CN109655559A - GC × GC-TOFMS detection method of volatile flavor in a kind of the operatic circle - Google Patents
GC × GC-TOFMS detection method of volatile flavor in a kind of the operatic circle Download PDFInfo
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Abstract
The invention discloses a kind of GC × GC-TOFMS detection methods of volatile flavor in the operatic circle.This method extracts the operatic circle aromatic substance using solid phase micro-extraction technique (SPME), the full spectrum scanning of volatile flavor in the operatic circle is realized by the instrument parameter that optimization GC × GC-TOFMS influences aromatic substance test analysis, it is qualitative that each component fragrance mass spectrum retrieves and match spectrum library data comparison progress through NIST/WILEY, using methyl n-heptyl ketone as inner mark solution, quantitative analysis is carried out to each aromatic substance in sample using internal standard method.This method is easy to operate, quick, high sensitivity, high resolution, can be used for the operatic circle place of production and traces to the source.
Description
Technical field
The present invention relates to the complete two-dimentional gas phase colors of the full spectrum scan method of volatile flavor in the operatic circle, in particular to application
Spectrum-flight time mass spectrum (GC × GC-TOFMS) realizes the full spectrum scanning of volatile flavor in the operatic circle, and passes through methyl n-heptyl ketone
Uantitative analytical is carried out, Food Science, analytical chemistry field are belonged to.
Background technique
As one of pears centre of origin, China has pears germ plasm resource abundant, occupies importantly in world's pears industry
Position.In recent years, no matter cultivated area or yield all rapidly developed, and pear new varieties are also increasing year by year.Fruit aroma can be with
The flavor characteristics and maturity of fruit are objectively responded, while directly decide the quality of fruit and its processed goods, are significantly affected
Its market competitiveness receives the extensive concern of a large amount of scholars in recent years.
Solid phase microextraction (solid phase micro-extraction, SPME) and gas chromatography combined with mass spectrometry (gas
Chromatography-mass spectrometry, GC-MS) it is the research most common method of aroma component.Have now
Influence of the person using this research bagging, maturity, picking time, storage period etc. to the operatic circle volatile aroma components；Analyze China four
In big system the operatic circle Volatile infochemicals and its between difference, it is special with the sense organ that the type of volatile materials describes the operatic circle
Property, and synthesis and the expression mechanisms of Volatile infochemicals are analyzed, good aroma component extraction side is established in research process
Method, and aroma component difference in the factor of influence the operatic circle fragrance, the operatic circle and formation correlation are described in detail.
With deepening constantly for testing requirements, GC-MS food volatilize and half volatilization research on limitation also gradually
It is exposed, such as sensitivity is lower, peak capacity is limited, detection ingredient is less.Comprehensive two dimensional gas chromatography has high resolution, sensitive
The advantages such as degree is high, peak capacity is big, can overcome the problems, such as that traditional single-column gas-chromatography is relatively poor to multicomponent sample separating capacity,
It is quite suitable for the analysis of complex system；Flight time mass spectrum has very high frequency acquisition, can be realized and complete two-dimentional gas phase
The best fit of chromatography, high-performance data processing software, has automatic peak identification and map deconvolutes and parses function, greatly in addition
The sensitivity for improving detection and analysis greatly, achieved good point in fields such as food, scent chemistry in recent years
Analyse effect.
Summary of the invention
It is an object of the invention to establish comprehensive two dimensional gas chromatography-flight time mass spectrum of volatile fragrances in the operatic circle
(GC × GC-TOFMS) detection method realizes that the operatic circle aromatic substance composes scanning entirely, is found by data analysis special in different the operatic circles
There is aromatised fraction, provides detailed, reliable data support for tracing to the source for the operatic circle.This method uses solid phase micro-extraction technique (SPME)
The operatic circle aromatic substance is extracted, is realized by the instrument parameter that optimization GC × GC-TOFMS influences aromatic substance test analysis
The full spectrum scanning of volatile flavor in the operatic circle.This method is easy to operate, quick, high sensitivity, high resolution, can be used for pears
It traces to the source in the fruit place of production.
The technical scheme adopted by the invention is as follows: the detection side GC × GC-TOFMS of volatile flavor in a kind of the operatic circle
Method, comprising the following steps:
(1) sample preparation: taking a part for the operatic circle, and pears block is cut into stoning, and each sample at least selects 3 the operatic circles, will
All pears blocks are uniformly mixed；
(2) volatile flavor extract: take mix pears it is packaged enter solid-phase micro-extracting device extraction flask in, be added dropwise 2- nonyl
Ketone inner mark solution is stood on pears block, covering tightly plug, and it is micro- that the operatic circle aroma substance is extracted to solid phase using solid-phase micro-extracting device
Extracting head；
(3) it desorbs: solid phase micro-extracting head insertion gas-chromatography end injection port being desorbed, guarantees the virtue of extracting head extraction
Studies of The Aromatic Substances fully enters comprehensive two dimensional gas chromatography system；
(4) it tests: by GC × GC-TOFMS detection method, test analysis being carried out to the operatic circle aromatic substance desorbed；
(5) qualitative: each component fragrance mass spectrum is retrieved through NIST/WILEY and matching spectrum library data comparison progress is qualitative, is only reported
Road matching degree is greater than 800 compound；
(6) quantitative: using methyl n-heptyl ketone inner mark solution as internal standard, each aromatic substance in sample being quantified using internal standard method
Analysis.
Preferably, pears block size is 0.5cm × 0.5cm in step (1) of the present invention.
Preferably, sampling amount is 6g in step (2) of the present invention, adds the methyl n-heptyl ketone inner mark solution of 5 μ L 10mg/L, is stood
Time is 10 ± 2min.
Preferably, solid phase microextraction condition in step (2) of the present invention are as follows: sample is placed in chromatography section solid-phase micro-extracting device
On, so that the temperature that module is added is maintained 40 ± 2 DEG C by constant temperature magnetic heating stirrer, 40 ± 5min of constant temperature extracting.
Preferably, desorption condition in step (3) of the present invention are as follows: solid phase micro-extracting head is inserted into gas-chromatography end injection port,
2min is parsed at 270 DEG C.
Preferably, the sensitivity of aromatic substance and the instrument parameter of resolution ratio are influenced in step (4) of the present invention by chromatostrip
Part and Mass Spectrometry Conditions two parts composition.
The chromatographic condition are as follows: chromatographic column 1 is Rxi-5MS, and chromatographic column 2 is Rxi-17Sil MS, and carrier gas is high-purity helium,
Sample introduction mode: shunt, split ratio 10:1, modulation period 3s.
Mass Spectrometry Conditions are EI ion source, collection voltages 1450V.
Further, chromatographic condition are as follows: 40 DEG C of the initial temperature of one-dimensional furnace box keeps 2min；With the speed of 5 DEG C/min
200 DEG C are risen to, with the speed of 20 DEG C/min, 280 DEG C is risen to and keeps 2min.The temperature of two-dimentional furnace box is higher than one-dimensional furnace box always
5 DEG C, the temperature of modulator is 15 DEG C higher than two-dimentional furnace box always.
Further, Mass Spectrometry Conditions are as follows: 250 DEG C of ion source temperature.
Matching spectrum library includes mainlib, replib, FF2017 in step (5) of the present invention.
Step (6) quantitative equation of the present invention be constituent content (ng/g)=[peak area of each component/interior target peak area ×
Internal standard concentration (mg/L) × inner mark solution volume (μ L)]/sample size (g).
The present invention uses comprehensive two dimensional gas chromatography-time-of-flight mass spectrometry (TOFMS), by optimizing temperature programming, split ratio, modulation
Period, collection voltages etc. determine optimal acquisition parameter, and the full spectrum scanning of volatile flavor in the operatic circle is realized with this, and pass through
Methyl n-heptyl ketone carries out uantitative analytical.This method overcome traditional single-column gas-chromatography sensitivity is lower, peak capacity is limited, detection
The problems such as ingredient is less.Unique two dimensional separation mode of GC × GC-TOFMS, is quite suitable for the analysis of complex system, one-dimensional color
Spectral peak is longitudinally separated on Two way chromatograms column by modem, is realized accurately identifying for superposition chromatographic peak, is mentioned significantly
The high sensitivity separating degree tested and analyzed.The present invention repeats input mode by sample, it is ensured that the accuracy of experiment.This method
Using the fruit optimal conditions that the operatic circle aroma substance is strong, a variety of the operatic circle analyses are adapted to.
Beneficial effects of the present invention:
(1) unique two-dimension analysis method of GC × GC-TOFMS is, it can be achieved that accurately identifying for superposition chromatographic peak, greatly improves
The sensitivity of volatile flavor detection, identification, accuracy is, it can be achieved that the full spectrum of the operatic circle fragrance information scans；
(2) it by the full spectrum information of the operatic circle aromatic substance, can fully understand the operatic circle volatile flavor information, excavate the operatic circle
Characteristic feature fragrance；
(3) the full spectrum information of the operatic circle volatile flavor traces to the source for the place of production and provides powerful data support, for the place of production
It is significant to realize that Hazard factor is traced to the source based on tracing to the source.
The method of the present invention is simple, quick, accurate, separating degree is high, accuracy and identification are high, it can be achieved that the operatic circle volatility virtue
The full spectrum of Studies of The Aromatic Substances scans, and can be used for research of tracing to the source based on the place of production of the operatic circle fragrance information.
Detailed description of the invention
Pears fragrance ingredient two-dimensional chromatogram under Fig. 1 difference heating rate；
Pear cv nanguo two-dimensional silhouette figure under Fig. 2 different modulating period；
The two-dimensional silhouette figure of 2- methyl naphthalene and 1- methyl naphthalene under Fig. 3 different modulating period；
Pear cv nanguo fragrance ingredient two-dimensional silhouette figure under Fig. 4 different voltages；
Fig. 5 pear cv nanguo fragrance ingredient two-dimensional silhouette figure；
Fig. 6 pear cv nanguo fragrance ingredient 3D figure；
Fig. 7 butyl acetate two-dimensional chromatogram；
Specific embodiment
For a better understanding of the present invention, below with reference to the embodiment content that the present invention is furture elucidated, but it is of the invention
Content is not limited solely to the following examples, and embodiment is not construed as limiting the scope of the present invention.
1 instrument and reagent
SUPELCO solid-phase micro-extracting device (company, chromatography section, the U.S.), including 50/30 μm of DVB/CAR/PDMS extracting head；
GC × GC-TOFMS:Agilent 7890B gas chromatograph (Agilent company of the U.S.) is equipped with PEGASUS mass spectrograph；
CORNING PC-420D magnetic stirring apparatus is purchased from Corning Incorporated；Sartorius BSA224S-CW assay balance is purchased from moral
Sai Duolisi company, state.
Methyl n-heptyl ketone (99.0%) is purchased from German Dr.Ehrensorfer company；Methanol (HPLC grades) is purchased from U.S. Fisher public affairs
Department.
2 instrument conditions
GC × GC-TOFMS method is as follows:
Chromatographic column 1 is Rxi-5MS (0.25 μm of the μ m of 30m × 250), and chromatographic column 2 is (2m × 250 μm Rxi-17Sil MS
× 0.25 μm), carrier gas is high-purity helium, sample introduction mode: flow velocity 1.4mL/min is shunted, split ratio 10:1.Preceding injection port and
Transmission line temperature is respectively 270 DEG C and 280 DEG C.40 DEG C of the initial temperature of one-dimensional furnace box keeps 2min；With the speed of 5 DEG C/min
200 DEG C are risen to, with the speed of 20 DEG C/min, 280 DEG C is risen to and keeps 2min.The temperature of two-dimentional furnace box is higher than one-dimensional furnace box always
5 DEG C, the temperature of modulator is 15 DEG C higher than two-dimentional furnace box always.Modulation period is that (the cold spray time is 0.9s to 3s, and the thermal jet time is
0.6s), coolant is liquid nitrogen, and heat modulation gas is compressed air, and cool tone gas is nitrogen.
Mass spectrum is EI ion source, and electron energy 70V, collection voltages 1450V, acquisition rate is 100 (spectra/s), is swept
Retouch range be 35-550amu, 250 DEG C of ion source temperature.
3 standard solution are prepared
0.1g (being accurate to 0.0001g) methyl n-heptyl ketone is weighed in volumetric flask, with methanol constant volume to 10mL, to be configured to
The standard reserving solution of 10000mg/L；It is spare that methyl n-heptyl ketone is diluted to 10mg/L with methanol；All standard solution are in -18 DEG C of refrigerators
Middle storage.
The optimization of 4 acquisition parameters
Influence of 4.1 programmed rates to aromatic substance separation confirmation
Temperature programming initial temperature is 40 DEG C, and 5 DEG C of heating rate/min and 8 DEG C/min of option program heating is tried
It tests, compares influence of two kinds of heating rates to the separation confirmation of volatile flavor in the operatic circle.
Influence of 4.2 split ratios to aromatic substance separation confirmation
The change of split ratio significantly affects sample volume, and setting tetra- gradients of 2:1,5:1,10:1,20:1 are tested, analyzed
Analyze the shadow of the peak separating phenomenon of the response of aroma substance in map, the shape of two-dimensional silhouette figure and high response aroma substance
It rings.
Influence of 4.3 modulation periods to aromatic substance separation confirmation
It is respectively set to 2s, 3s, 4s modulation period, investigates response, fragrance type sum and the identification of two-dimensional silhouette figure
Variation.
Influence of 4.4 collection voltages to aromatic substance separation confirmation
Voltage has a significant impact the response of object spectral peak, and 1400V is arranged, and 1450V, 1500V are optimized, and investigates
Aroma substance responds the variation of overload situations and peak type.
The extraction of 5 volatile aromatic ingredients and detection
Each the operatic circle is divided into 4 parts according to quartering, randomly chooses the perpendicular pears for cutting 0.5cm thickness in a part of the operatic circle
Piece, removes drupe, takes pulp on 5 the operatic circles every time, and belt leather is cut into 0.5cm × 0.5cm pears block, is uniformly mixed, 6g is taken to be packed into
In the extraction flask of SUPELCO solid-phase micro-extracting device, be added 5 μ L 10mg/L methyl n-heptyl ketones on pears block, cover tightly plug stand
10min extracts 40min under the conditions of 40 DEG C, solid phase micro-extracting head is then inserted into gas-chromatography end injection port, at 270 DEG C
2min is parsed, is detected under with optimal conditions.Each kind the operatic circle repeats test 3 times.
6 qualitative and quantitative analysis
Sample is after gas-chromatography is separated, and each component mass spectrum is retrieved through NIST/WILEY and analysis is determined
Property, only report the compound that matching degree is greater than 800；Quantitative calculating is carried out using methyl n-heptyl ketone as internal standard, additive amount is 5 μ L
10mg/L.Calculation formula is referring to forefathers' research method, constituent content (ng/g)=[peak area of each component/interior target peak area
× internal standard concentration (mg/L) × 5 μ L]/sample size (g).
7 results and discussion
7.1 full spectrum scanning analysis condition optimizings
7.1.1 the determination of temperature programming condition
The heating rate that the complicated multiplicity of fragrance ingredient in the operatic circle, first selection initial temperature are set as 40 DEG C and 8 DEG C/min, this
Fragrance component appearance time compares concentration in Shi Liguo, as shown in Figure 1, when heating rate is reduced to 5 DEG C/min, chromatographic peak separation
Preferably, more dispersed, it since GC × GC uses two dimensional separation, is not easy that complex temperature programming order is arranged, so final choosing
It selects heating rate and is reduced to 5 DEG C/min.
7.1.2 split ratio optimizes
The change of split ratio significantly affects sample volume, and setting tetra- gradients of 2:1,5:1,10:1,20:1 are tested, analyzed
The peak separating phenomenon of the response of aromatic substance in map, the shape of two-dimensional silhouette figure and high response aroma substance is analyzed, finally
Select split ratio 10:1 for optimal split ratio.
7.1.3 modulation period optimizes
Modulation period becomes smaller, and peak number amount increases, and peak type becomes more regular spindle, and peak separating degree is higher, accuracy
Higher, two-dimentional spectral peak identification is higher.Thus it is respectively 2s, 3s, 4s that modulation period, which is arranged, observes the variation at Two way chromatograms peak,
It was found that compound peak shape is the spindle of standard, such as Fig. 2 when modulation period is 3s.But modulation period is smaller, and peak is easy to occur
Crack produces a very large impact quantitative result as shown in figure 3,2- methyl naphthalene chromatographic peak is split into two parts, 1- methyl naphthalene
In the lowermost end of entire map, so being determined as modulating to guarantee the peak shape of all compounds and the accuracy of quantitative result
Period is 3s.
7.1.4 collection voltages value optimizes
Voltage has a significant impact the response of object spectral peak, and voltage is higher, and peak response is stronger, thus according to the operatic circle virtue
Perfume test preliminary experiment setting different voltages (1400V, 1450V, 1500V) optimizes.Such as Fig. 4, as voltage increases, object
Response is continuously increased, but voltage value is higher, and object instrument response is easy overload, causes peak type to be deteriorated, and same compound
There are multiple matching peaks in different retention times and two-dimensional time axis, same compound needs to close the increase of peak number amount.Thus according to
Experimental result determines that voltage value is 1450V.
The full spectrum scanning analysis of Volatile infochemicals in 7.2 pear cv nanguos
Pear cv nanguo two-dimensional silhouette figure and 3D figure, are shown in Fig. 5 and Fig. 6.Through counting, 130 kinds of fragrance ingredients are detected altogether, are detailed in table
1,66 kinds of esters, 10 kinds of olefines, 7 kinds of aldehydes, 9 kinds of alcohols, 5 kinds of ketone, 23 kinds of alkanes, 10 kinds of other classes.Esters always contain
Amount is up to 529.602ng/g (68.75%), and it is 143.541ng/g (18.6%) that next, which is olefines, and alcohols total content is
6.35ng/g (9.24%), aldehydes total content are 25.77ng/g (3.35%), amount to and account for 99% or more of sum.In pear cv nanguo
Main aromatic components be α-farnesene (132.33ng/g, 17.18%), ethyl acetate (80.14ng/g, 10.40%), butyric acid
Methyl esters (58.68ng/g, 7.62%), ethyl caprilate (43.03ng/g, 5.59%), ethyl alcohol (36.81ng/g, 4.78%), octanoic acid
Methyl esters (30.55ng/g, 3.97%), 2- hexen-1-ol acetic acid esters (30.31ng/g, 3.93%), butyl acetate (27.82ng/
G, 3.61%), ethyl propionate (22.55ng/g, 2.93%), 2- Methyl-butanoic acid ethyl ester (21.73ng/g, 2.82%), acetic acid heptan
Ester (19.98ng/g, 2.59%), octyl acetate (18.95ng/g, 2.46%), acetaldehyde (18.29ng/g, 2.37%), acetic acid third
Ester (16.80ng/g, 2.18%), methyl acetate (13.36ng/g, 1.73%), pentyl acetate (12.91ng/g, 1.68%), fourth
Acetoacetic ester (12.01ng/g, 1.56%), 2- butenoic acid ethyl (11.15ng/g, 1.45%), (Z) -2- hexenoic acid ethyl ester
(10.65ng/g, 1.38%), total account for the 67% of fragrance total amount.
Main volatile aromatic substance in 1 pear cv nanguo of table
7.3 GCxGC/TOFMS compose the unique advantage of scanning entirely
GCxGC/TOFMS has unique two dimensional separation mode, by taking butyl acetate in pear cv nanguo as an example, in a two dimensional 1,
2,3 be three of butyl acetate slices, responds highest 2nd slice and is set to base peak B, sees Fig. 7, that is to say, that in two-dimensional time
Butyl acetate confirmed 3 times by three slices in axis, mass spectrometry information is stayed plus the first dimension retention time, the second maintenance
Time constitutes 3 orthogonal dimension qualitative informations, guarantees the qualitative quality of butyl acetate, it is made to have high score in complicated component
Resolution.
Simultaneously in such a mode, GCxGC/TOFMS has high sensitivity, can be seen that with the additive amount of internal standard methyl n-heptyl ketone,
When being analyzed using comprehensive two dimensional gas chromatography, additive amount is only 1/200 when using GC/MS instrument, even if being 10:1 item in split ratio
Under part, response is also up to 107, and clear two-dimensional silhouette figure can be obtained.
It can be seen that high-resolution possessed by GCxGC/TOFMS and high sensitivity can make complex sample component
It is isolated to substantially improve, mass spectrometry Quality advance, it is possible to identify trace components kind number increases.
Compared with GC/MS, by taking pear cv nanguo as an example, GCxGC-TOFMS, which identifies component of the matching degree greater than 800,133 kinds,
And GC/MS detects 79 kinds of aroma substance altogether, the test data much smaller than GCxGC/TOFMS, is shown in Table 2.GC × GC/TOFMS analysis
Ester, alkanes, aldehydes, alcohols kind number are more than GC/MS data in fragrance data, the aroma substance kind number difference having more
For 32 kinds, 13 kinds, 4 kinds, 4 kinds, other kinds substance kind number is not much different.
The Ester and the alkanes substance overwhelming majority that detect in GC/MS appear at the test number of GC × GC/TOFMS
In；The kind number of olefin compound is not much different in two methods, and Species differences are larger, but major olefinic substance is all α-
Farnesene；Aldehyde material, alcohols material, ketone type similarly differ greatly, comprehensive two dimensional gas chromatography detect acetaldehyde, ethyl alcohol and third
Ketone, and relative amount highest, and these three substances are not detected in GC/MS.
The main Ester for being not detected in GC/MS, and being detected in GC × GC-TOFMS are as follows: 2- hexen-1-ol acetic acid esters
(30.30ng/g), butyl acetate (27.82ng/g), octyl acetate (18.95ng/g), propyl acetate (16.80ng/g), acetic acid
Methyl esters (13.36ng/g), 2- Methylbutyl acetate (7.86ng/g), (E)-blatter alcohol acetic acid esters (4.90ng/g), second
Sour isobutyl ester (4.41ng/g), methyl valerate (4.33ng/g), methyl propionate (2.72ng/g), 2- M Cr (2.68ng/
G), (E) -2- hexenoic acid methyl ester (1.44ng/g), acetic acid -3- methyl-3-butene-1-alcohol ester (1.28ng/g).
It can be seen that the unique two dimensional separation mode of GC × GC/TOFMS makes it have high-resolution and high sensitivity, it can
To realize the full spectrum scanning analysis of volatile flavor in the operatic circle, detailed volatile flavor information abundant is the operatic circle production
Ground, which is traced to the source, provides reliable data source.
Aromatic substance type variation in pear cv nanguo under the different detection methods of table 2
Embodiment 1:
Volatile flavor analysis detection in Cuiguan pear
1, sample extraction
Each the operatic circle is divided into 4 parts according to quartering, randomly chooses the perpendicular pears for cutting 0.5cm thickness in a part of the operatic circle
Piece, removes drupe, takes pulp on 5 the operatic circles every time, and belt leather is cut into 0.5cm × 0.5cm pears block, is uniformly mixed, 6g is taken to be packed into
In the extraction flask of SUPELCO solid-phase micro-extracting device, be added 5 μ L 10mg/L methyl n-heptyl ketones on pears block, cover tightly plug stand
10min, extracts 40min under the conditions of 40 DEG C, and each kind the operatic circle repeats test 3 times.
2, it tests
By solid phase micro-extracting head be inserted into gas-chromatography end injection port, parse 2min at 270 DEG C, under with optimal conditions into
Row detection.
3 results and analysis
As can be seen from Table 3,108 kinds of fragrance component are detected altogether in emerald green hat, wherein 47 kinds of Ester, 12 kinds of aldehydes, alcohol
5 kinds of class, 3 kinds of ketone, 19 kinds of aromatic hydrocarbons, 7 kinds of olefines, 8 kinds of alkanes, other 7 kinds.Further analysis, kingfisher are preced with each fragrance classification
The ratio for accounting for fragrance component total amount is summarized as follows, esters (61%), aldehydes (9%), alcohols (8%), ketone (0.5%), aromatic hydrocarbons
Class (20.4%), olefines (0.5%), alkanes (0.1%), ethers (0.2%), other (0.3%).Specifically, from fragrance
The quantity and comparision contents of ingredient, the fragrance component of kingfisher hat is based on esters, and esters fragrance threshold value is lower, has fruit flavor,
It is the main contributions ingredient of emerald green hat fragrance.Aldehydes general proportion in Chinese pear is larger, in the fragrance component of Chinese pear kingfisher hat,
Content is more than that olefine aldehydr (2.6%) imparts emerald green hat green grass fragrance by 1% just have acetaldehyde (1.6%), n-hexyl aldehyde (4.4%), 2-.
Kingfisher hat fragrance type is more, but the quantity such as high aromatic hydrocarbons, alkene of fragrance threshold value are more, content is larger, and human sensory judges
Fragrance it is less.
Main volatile aromatic substance in 3 Cuiguan pear fruit of table
Claims (10)
1. GC × GC-TOFMS detection method of volatile flavor in a kind of the operatic circle, characterized in that the following steps are included:
(1) sample preparation: taking a part for the operatic circle, and stoning is cut into pears block, each sample at least selects 3 the operatic circles, will own
Pears block is uniformly mixed；
(2) volatile flavor extract: take mix pears it is packaged enter solid-phase micro-extracting device extraction flask in, be added dropwise methyl n-heptyl ketone in
The operatic circle aroma substance is extracted to solid phase microextraction using solid-phase micro-extracting device on pears block, covering tightly plug standing by mark solution
Head；
(3) it desorbs: solid phase micro-extracting head insertion gas-chromatography end injection port being desorbed, guarantees the aromatic substance of extracting head extraction
Matter fully enters comprehensive two dimensional gas chromatography system；
(4) it tests: by GC × GC-TOFMS detection method, test analysis being carried out to the operatic circle aromatic substance desorbed；
(5) qualitative: it is qualitative that each component fragrance mass spectrum retrieves and match spectrum library data comparison progress through NIST/WILEY；
(6) quantitative: using methyl n-heptyl ketone inner mark solution as internal standard, each aromatic substance in sample quantitatively being divided using internal standard method
Analysis.
2. GC × GC-TOFMS detection method of volatile flavor, feature in a kind of the operatic circle as described in claim 1
It is GC × GC-TOFMS detection,
Its chromatographic condition are as follows: chromatographic column 1 is Rxi-5MS, and chromatographic column 2 is Rxi-17Sil MS, and carrier gas is high-purity helium, sample introduction mould
Formula: shunt, split ratio 10:1, modulation period 3s；
Its Mass Spectrometry Conditions are as follows: EI ion source, collection voltages 1450V.
3. GC × GC-TOFMS detection method of volatile flavor, feature in a kind of the operatic circle as claimed in claim 2
It is,
40 DEG C of the initial temperature of one-dimensional furnace box in the chromatographic condition keeps 2min；200 DEG C are risen to the speed of 5 DEG C/min, with
The speed of 20 DEG C/min rises to 280 DEG C and keeps 2min；The temperature of two-dimentional furnace box is 5 DEG C higher than one-dimensional furnace box always, modulator
Temperature is 15 DEG C higher than two-dimentional furnace box always.
4. GC × GC-TOFMS detection method of volatile flavor, feature in a kind of the operatic circle as claimed in claim 2
It is that the mass spectrographic ion source temperature is 250 DEG C.
5. GC × GC-TOFMS detection of volatile flavor in a kind of the operatic circle as described in any one of claim 1-4
Method, characterized in that pears block size is 0.5cm × 0.5cm in the step (1).
6. GC × GC-TOFMS detection of volatile flavor in a kind of the operatic circle as described in any one of claim 1-4
Method, characterized in that step (2) extraction temperature is 40 ± 2 DEG C, and extraction time is 40 ± 5min.
7. GC × GC-TOFMS detection of volatile flavor in a kind of the operatic circle as described in any one of claim 1-4
Method, characterized in that it is 6g that pears block sampling amount is mixed in the step (2), adds the methyl n-heptyl ketone inner mark solution of 5 μ L 10mg/L,
Time of repose is 10 ± 2min.
8. GC × GC-TOFMS detection of volatile flavor in a kind of the operatic circle as described in any one of claim 1-4
Method, characterized in that desorption condition in the step (3) are as follows: solid phase micro-extracting head is inserted into gas-chromatography end injection port, in
2min is parsed at 270 DEG C.
9. GC × GC-TOFMS detection of volatile flavor in a kind of the operatic circle as described in any one of claim 1-4
Method, characterized in that matching spectrum library is mainlib, replib or FF2017 in the step (5).
10. GC × GC-TOFMS inspection of volatile flavor in a kind of the operatic circle as described in any one of claim 1-4
Survey method, characterized in that the qualitative only report matching degree in the step (5) is greater than 800 compound.
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