum of the relative contents is 93.14% and 85.98% respectively; the unique components of the fresh rose flower cell sap comprise 16 kinds of neryl acetate, benzyl acetate, benzaldehyde, citral and the like, and the relative total content is 1.89%; the specific components of the rose water comprise 10 types of ocimene, (E) -linalool oxide, isoamylol, myrcenol and the like, and the relative total content is 4.17%.
As can be seen from FIG. 6, the relative contents of alcohol compounds in the cellular fluid of fresh rose flower and the rose water were high, and 39 types were identified, 33 types of cellular fluid of fresh rose flower were identified, 32 types of cellular fluid of rose flower were identified, and the alcohol content (the sum of the relative contents: 79.35%) of cellular fluid of fresh rose flower was significantly higher than that (the sum of the relative contents: 66.37%) of rose water. The content difference of the phenols in the fresh rose flower cell sap and the rose water is large, and the sum of the relative contents is 7.07 percent and 9.89 percent respectively. The total content of ether substances in the cell sap of the fresh rose and the water of the rose is 4.63 percent and 7.45 percent respectively, and the unique component of the cell sap of the fresh rose is rose ether B (0.05 percent). 5 ketones were identified, and the relative amounts of the ketones in the fresh rose flower cellular fluid and rose water were 0.82% and 2.12%, respectively. 3 ester substances are identified in fresh rose flower cell sap and rose flower water, and the unique benzyl acetate (0.17%), neryl acetate (0.11%) and phenethyl acetate (0.25%) of the rose flower water. The cell sap of fresh rose flower contains 3 kinds of aldehydes with relative content of 0.17%, and the cell sap of fresh rose flower contains 2 kinds of aldehydes with relative content of 0.54%. Acid compounds identified 3, the unique (R) - (+) -citronellac acid (0.28%), (2E) -3,7-dimethyl-2,6-octadienoic acid (0.25%), the unique heptanoic acid of rose water (0.82%). In addition, 9 other classes of compounds were identified with relative contents of 1.86% and 2.82% in fresh rose flower cellular fluid and rose water, respectively. As analyzed by the above discussion, the aroma components of rose water and rose cellular fluids differ in their relative contents and composition.
3) Analysis of fragrance components of rose dew obtained by different processing techniques
The rose dew is a byproduct generated in the distillation and extraction process of rose essential oil, the distillation and extraction process of the rose essential oil is divided into two processes of flower direct extraction and flower pickling extraction, the rose dew (flower water and pickled flower water) generated by the two extraction processes is extracted and subjected to gas quality detection according to the method of the embodiment 1, and the obtained aroma component classification chart is shown in fig. 7.
FIG. 7 is a chart showing the classification analysis of the aroma components of the rose water of different processing technologies, and it can be seen from FIG. 7 that the fresh flower water and the pickled flower water identify 62 kinds of aroma components, wherein the fresh flower water identifies 53 kinds and the pickled flower water 55 kinds, the common components include 46 kinds of citronellol, nerol, geraniol, phenethyl alcohol and the like, and the sum of the relative contents in the fresh flower water and the pickled flower water is 92.84% and 87.25%, respectively; the flower water contains 7 kinds of specific components including dihydrocarveol, 4-terpene alcohol, trans-rosinol, etc. and the relative total content is 0.97%; the pickled flower water contains 9 kinds of benzyl methyl ether, furfuryl alcohol, isopulegol, benzoic acid, etc. and has a total content of 5.71%.
33 alcohol compounds are identified in the fresh flower water and the pickled flower water, and the sum of the relative contents is 76.05% and 66.85% respectively. The alcohol compounds are main aroma components of the rose, the content of the compounds determines the quality of the rose dew, wherein citronellol is sweet rose aroma, linalool is green tea faint scent, and phenethyl alcohol has sweet honey flavor and is a main source of the rose aroma in the rose dew. Flower water is characterized by 4 kinds of dihydrocarveol (0.08%), 4-terpene alcohol (0.13%), L-menthol (0.13%), (-) -trans-rosinol (0.15%), pickling flower water is characterized by 4 kinds of furfuryl alcohol (0.12%), isopulegol (0.15%), 2,7-dimethyl-2,7-octanediol (0.11%), and bisabolol (0.11%). 1 ether (0.15%), 2 acid (2.59%) and 2 ketone (2.48%) peculiar to the pickled flower water; 2 aldehydes (0.41%) and 1 ester (0.07%) are peculiar to fresh flower water; in addition to the above, 7 other classes of compounds were identified, with relative contents of 2.57% and 2.90% in fresh flower and pickled flower water, respectively.
4) Analysis of fragrance components of rose dew from different manufacturers
The unique fragrance type of the rose dew is that one or more fragrance components play a leading role, the rest play a coordinating role, different fragrance notes are shown due to different proportions of various components, and the classification chart of the fragrance components of the rose dew of different manufacturers is shown in a figure 8. The data analysis of the rose dew (manufacturer 1) and the salt-soaked flower water (manufacturer 2) in the table 1 is used for discussing the fragrance component compositions of the rose dew of different manufacturers, and the fragrance component classification chart is shown in fig. 8. The rose lotions of manufacturer 1 and manufacturer 2 identified 68 aroma components, of which 55 were identified for both manufacturer 1 and manufacturer 2. As shown in Table 1, the rose flower syrup (manufacturer 1) and the salted floral water (manufacturer 2) have different types and contents, the common components of the rose flower syrup and the salted floral water comprise 42 types of citronellol, nerol, eugenol, methyl eugenol and the like, and the sum of the relative contents of the rose flower syrup and the salted floral water in the manufacturers 1 and 2 is 75.81% and 88.01% respectively; the rose flower lotion of manufacturer 1 contains 13 ingredients such as ocimene, 1-cyclohexyl-1-butanone, cinnamyl alcohol, 2-ethyl-2-hexenal, benzyl alcohol and the like, and the relative total content is 13.34%; the specific components of the pickled flower water comprise 13 kinds of guaiacol, farnesol, benzyl methyl ether, lavender alcohol, citral, benzyl acetate, (R) - (+) -citronellac acid, benzoic acid and the like, and the relative total content is 4.95%.
The content of alcohol compounds in the rose dew is obviously higher than that of other compounds, 35 alcohol compounds are identified, 32 alcohol compounds are identified by the manufacturer 1, 29 alcohol compounds are identified by the manufacturer 2, the relative contents are 66.37% and 66.85%, the main alcohol substances comprise citronellol, hydroxycitronelol, linalool, alpha-terpineol, phenethyl alcohol and the like, and the compounds actively contribute to the aroma characteristics of the rose dew. The compounds of ketone, aldehyde, ester and ether are also important components in the fragrance component of rose dew. The ketone substances in the rose dew of different manufacturers have obvious difference, the relative total content is respectively 2.12 percent and 3.37 percent, the rose dew contains grease gas, the rose dew of the manufacturers has the characteristics of 1-cyclohexyl-1-butanone (0.11 percent) and 2 rose dew of the manufacturers has the characteristics of 4-tert-butyl phenylacetone (0.16 percent) and decyl-7-alkene-2-ketone (0.21 percent). The types and the contents of aldehyde substances in the rose lotions of different manufacturers are different, 3 types of the rose lotions of the manufacturer 1 are unique, and the sum of the relative contents is 0.68 percent; manufacturer 2 identified 1 species with a relative content of 0.19%. 2 esters are identified in the rose flower water of the manufacturer 2, and the relative content is 0.50%. A total of 4 acids were identified, 1 for the manufacturer 1-specific heptanoic acid (0.82%), and 3 for the manufacturer 2-specific (R) - (+) -citronellaic acid (0.72%), farnesoic acid (0.13%), benzoic acid (2.46%). The rose water identifies 4 ethers, and the sum of the relative contents is 7.45% and 7.02%, wherein the manufacturer 2 has benzyl methyl ether (0.15%); the rose ether is identified in the rose dew of different manufacturers, and because the levorotatory rose ether and the dextrorotatory rose ether are difficult to distinguish and characterize, the rose ether A is tentatively determined, the rose ether has green and sweet fragrance, and the diluted rose ether has fragrance of rose and fresh bay leaves; (+) -rose ether has sweet and delicate fragrance, and (-) -rose ether has green fragrance, and the fragrance of the levorotatory body is sweeter than that of the dextrorotatory body, and the dextrorotatory body has slight pungent fragrance. In addition, phenols and other compounds are also essential components of the fragrance of rose dew, guaiacol (0.08%) specific to manufacturer 2, ocimene (0.10%) specific to manufacturer 1, both grass and floral with orange oil odour. The above discussion shows that the contribution of alcohols, ketones, aldehydes, esters, phenols, ethers, acids and others in rose water from different manufacturers is different.
3. Quantitative test
1. 1) Standard Mixed stock solution I and Standard series Mixed working solution
Taking dichloromethane as a solvent, accurately weighing a proper amount of linalool, citronellyl acetate, geranyl acetate, citronellol, nerol, geraniol, benzyl alcohol, phenethyl alcohol, methyl eugenol and eugenol standard substances (the accuracy is 0.1 mg), respectively using dichloromethane to fix the volume to 25mL, preparing single-standard solutions with mass concentrations of 2000mg/L, 4340mg/L, 4788mg/L, 3632mg/L, 2572mg/L, 4536mg/L, 4120mg/L, 4496mg/L, 4864mg/L and 5720mg/L, accurately measuring 750 mu L, 400 mu L and 400 mu L of the single-standard solutions in a 5mL volumetric flask to fix the volume, and preparing a standard mixed stock solution I, wherein the mass concentration of the standard mixed stock solution I is shown in a table 2.
Taking dichloromethane as a solvent, and taking the standard mixed stock solution I to dilute step by step.
Taking 700 mu L of standard mixed stock solution I, and preparing standard mixed working solution 1 after constant volume is 1.0 mL; taking 500 mu L of standard mixed stock solution I, and preparing standard mixed working solution 2 after the constant volume is 1.0 mL; taking 350 mu L of standard mixed stock solution I, and preparing standard mixed working solution 3 after the constant volume is 1.0 mL; taking 170 mu L of standard mixed stock solution I, and fixing the volume to 1.0mL to prepare standard mixed working solution 4; taking 70 mu L of standard mixed stock solution I, and preparing standard mixed working solution 5 after the constant volume is 1.0 mL; taking 20 mu L of standard mixed stock solution I, and preparing a standard mixed working solution 6 after the constant volume is 1.0 mL; taking 10 mu L of standard mixed stock solution I, and preparing a standard mixed working solution 6 after the constant volume is 1.0 mL; the mass concentrations of the standard series of mixed working solutions are shown in table 2.
TABLE 2 Standard series working solution concentration (mg/L)
2) Standard Mixed stock solution II and Standard Mixed stock solution III
Accurately weighing a proper amount of linalool, citronellyl acetate, geranyl acetate, citronellol, nerol, geraniol, benzyl alcohol, phenethyl alcohol, methyl eugenol and eugenol standard substances (accurate to 0.1 mg) by taking absolute ethyl alcohol as a solvent, dissolving the standard substances by using the absolute ethyl alcohol and fixing the volume to 25mL to prepare a standard mixed stock solution II with the mass concentrations of 3352mg/L, 4645mg/L, 4511mg/L, 4180mg/L, 4332mg/L, 4351mg/L, 4445mg/L, 4226mg/L, 4286mg/L and 4220mg/L respectively; taking 40 mu L of standard mixed stock solution II, using absolute ethyl alcohol to fix the volume to 1.0mL, preparing standard mixed stock solution III with the mass concentrations of 134.08mg/L, 185.80mg/L, 180.44mg/L, 167.20mg/L, 173.28mg/L, 174.04mg/L, 177.80mg/L, 169.04mg/L, 171.44mg/L and 168.80mg/L respectively, and using the standard mixed stock solution III for addition and recovery experiments.
2. Standard curve, method detection limit and quantitative lower limit
After preparing a standard series of mixed standard working solutions, performing gas chromatography-mass spectrometry detection according to the method of example 10, and obtaining a total ion flow diagram of the standard substances of 10 aroma components as shown in fig. 9; the peak area (Y) was used to plot a standard curve for the mass concentration (X, mg/L), and a regression calculation was performed, and the results are shown in Table 3.
TABLE 3 Linear relationship, detection limits and quantitation limits of 10 characteristic aroma components
As can be seen from Table 3, the 10 aroma components have good linear relationship and correlation coefficient (R) within a certain mass concentration range 2 ) The detection Limit (LOD) of the method is 0.050 to 0.078mg/L and the lower limit of quantitation (LOQ) is 0.166 to 0.261mg/L, both calculated as 3-fold signal-to-noise ratio (S/N = 3) and 10-fold signal-to-noise ratio (S/N = 10) when the values are larger than 0.9991.
3. Method accuracy and precision
Considering that dichloromethane is insoluble in water and the matrix of the rose water is a water sample, the accuracy of the result of the addition recovery test is to be confirmed by adding a mixed standard solution with dichloromethane as a solvent into the rose water sample. Standard mixed stock solutions iii of 10 aroma components were added to ultrapure water at 3 concentration levels, respectively, and each concentration level was measured in parallel 6 times to perform accuracy and precision tests, and the results are shown in table 4.
Accuracy and precision of table 410 aroma components
As can be seen from Table 4, the recovery rates of the 10 aroma components are 79.806% -113.780%, the Relative Standard Deviation (RSD) is 2.016% -9.576%, and the accuracy and precision of the method meet the detection requirements.
4. Analysis of actual samples
After GC/MS separation of the fragrance characteristic components of the rose flower water according to the protocol of example 10, the total ion flow diagram of the fragrance components of the rose flower water is shown in fig. 10, wherein a is a total ion flow diagram of cellular fluid of the rose flower (split ratio 50.
The contents of the cell sap of fresh rose, the dew of rose, the water of fresh rose and the water of salted rose were measured according to the standard curves in Table 3 using the method of example 10 for 10 characteristic aroma components in the samples of cell sap of fresh rose, water of fresh rose and water of salted rose, and the results are shown in Table 5.
TABLE 5 results of actual sample measurement
As can be seen from Table 5, the content of citronellol (120.726 mg/L), nerol (10.176 mg/L), geraniol (47.775 mg/L), benzyl alcohol (94.809 mg/L), phenethyl alcohol (20.499 mg/L), eugenol (8.817 mg/L) in the cellular fluid of fresh roses is significantly higher than that of the samples of rose water, fresh rose water and rose salted flower water; the content of citronellol (50.177 mg/L) and phenethyl alcohol (7.691 mg/L) in the rose salted flower water is obviously higher than that of the rose flower water, and the content of linalool (9.242 mg/L) in the rose flower water is far higher than that of linalool (3.343 mg/L) in the rose salted flower water. The method for measuring 10 aroma components in the rose water and rose dew is simple to operate, low in organic solvent consumption and suitable for high-throughput analysis of large-batch samples.
The foregoing is only a preferred embodiment of the present invention, and it should be noted that, for those skilled in the art, various modifications and decorations can be made without departing from the principle of the present invention, and these modifications and decorations should also be regarded as the protection scope of the present invention.
Claims (7)
1. The method for detecting the fragrance components of the rose dew is characterized by comprising the following steps of:
mixing the rose dew and the dispersed micro-extraction solution, and extracting under an ultrasonic condition to obtain an extract liquid; the dispersed micro-extraction solution is a mixed solution of an extracting agent and a dispersing agent;
performing gas chromatography-mass spectrometry detection on the extract, and performing qualitative detection on aroma components by using an NIST11 standard library to retrieve the obtained GC-MS spectrogram to obtain the aroma components of the rose dew;
the gas chromatography conditions in the gas chromatography-mass spectrometry detection comprise: a chromatographic column: HP-INNOWAX; temperature programming: the initial temperature is 60 ℃, the temperature is kept for 1min, the temperature is increased to 245 ℃/min at the speed of 2 ℃/min, and the temperature is kept for 5min; carrier gas: high purity helium gas; sample inlet temperature: 250 ℃; no-shunt sample introduction;
the conditions of the mass spectrum in the gas chromatography-mass spectrometry detection comprise: electron bombardment ion source; electron energy: 70eV; mass spectrum voltage: 0.4kv; the transmission line temperature is 250 ℃; ion source temperature: 230 ℃; mass spectrum voltage: 0.4kv; scanning mode: a scan mode; mass scan range: m/z is 35-500u;
the fragrance component of the rose flower dew comprises 2-heptanone, n-dodecane, isoamyl alcohol, 2,6,11-trimethyldodecane, 3-methyl-1,5-pentanediol, 2-ethyl-2-hexenal, cyclohexanone, 2-heptanol, methylheptenone, n-hexanol, rose ether A, rose ether B, folyl alcohol, tetradecane, benzyl methyl ether, (S) -linalool oxide, n-heptanol, 6-methyl-5-hepten-2-ol, (E) -linalool oxide, benzaldehyde, linalool, dihydrocarveol, n-heneicosane, 4-terpenol, myrcenol, (-) -trans-rosinol, furfuryl alcohol, L-menthol, (Z) -3,7-dimethyl-2,6-octadienal, 2- (4-methyl-3-cyclohexenyl) propionaldehyde, 2-methyl-3-cyclohexenyl) propionaldehyde alpha-terpineol, verbenol, benzyl acetate, citral, 3,7-dimethyl-7-octenol, citronellol, lavandiol, (-) -myrtenol, nerol, isogeraniol, caryophyllene oxide, phenylethyl acetate, verbenol, geraniol, guaiacol, benzyl alcohol, ocimene, isopulegol, phenethyl alcohol, 3- (2,6,6-trimethyl-1-cyclohexene-1-yl) acrolein, 2,6-dimethyloct-7-ene-2,6-diol, perillyl alcohol, methyl eugenol, heptanoic acid, 4-tert-butyl phenyl acetone, 3-phenylpropanol, 4,8-dimethyl-3,7-nonadien-2-yl acetate, methyl eugenol, heptanoic acid, 4-tert-butyl phenyl acetone, 3-phenylpropanol, 4,8-3525-zxft 3525-nonadien-2-yl acetate, P-menthane-1,8-diol, 2,7-dimethyl-2,7-octanediol, 1-cyclohexyl-1-butanone, eucalyptol, bisabolol oxide B, eugenol, hydroxycitronelrol, elemene, dec-7-en-2-one, isopulegol, cinnamyl alcohol, 2,4-di-tert-butylphenol, (R) - (+) -citronellac acid, farnesol, farnesic acid, neryl acetate, (2E) -3,7-dimethyl-2,6-octadienoic acid, 4- (2,2,6-trimethylcyclohexyl) -2-butanone, 3-ethoxy-3,7-dimethyloctyl-1,6-diene, geraniol, cedrene, bisabolol, and benzoic acid.
2. The method of claim 1, wherein the volume ratio of the rose water to the dispersed micro-extraction solution is (5.0-7.0) mL (600-800) μ L.
3. The method of claim 1, wherein the extractant comprises dichloromethane; the dispersant comprises acetonitrile.
4. The method of claim 3, wherein the volume ratio of the extractant to the dispersant is 1 (2-3).
5. The method of claim 1, 3 or 4, wherein the extraction time is 1-3 min.
6. The method according to any one of claims 1 to 5, wherein the volume ratio of the rose water to the dispersed micro-extraction solution is 7.0 mL; the volume ratio of the extracting agent to the dispersing agent is 1:2; the extraction time is 3min.
7. The method for measuring the content of the fragrance components of the rose dew is characterized by comprising the following steps of:
preparing standard series of 10 rose dew aroma components mixed standard working solutions with different mass concentrations, performing gas chromatography-mass spectrometry detection to obtain a standard substance total ion flow graph of the 10 rose dew aroma components, and establishing a standard curve by taking peak areas as vertical coordinates and mass concentrations as horizontal coordinates;
mixing the rose dew and the dispersed micro-extraction solution, and extracting under an ultrasonic condition to obtain an extract liquid; the dispersed micro-extraction solution is a mixed solution of an extracting agent and a dispersing agent;
performing gas chromatography-mass spectrometry detection on the extract, and comparing the obtained GC-MS spectrogram with a standard substance spectrogram to determine 10 aroma components of the rose dew;
the gas chromatography conditions in the gas chromatography-mass spectrometry detection comprise: a chromatographic column: HP-INNOWAX; temperature programming: the initial temperature is 60 ℃, the temperature is kept for 1min, the temperature is increased to 245 ℃/min at the speed of 2 ℃/min, and the temperature is kept for 5min; carrier gas: high purity helium gas; sample inlet temperature: 250 ℃; the split ratio is as follows: 50;
the conditions of the mass spectrum in the gas chromatography-mass spectrometry detection comprise: electron bombardment ion source; energy of electrons: 70eV; mass spectrum voltage: 0.4kv; the transmission line temperature is 250 ℃; ion source temperature: 230 ℃; mass spectrum voltage: 0.4kv; scanning mode: a scan mode; mass scan range: m/z is 35-500u;
comparing the peak areas of the spectrograms of the 10 fragrance components of the rose dew with the standard curve to obtain the content of the fragrance components of the rose dew;
the 10 rose flower dew aroma components comprise citronellol, linalool, citronellyl acetate, methyl eugenol, phenethyl alcohol, geraniol acetate, nerol, eugenol, geraniol and benzyl alcohol.
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|---|---|---|---|---|
| CN117630252A (en) * | 2024-01-25 | 2024-03-01 | 中国海洋大学三亚海洋研究院 | Method for extracting and detecting farnesic acid in shrimp and crab blood sample |
| CN117630252B (en) * | 2024-01-25 | 2024-04-26 | 中国海洋大学三亚海洋研究院 | Method for extracting and detecting farnesic acid in shrimp and crab blood sample |
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