CN107085051B - A kind of construction method and discrimination method of Huanghua Pear redwood tree species finger-print - Google Patents

A kind of construction method and discrimination method of Huanghua Pear redwood tree species finger-print Download PDF

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CN107085051B
CN107085051B CN201710258633.6A CN201710258633A CN107085051B CN 107085051 B CN107085051 B CN 107085051B CN 201710258633 A CN201710258633 A CN 201710258633A CN 107085051 B CN107085051 B CN 107085051B
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huanghua pear
redwood
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finger
print
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CN107085051A (en
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吴惠勤
黄晓兰
侯思润
林晓珊
黄芳
马艳芳
马叶芬
罗辉泰
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Institute Of Testing And Analysis Guangdong Academy Of Sciences Guangzhou Analysis And Testing Center China
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    • GPHYSICS
    • G01MEASURING; TESTING
    • G01NINVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
    • G01N30/00Investigating or analysing materials by separation into components using adsorption, absorption or similar phenomena or using ion-exchange, e.g. chromatography or field flow fractionation
    • G01N30/02Column chromatography
    • GPHYSICS
    • G01MEASURING; TESTING
    • G01NINVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
    • G01N30/00Investigating or analysing materials by separation into components using adsorption, absorption or similar phenomena or using ion-exchange, e.g. chromatography or field flow fractionation
    • G01N30/02Column chromatography
    • G01N30/04Preparation or injection of sample to be analysed
    • G01N30/06Preparation
    • GPHYSICS
    • G01MEASURING; TESTING
    • G01NINVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
    • G01N30/00Investigating or analysing materials by separation into components using adsorption, absorption or similar phenomena or using ion-exchange, e.g. chromatography or field flow fractionation
    • G01N2030/009Extraction
    • GPHYSICS
    • G01MEASURING; TESTING
    • G01NINVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
    • G01N30/00Investigating or analysing materials by separation into components using adsorption, absorption or similar phenomena or using ion-exchange, e.g. chromatography or field flow fractionation
    • G01N30/02Column chromatography
    • G01N2030/022Column chromatography characterised by the kind of separation mechanism
    • G01N2030/025Gas chromatography
    • GPHYSICS
    • G01MEASURING; TESTING
    • G01NINVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
    • G01N30/00Investigating or analysing materials by separation into components using adsorption, absorption or similar phenomena or using ion-exchange, e.g. chromatography or field flow fractionation
    • G01N30/02Column chromatography
    • G01N30/04Preparation or injection of sample to be analysed
    • G01N30/06Preparation
    • G01N2030/062Preparation extracting sample from raw material

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Abstract

The invention discloses the construction methods and discrimination method of a kind of Huanghua Pear redwood tree species finger-print.The odour component of Huanghua Pear redwood sample to be measured is enriched with using the method for headspace solid-phase microextraction, again using the odour component of gas chromatography/mass spectrometry measurement Huanghua Pear redwood, total ion chromatogram is recorded in mass spectrum full scan method, obtain the GC/MS finger-print of Huanghua Pear to be measured, determine 5 kinds of common characteristic ingredients, and the relative amount of this five kinds of common characteristic ingredients is calculated, relative amount and GC/MS the finger-print identification of root Ju characteristic component are Hainan Huanghua Pear redwood or Vietnam's Huanghua Pear redwood.Method amount of samples provided by the invention is small, it is easy to operate quickly, high sensitivity, chromatographic fingerprint information and odour component chemical composition combine, as a result accurate and reliable, the tree species for being suitable for each component in finished product furniture identify, furniture overall structure is not destroyed, and the tree species that can be used for redwood and mahogany furniture identify.

Description

A kind of construction method and discrimination method of Huanghua Pear redwood tree species finger-print
Technical field:
The invention belongs to analyze testing field, and in particular to a kind of construction method of Huanghua Pear redwood tree species finger-print and Discrimination method.
Background technique:
Hainan Huanghua Pear Chinese scientific name is dalbergia odorifera, and source area is Chinese Second Class Key Protected Plant in the southern Chinese island of Hainan.Cause Its become a useful person it is slow, wooden it is solid, decorative pattern is beautiful, rank one of five big name wood always, it is ornamental, medicinal, especially in Furniture manufacture In have extremely important status.Since Hainan Huanghua Pear is expensive, the case where mixing the spurious with the genuine, adulterating in the market, is not fresh See, wherein pretending to be high price Hainan Huanghua Pear for typical case with low price Vietnam Huanghua Pear.Currently, there is no both at home and abroad to Hainan Huanghua Pear and The relevant report of the chemical composition analysis of Vietnam's Huanghua Pear can not carry out scientific identification to the classification of mahogany furniture wood kind, be badly in need of It establishes a kind of quick energy, simplicity, the wooden kind of method for distinguishing that reflects non-destructively carried out to mahogany furniture.
Summary of the invention:
The purpose of the present invention is to provide the construction methods and discrimination method of a kind of Huanghua Pear redwood tree species finger-print, use Identify in mahogany furniture wood kind, solves the problems, such as that mahogany furniture wood kind identifies, high price is pretended to be with low price Vietnam Huanghua Pear to hit The malfeasance of Hainan Huanghua Pear provides the detection method of science.
The first purpose of the invention is to provide a kind of construction method of Huanghua Pear redwood tree species finger-print, feature exists In, comprising the following steps: Hainan Huanghua Pear redwood is enriched with using the method for headspace solid-phase microextraction respectively and Vietnam's Huanghua Pear is red The odour component of wood, then odour component is measured using gas chromatography/mass spectrometry, total ion current is recorded in mass spectrum full scan method Chromatogram obtains the GC/MS finger-print of Hainan Huanghua Pear and Vietnam's Huanghua Pear, to Hainan Huanghua Pear and Vietnam's Huanghua Pear The corresponding mass spectrogram of each chromatographic peak is parsed in GC/MS finger-print, is determined in Hainan Huanghua Pear and Vietnam's Huanghua Pear and is contained 5 Kind common characteristic ingredient: 1. penta ring -4- ketone of 2- (1,1- dimethyl ethyl) -5- heptyl -5- methyl-1,3-dioxy, 2. 2,6,10- 12 carbon diene -6- alcohol of trimethyl -7,10- epoxy -2,11-, 3. nerolidol, 4. (2- methylbutylene)-pentamethylene and 5. 2- (5- methyl -2- furyl) propionic aldehyde.
It is preferred that the method using headspace solid-phase microextraction is enriched with Hainan Huanghua Pear redwood and Vietnam's Huanghua Pear respectively The odour component of redwood specifically: Hainan Huanghua Pear redwood and Vietnam's Huanghua Pear redwood powder are taken respectively, are fitted into ml headspace bottle, it is close Solid phase microextraction needle is passed through in sealing-plug insertion ml headspace bottle, releases extracting head, extract 20min at 50 DEG C~80 DEG C by envelope.
A second object of the present invention is to provide a kind of identification Hainan Huanghua Pear redwood tree species and Vietnam Huanghua Pear redwood The method of kind, which is characterized in that the odour component of Huanghua Pear redwood sample to be measured is enriched with using the method for headspace solid-phase microextraction, Again using the odour component of gas chromatography/mass spectrometry measurement Huanghua Pear redwood, total ion current is recorded in mass spectrum full scan method Chromatogram obtains the GC/MS finger-print of Huanghua Pear to be measured, determines 5 kinds of common characteristic ingredients: 1. 2- (1,1- dimethyl second Base) penta ring -4- ketone of -5- heptyl -5- methyl-1,3-dioxy, 2. 12 carbon two of 2,6,10- trimethyl -7,10- epoxy -2,11- Alkene -6- alcohol, 3. nerolidol, 4. (2- methylbutylene)-pentamethylene and 5. 2- (5- methyl -2- furyl) propionic aldehyde, and calculate The relative amount of this five kinds of common characteristic ingredients, if the GC/MS finger-print of Huanghua Pear redwood sample to be measured and Hainan chrysanthemum The GC/MS finger-print of pears is almost the same, and contains 1. 2- (1,1- dimethyl ethyl) -5- heptyl -5- methyl-1,3- dioxy Penta ring -4- ketone, 2. 12 carbon diene -6- alcohol of 2,6,10- trimethyl -7,10- epoxy -2,11-, 3. nerolidol, 4. (2- methyl Butylidene)-pentamethylene and 5. 2- (5- methyl -2- furyl) 5 kinds of characteristic components of propionic aldehyde, while the relative amount of characteristic component 1. Less than 2., 5. relative amount 4. is greater than, and is determined as Hainan Huanghua Pear;If the GC/MS finger-print of sample to be tested and Vietnam The GC/MS finger-print of Huanghua Pear is almost the same, and contains 1. 2- (1,1- dimethyl ethyl) -5- heptyl -5- methyl-1,3- Dioxolanes -4- ketone, 2. 12 carbon diene -6- alcohol of 2,6,10- trimethyl -7,10- epoxy -2,11-, 3. nerolidol, 4. (2- Methylbutylene)-pentamethylene and 5. 2- (5- methyl -2- furyl) 5 kinds of characteristic components of propionic aldehyde, while characteristic component 1. opposite 2. content is greater than, 5. relative amount 4. is less than, and is determined as Vietnam's Huanghua Pear.
The method using headspace solid-phase microextraction is enriched with the odour component of Huanghua Pear redwood sample to be measured, then uses Gas chromatography/mass spectrometry measures the odour component of Huanghua Pear redwood, records total ion chromatogram in mass spectrum full scan method, Obtain the GC/MS finger-print specific steps of Huanghua Pear to be measured are as follows:
A) it is enriched with the odour component of Huanghua Pear redwood sample to be measured using the method for headspace solid-phase microextraction: taking chrysanthemum to be measured Pears redwood sample powder, is fitted into ml headspace bottle, sealing, and solid phase microextraction needle is passed through in sealing-plug insertion ml headspace bottle, extraction is released Head is taken, extracts 20min at 50 DEG C~80 DEG C;
B) odour component of Huanghua Pear redwood sample to be measured is measured using gas chromatography/mass spectrometry: taking out step a's) Solid phase micro-extracting head is rapidly inserted into gas chromatographic sample introduction mouth, 10min is desorbed at 240 DEG C, it is red that GC-MS measures Huanghua Pear to be measured The odour component of the wooden sample records total ion chromatogram in mass spectrum full scan method, obtains the GC/MS of Huanghua Pear sample to be measured Finger-print.
Method amount of samples provided by the invention is small, it is easy to operate quickly, high sensitivity, chromatographic fingerprint information and smell at Point chemical composition combines, and as a result accurately and reliably, the tree species for being suitable for each component in finished product furniture identify, and does not destroy furniture entirety Structure, the tree species that can be used for redwood and mahogany furniture identify.
Compared with the prior art, the invention has the following advantages and beneficial effects:
(1) method of the invention is established complete using solid phase microextraction-gas chromatography/mass spectrometry (SPME-GC/MS) technology New redwood tree species discrimination method;Science is objective, and uniqueness is strong, does not destroy the globality of furniture, is suitable for identifying Hainan chrysanthemum The true and false of pear wood material and furniture.
(2) method of the invention is simple and practical, is to discriminate between the effective ways of Hainan Huanghua Pear Yu Vietnam's Huanghua Pear, has non- Normal apparent Social benefit and economic benefit.
Detailed description of the invention:
Fig. 1 is the total ion chromatogram (TIC) of Hainan Huanghua Pear odour component;Wherein, 1,2- (1,1- dimethyl second Base) penta ring -4- ketone of -5- heptyl -5- methyl-1,3-dioxy;2,12 carbon two of 2,6,10- trimethyl -7,10- epoxy -2,11- Alkene -6- alcohol;3, nerolidol;4, (2- methylbutylene)-pentamethylene;5,2- (5- methyl -2- furyl) propionic aldehyde;
Fig. 2 is the total ion chromatogram (TIC) of Vietnam's Huanghua Pear odour component;Wherein, 1,2- (1,1- dimethyl second Base) penta ring -4- ketone of -5- heptyl -5- methyl-1,3-dioxy;2,12 carbon two of 2,6,10- trimethyl -7,10- epoxy -2,11- Alkene -6- alcohol;3, nerolidol;4, (2- methylbutylene)-pentamethylene;5,2- (5- methyl -2- furyl) propionic aldehyde;
The total ion chromatogram (TIC) of Fig. 3 rosewood log sample odour component;Wherein, 1,2- (1,1- dimethyl Ethyl) penta ring -4- ketone of -5- heptyl -5- methyl-1,3-dioxy;2,12 carbon two of 2,6,10- trimethyl -7,10- epoxy -2,11- Alkene -6- alcohol;3, nerolidol;4, (2- methylbutylene)-pentamethylene;5,2- (5- methyl -2- furyl) propionic aldehyde;
Fig. 4 is the total ion chromatogram (TIC) of certain mahogany furniture sample odour component;Wherein, 1,2- (1,1- dimethyl Ethyl) penta ring -4- ketone of -5- heptyl -5- methyl-1,3-dioxy;2,12 carbon two of 2,6,10- trimethyl -7,10- epoxy -2,11- Alkene -6- alcohol;3, nerolidol;4, (2- methylbutylene)-pentamethylene;5,2- (5- methyl -2- furyl) propionic aldehyde;
Fig. 5 is the total ion chromatogram (TIC) of redwood board samples odour component;Wherein, 1,2- (1,1- dimethyl second Base) penta ring -4- ketone of -5- heptyl -5- methyl-1,3-dioxy;2,12 carbon two of 2,6,10- trimethyl -7,10- epoxy -2,11- Alkene -6- alcohol;3, nerolidol;4, (2- methylbutylene)-pentamethylene;5,2- (5- methyl -2- furyl) propionic aldehyde.
Specific embodiment:
Present invention will now be described in further detail with reference to the embodiments and the accompanying drawings, but embodiments of the present invention are unlimited In this.
Embodiment 1: Hainan Huanghua Pear and Vietnam's Huanghua Pear
(1) Hainan Huanghua Pear mahogany furniture and Vietnam's Huanghua Pear mahogany furniture are taken respectively, are drilled through wood powder with electric drill, are weighed about 0.10g sample is fitted into 20mL in the ml headspace bottle of teflon seal plug, and sealing, sample is put into sample injector;
(2) the solid phase microextraction needle with PDMS/DVB (65 μm) extracting head is passed through in sealing-plug insertion ml headspace bottle, is pushed away Extracting head (extracting head is away from sample surfaces about 1cm) out, the odour component of solid phase microextraction Hainan Huanghua Pear or Vietnam's Huanghua Pear, in 20min is extracted at 60 DEG C, is taken out solid phase microextraction needle and is rapidly inserted into HP 7890BGC/5977AMSD gas chromatography/mass spectrometry In the gas chromatographic sample introduction mouth of instrument, 10min is desorbed at 250 DEG C, GC-MS measures odour component.
GC conditions are: chromatographic column: AB-FFAP (30m × 0.25mm × 0.25 μm) polarity capillary gas chromatography Column.Carrier gas: He (99.999%);Column flow: 0.7mL/min, constant current;Splitless injecting samples, Purge flow to split Vent:20mL/min, Purge time:0.25min;Injector temperature: 250 DEG C;50 DEG C of column initial temperature, temperature programming with 8 DEG C/ Min to 80 DEG C, then with 12 DEG C/min to 240 DEG C, retain 2min, runing time 19.08min.The desorption time of solid phase microextraction For 10min.
Mass Spectrometry Conditions are: ion source: the source EI;Ion source temperature: 230 DEG C;Quadrupole rod temperature: 150 DEG C;Chromatography-mass spectroscopy connects Interface temperature: 280 DEG C;Electron energy: 70eV;Electron multiplier voltage: add 200V on the basis of automatic tuning;Scanning mode: SCAN, scanning range 33~250u, Threshold:50.
The solid phase microextraction of Hainan Huanghua Pear redwood sample-gas chromatography/mass spectrometry odour component total ion chromatogram (TIC) see Fig. 1, as the GC/MS finger-print of Hainan Huanghua Pear;Solid phase microextraction-gas phase of Vietnam's Huanghua Pear redwood sample Chromatography/Mass Spectrometry odour component total ion chromatogram (TIC) is shown in Fig. 2, as the GC/MS finger-print of Vietnam's Huanghua Pear.Through composing Library searching and artificial parsing, the key odor ingredient for identifying Hainan Huanghua Pear and Vietnam's Huanghua Pear have 5, and molecular formula is divided Son amount and relative amount are shown in Table 1.
The odour component of 1 Hainan Huanghua Pear of table and Vietnam's Huanghua Pear composition and relative amount
Hainan Huanghua Pear and Vietnam's Huanghua Pear contain 1. 2- (1,1- dimethyl ethyl) -5- heptyl -5- methyl-1,3- bis- Butyl oxide link -4- ketone, 2. 12 carbon diene -6- alcohol of 2,6,10- trimethyl -7,10- epoxy -2,11-, 3. nerolidol, 4. (2- first Base butylidene)-pentamethylene, 5. 2- (5- methyl -2- furyl) five kinds of odour components of propionic aldehyde, but unlike: Hainan Huanghua Pear In each ingredient relative amount it is apparent be 1. less than 2., be 4. greater than 5., Vietnam's Huanghua Pear is then on the contrary.According in redwood sample Odour component is compared with the GC/MS finger-print of above-mentioned 5 kinds of characteristic components and its relative amount, it can be determined that this kind of redwood The tree species of sample.
Embodiment 2: the tree species of certain rosewood log identify
(1) the rosewood log is taken, drills through wood powder with electric drill, weighs about 0.10g sample, 20mL is packed into and has polytetrafluoroethyl-ne In the ml headspace bottle of alkene sealing-plug, sealing, sample is put into sample injector;
(2) the solid phase microextraction needle with PDMS/DVB (65 μm) extracting head is passed through in sealing-plug insertion ml headspace bottle, is pushed away Extracting head (extracting head is away from sample surfaces about 1cm) out, solid phase microextraction rosewood log odour component extract in 50 DEG C of heating water baths 20min is taken, solid phase micro-extracting head is rapidly inserted into the gas of HP 7890BGC/5977AMSD Gc/ms Analyser later In phase chromatography column feed materials mouth, 10min is desorbed at 250 DEG C, is carried out the separation of gas chromatography/mass spectrometry (GC/MS) method, is measured flower pears Wood gas taste Components Chemical composition.
GC conditions are: chromatographic column: AB-FFAP (30m × 0.25mm × 0.25 μm) polarity capillary gas chromatography Column.Carrier gas: He (99.999%);Column flow: 0.7mL/min, constant current;Splitless injecting samples, Purge flow to split Vent:20mL/min, Purge time:0.25min;Injector temperature: 250 DEG C;50 DEG C of column initial temperature, temperature programming with 8 DEG C/ Min to 80 DEG C, then with 12 DEG C/min to 240 DEG C, retain 2min, runing time 19.08min.The desorption time of solid phase microextraction For 10min.
Mass Spectrometry Conditions are: ion source: the source EI;Ion source temperature: 230 DEG C;Quadrupole rod temperature: 150 DEG C;Chromatography-mass spectroscopy connects Interface temperature: 280 DEG C;Electron energy: 70eV;Electron multiplier voltage: add 200V on the basis of automatic tuning;Scanning mode: SCAN, scanning range 33~250u, Threshold:50.
The solid phase microextraction of certain rosewood log sample-gas chromatography/mass spectrometry odour component total ion chromatogram (TIC) See Fig. 3, the characteristic component through the Mass Spectrometric Identification rosewood log sample is as shown in table 2.
The odour component of certain the rosewood log sample of table 2 forms and relative amount
The chromatographic retention of the rosewood log sample and the GC/MS finger-print (Fig. 1) of Hainan Huanghua Pear coincide, and Penta ring -4- of the apparent 2- of the relative amount of its each chromatographic peak (1,1- dimethyl ethyl) -5- heptyl -5- methyl-1,3-dioxy Ketone is less than 12 carbon diene -6- alcohol of 2,6,10- trimethyl -7,10- epoxy -2,11-, (2- methylbutylene)-pentamethylene is greater than 2- (5- methyl -2- furyl) propionic aldehyde is also close with Hainan Huanghua Pear standard items, it may be determined that the tree species of the rosewood log sample For Hainan Huanghua Pear.The result is consistent with actual result.
Embodiment 3: the tree species of certain mahogany furniture identify
(1) mahogany furniture is taken, drills through wood powder with electric drill, weighs about 0.10g sample, 20mL is packed into and has polytetrafluoroethylene (PTFE) In the ml headspace bottle of sealing-plug, sealing, sample is put into sample injector;
(2) the solid phase microextraction needle with PDMS/DVB (65 μm) extracting head is passed through in sealing-plug insertion ml headspace bottle, is pushed away Extracting head (extracting head is away from sample surfaces about 1cm) out, solid phase microextraction mahogany furniture odour component are extracted in 80 DEG C of heating water baths Solid phase microextraction needle is rapidly inserted into the gas phase of HP 7890BGC/5977AMSD Gc/ms Analyser by 20min later In chromatography column feed materials mouth, 10min is desorbed at 250 DEG C, carries out the separation of gas chromatography/mass spectrometry (GC/MS) method, measurement redwood gas Taste Components Chemical composition.
GC conditions are: chromatographic column: AB-FFAP (30m × 0.25mm × 0.25 μm) polarity capillary gas chromatography Column.Carrier gas: He (99.999%);Column flow: 0.7mL/min, constant current;Splitless injecting samples, Purge flow to split Vent:20mL/min, Purge time:0.25min;Injector temperature: 250 DEG C;50 DEG C of column initial temperature, temperature programming with 8 DEG C/ Min to 80 DEG C, then with 12 DEG C/min to 240 DEG C, retain 2min, runing time 19.08min.The desorption time of solid phase microextraction For 10min.
Mass Spectrometry Conditions are: ion source: the source EI;Ion source temperature: 230 DEG C;Quadrupole rod temperature: 150 DEG C;Chromatography-mass spectroscopy connects Interface temperature: 280 DEG C;Electron energy: 70eV;Electron multiplier voltage: add 200V on the basis of automatic tuning;Scanning mode: SCAN, scanning range 33~250u, Threshold:50.
The solid phase microextraction of certain mahogany furniture sample-gas chromatography/mass spectrometry odour component total ion chromatogram (TIC) is shown in Fig. 4, the characteristic component through the Mass Spectrometric Identification mahogany furniture sample are as shown in table 3.
The odour component of certain the mahogany furniture sample of table 3 forms and relative amount
The chromatographic retention of the mahogany furniture sample and the GC/MS finger-print (Fig. 2) of Vietnam's Huanghua Pear coincide, and its Penta ring -4- ketone of the apparent 2- of the relative amount of each chromatographic peak (1,1- dimethyl ethyl) -5- heptyl -5- methyl-1,3-dioxy It is less than 2- greater than 12 carbon diene -6- alcohol of 2,6,10- trimethyl -7,10- epoxy -2,11-, (2- methylbutylene)-pentamethylene (5- methyl -2- furyl) propionic aldehyde is also close with Vietnam's Huanghua Pear standard items, it may be determined that the tree species of the mahogany furniture sample are more Southern Huanghua Pear.The result is consistent with actual result.
Embodiment 4: the tree species of certain redwood plate identify
(1) the redwood board samples are taken, drill through wood powder with electric drill, weigh about 0.10g sample, 20mL is packed into and has polytetrafluoro In the ml headspace bottle of ethylene sealing-plug, sealing, sample is put into sample injector;
(2) the solid phase microextraction needle with PDMS/DVB (65 μm) extracting head is passed through in sealing-plug insertion ml headspace bottle, is pushed away Extracting head (extracting head is away from sample surfaces about 1cm) out, solid phase microextraction redwood plate odour component are extracted in 80 DEG C of heating Solid phase micro-extracting head is rapidly inserted into the gas phase of HP 7890BGC/5977AMSD Gc/ms Analyser by 20min later In chromatography column feed materials mouth, 10min is desorbed at 250 DEG C, carries out the separation of gas chromatography/mass spectrometry (GC/MS) method, measurement redwood gas Taste Components Chemical composition.
GC conditions are: chromatographic column: AB-FFAP (30m × 0.25mm × 0.25 μm) polarity capillary gas chromatography Column.Carrier gas: He (99.999%);Column flow: 0.7mL/min, constant current;Splitless injecting samples, Purge flow to split Vent:20mL/min, Purge time:0.25min;Injector temperature: 250 DEG C;50 DEG C of column initial temperature, temperature programming with 8 DEG C/ Min to 80 DEG C, then with 12 DEG C/min to 240 DEG C, retain 2min, runing time 19.08min.The desorption time of solid phase microextraction For 10min.
Mass Spectrometry Conditions are: ion source: the source EI;Ion source temperature: 230 DEG C;Quadrupole rod temperature: 150 DEG C;Chromatography-mass spectroscopy connects Interface temperature: 280 DEG C;Electron energy: 70eV;Electron multiplier voltage: add 200V on the basis of automatic tuning;Scanning mode: SCAN, scanning range 33~250u, Threshold:50.
The solid phase microextraction of the redwood board samples-gas chromatography/mass spectrometry odour component total ion chromatogram (TIC) is shown in Fig. 5, the characteristic component through the Mass Spectrometric Identification redwood sample are as shown in table 4:
The odour component of certain the redwood board samples of table 4 forms and relative amount
The chromatographic retention of the redwood board samples and the GC/MS finger-print (Fig. 1) of Hainan Huanghua Pear coincide, and its Penta ring -4- ketone of the apparent 2- of the relative amount of each chromatographic peak (1,1- dimethyl ethyl) -5- heptyl -5- methyl-1,3-dioxy It is greater than 2- less than 12 carbon diene -6- alcohol of 2,6,10- trimethyl -7,10- epoxy -2,11-, (2- methylbutylene)-pentamethylene (5- methyl -2- furyl) propionic aldehyde is also close with Hainan Huanghua Pear standard items, it may be determined that the tree species of the redwood board samples are sea Southern Huanghua Pear.
The above embodiment is a preferred embodiment of the present invention, but embodiments of the present invention are not by above-described embodiment Limitation, other any changes, modifications, substitutions, combinations, simplifications made without departing from the spirit and principles of the present invention, It should be equivalent substitute mode, be included within the scope of the present invention.

Claims (2)

1. a kind of method for identifying Hainan Huanghua Pear redwood tree species and Vietnam Huanghua Pear redwood tree species, which is characterized in that using top The method of empty solid phase microextraction is enriched with the odour component of Huanghua Pear redwood sample to be measured, then is surveyed using gas chromatography/mass spectrometry Determine the odour component of Huanghua Pear redwood, records total ion chromatogram in mass spectrum full scan method, obtain the GC/ of Huanghua Pear to be measured MS finger-print determines 5 kinds of common characteristic ingredients: 1. 2- (1,1- dimethyl ethyl) -5- heptyl -5- methyl-1,3- dioxy penta Ring -4- ketone, 2. 12 carbon diene -6- alcohol of 2,6,10- trimethyl -7,10- epoxy -2,11-, 3. nerolidol, 4. (2- methyl is sub- Butyl)-pentamethylene and 5. 2- (5- methyl -2- furyl) propionic aldehyde, and the relative amount of this five kinds of common characteristic ingredients is calculated, such as The GC/MS finger-print and the GC/MS finger-print of Hainan Huanghua Pear of fruit Huanghua Pear redwood sample to be measured are almost the same, and contain There are 1. penta ring -4- ketone of 2- (1,1- dimethyl ethyl) -5- heptyl -5- methyl-1,3-dioxy, 2. 2,6,10- trimethyl -7,10- 12 carbon diene -6- alcohol of epoxy -2,11-, 3. nerolidol, 4. (2- methylbutylene)-pentamethylene and 5. 2- (5- methyl -2- Furyl) 5 kinds of characteristic components of propionic aldehyde, while 2. the relative amount of characteristic component 1. is less than, 5. relative amount 4. is greater than, determine For Hainan Huanghua Pear;If the GC/MS finger-print of sample to be tested and the GC/MS finger-print of Vietnam's Huanghua Pear are almost the same, And contain 1. penta ring -4- ketone of 2- (1,1- dimethyl ethyl) -5- heptyl -5- methyl-1,3-dioxy, 2. 2,6,10- trimethyl - 12 carbon diene -6- alcohol of 7,10- epoxy -2,11-, 3. nerolidol, 4. (2- methylbutylene)-pentamethylene and 5. 2- (5- first Base -2- furyl) 5 kinds of characteristic components of propionic aldehyde, while 2. the relative amount of characteristic component 1. is greater than, relative amount 4. is less than 5. being determined as Vietnam's Huanghua Pear;
The gas chromatography/mass spectrometry measurement, GC conditions are: chromatographic column: AB-FFAP polarity capillary gas phase Chromatographic column 30m × 0.25mm × 0.25 μm;Carrier gas: He;Column flow: 0.7mL/min, constant current;Splitless injecting samples, Purge flow To split vent:20mL/min, Purge time:0.25min;Injector temperature: 250 DEG C;50 DEG C of column initial temperature, program liter Temperature retains 2min, runing time 19.08min with 8 DEG C/min to 80 DEG C, then with 12 DEG C/min to 240 DEG C;Solid phase microextraction Desorption time is 10min;
Mass Spectrometry Conditions are: ion source: the source EI;Ion source temperature: 230 DEG C;Quadrupole rod temperature: 150 DEG C;Chromatography-mass spectroscopy connector Temperature: 280 DEG C;Electron energy: 70eV;Electron multiplier voltage: add 200V on the basis of automatic tuning;Scanning mode: SCAN, Scanning range 33~250u, Threshold:50.
2. the method according to claim 1, wherein the method enrichment using headspace solid-phase microextraction to The odour component of Huanghua Pear redwood sample is surveyed, then measures the odour component of Huanghua Pear redwood using gas chromatography/mass spectrometry, with Mass spectrum full scan method records total ion chromatogram, obtains the GC/MS finger-print specific steps of Huanghua Pear to be measured are as follows:
A) it is enriched with the odour component of Huanghua Pear redwood sample to be measured using the method for headspace solid-phase microextraction: taking Huanghua Pear to be measured red The wooden sample powder, is fitted into ml headspace bottle, sealing, and solid phase microextraction needle is passed through in sealing-plug insertion ml headspace bottle, extracting head is released, 20min is extracted at 50 DEG C~80 DEG C;
B) odour component of Huanghua Pear redwood sample to be measured is measured using gas chromatography/mass spectrometry: taking out the solid phase of step a) Micro-extracting head is rapidly inserted into gas chromatographic sample introduction mouth, and 10min is desorbed at 240 DEG C, and GC-MS measures Huanghua Pear redwood sample to be measured The odour component of product records total ion chromatogram in mass spectrum full scan method, obtains the GC/MS fingerprint of Huanghua Pear sample to be measured Map.
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