CN106526040B - Differentiate the method for fresh cocoon/dried cocoon raw silk based on GC or GC-MS technologies - Google Patents

Differentiate the method for fresh cocoon/dried cocoon raw silk based on GC or GC-MS technologies Download PDF

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CN106526040B
CN106526040B CN201610997303.4A CN201610997303A CN106526040B CN 106526040 B CN106526040 B CN 106526040B CN 201610997303 A CN201610997303 A CN 201610997303A CN 106526040 B CN106526040 B CN 106526040B
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dried cocoon
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CN106526040A (en
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马明波
周文龙
董锁拽
王聪磊
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Zhejiang University of Technology ZJUT
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    • G01—MEASURING; TESTING
    • G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
    • G01N30/00—Investigating or analysing materials by separation into components using adsorption, absorption or similar phenomena or using ion-exchange, e.g. chromatography or field flow fractionation
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    • G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
    • G01N30/00—Investigating or analysing materials by separation into components using adsorption, absorption or similar phenomena or using ion-exchange, e.g. chromatography or field flow fractionation
    • G01N30/02—Column chromatography
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    • G01N30/8624—Detection of slopes or peaks; baseline correction
    • G01N30/8631—Peaks
    • G01N30/8634—Peak quality criteria
    • G—PHYSICS
    • G01—MEASURING; TESTING
    • G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
    • G01N30/00—Investigating or analysing materials by separation into components using adsorption, absorption or similar phenomena or using ion-exchange, e.g. chromatography or field flow fractionation
    • G01N30/02—Column chromatography
    • G01N30/88—Integrated analysis systems specially adapted therefor, not covered by a single one of the groups G01N30/04 - G01N30/86

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Abstract

The invention discloses a kind of method differentiating fresh cocoon/dried cocoon raw silk based on GC or GC MS technologies, using raw silks of fresh cocoons, dried cocoon raw silk as sample to be tested；Include the following steps：1), sample to be tested extracts after organic solvent is added, and extract is obtained after extracting solution concentration；2) organic solvent, is added to re-dissolve extract, filters, gained filtrate is test liquid；3), GC MS differential methods：When chemical composition corresponding to the maximum chromatographic peak of peak area in the GC figures of sample to be tested is 1 acetic acid hexacosane base ester；Judge the sample to be tested for dried cocoon raw silk；Otherwise, it is determined that the sample to be tested is raw silks of fresh cocoons；GC differential methods：When gap absolute value≤1min of retention time and the retention time of 1 acetic acid hexacosane base ester standard items corresponding to the maximum chromatographic peak of GC middle peak of spectrogram areas of sample to be tested, judge the sample to be tested for dried cocoon raw silk；Otherwise, it is determined that sample is raw silks of fresh cocoons.

Description

Differentiate the method for fresh cocoon/dried cocoon raw silk based on GC or GC-MS technologies
Technical field
The present invention relates to Raw Silk detection fields, specially utilize gas-chromatography (GC) or gas chromatography-mass spectrum (GC-MS) technology differentiates raw silks of fresh cocoons and the method for dried cocoon raw silk.
Background technology
Reel silk from cocoons raw silks of fresh cocoons need not move through the processes such as cocoon drying, cocoon cooking, can also recycle silkworm chrysalis, and therefore, production is fresh Cost needed for cocoon raw silk is less than reel silk from cocoons dried cocoon raw silk.Since raw silks of fresh cocoons do not mark clearly, market price is again substantially equivalent In the price of homogeneity dried cocoon raw silk, significant economic interests have highlighted the great advantage of fresh cocoon reeling.Recent years, fresh silkworm chrysalis warp The promotion for value of helping, has greatly transferred the enthusiasm for production of reeling enterprises, has promoted the large-scale development process of fresh cocoon reeling. This, which is directly resulted in, is flooded with a large amount of raw silks of fresh cocoons on current Raw Silk Market.Research report shows that the gum content of raw silks of fresh cocoons is inclined Height, cohesive force is relatively low, and bar evenness is poor, rough line is more, and grade is not so good as dried cocoon raw silk.More and more silk production enterprises The weaving performance of reflection, raw silks of fresh cocoons is not so good as dried cocoon raw silk, and various problems are will appear in weaving process, influence the matter of product Amount.Therefore, raw silk is detected, it is particularly significant to business transaction and specification Raw Silk Market distinguishes fresh cocoon and dried cocoon raw silk.
Currently, researcher, which proposes a variety of methods, differentiates raw silks of fresh cocoons and dried cocoon raw silk, such as patent CN 201410379015.3, CN 201310017273.2, CN 201310017296.3 etc., these methods be all based on fresh silk and The difference of the physical property of dried cocoon silk, such as whiteness, strength, are scientific.But these methods exist very Significant defect, i.e.,：The rule that these methods are based on is built upon on general, significant difference.Fresh, dried cocoon silk these The difference of physical property is not absolute, is not this qualitative difference of the two, it is impossible to make discriminating of a certain index as the two Standard.
Invention content
The technical problem to be solved in the present invention is to provide a kind of raw silks of fresh cocoons based on GC GC-MS technologies and dried cocoon to give birth to Silk discrimination method, this method are identified raw silk sample based on volatile chemical component information, and accuracy is high.
In order to solve the above technical problem, the present invention provides one kind differentiating fresh cocoon/dried cocoon raw silk based on GC or GC-MS technologies Method, using raw silks of fresh cocoons, dried cocoon raw silk as sample to be tested；Include the following steps：
1), sample to be tested is shredded or is crushed, (preferably ultrasonic wave assisted extraction) is extracted after organic solvent is added, It (is concentrated to dryness) after the extracting solution concentration of gained, obtains extract；
2) organic solvent, is added to re-dissolve extract, filters, gained filtrate is test liquid (that is, test solution)；
3) any one following identification method, is selected：
Mode one, GC-MS differential methods：
Test liquid is analyzed with GC-MS combined instruments, to obtain GC the and MS spectrograms of sample to be tested；
Judgement silk is the standard of raw silks of fresh cocoons or dried cocoon raw silk：When peak area is maximum in the GC figures of sample to be tested Chemical composition corresponding to chromatographic peak (is 1- acetic acid two by the conclusion that mass spectrometry database provides when being 1- acetic acid hexacosane base esters When cetyl ester)；Judge the sample to be tested for dried cocoon raw silk；Otherwise, it is determined that the sample to be tested is raw silks of fresh cocoons；
Remarks explanation：The structural information of above-mentioned chemical composition is provided by online NIST databases；
Mode two, GC differential methods：
Test liquid and 1- acetic acid hexacosane base esters (C are analyzed respectively with GC instrument28H56O2, CAS#822-32-2) and standard items are molten Liquid；
Judgement silk is the standard of raw silks of fresh cocoons or dried cocoon raw silk：When the GC middle peak of spectrograms area of sample to be tested is maximum Chromatographic peak corresponding to retention time and 1- acetic acid hexacosane base ester standard items retention time gap absolute value≤ When 1min, judge the sample to be tested for dried cocoon raw silk；Otherwise, it is determined that sample is raw silks of fresh cocoons.
The improvement of the method for differentiating fresh cocoon/dried cocoon raw silk based on GC or GC-MS technologies as the present invention：
Organic solvent in the step 1) and step 2) is ethyl alcohol, ethyl acetate, n-hexane or petroleum ether.
Remarks explanation：The target of the step 1) extraction is the volatile chemical component obtained in raw silk sample.
The further improvements in methods for differentiating fresh cocoon/dried cocoon raw silk based on GC or GC-MS technologies as the present invention：
In the step 1), the solid-liquid ratio of sample to be tested and organic solvent is 1g/5~200mL.
The further improvements in methods for differentiating fresh cocoon/dried cocoon raw silk based on GC or GC-MS technologies as the present invention：
In the step 1), extracting mode is ultrasonic wave assisted extraction, and extraction time is 2 minutes~10 hours.
The further improvements in methods for differentiating fresh cocoon/dried cocoon raw silk based on GC or GC-MS technologies as the present invention：
In the step 2), the aperture of filtering is 0.22 μm~0.45 μm.
Remarks explanation：The syringe filter that general selection aperture is 0.22 μm or 0.45 μm.
The further improvements in methods for differentiating fresh cocoon/dried cocoon raw silk based on GC or GC-MS technologies as the present invention：It is described In step 3),
GC conditions in mode one and mode two are：It is warming up to 200~350 DEG C from initial temperature (20~60 DEG C)；It carries Gas is helium, hydrogen or nitrogen, flow rate of carrier gas 1ml/min；Sample size：1μL；
Remarks explanation：Above-mentioned heating rate is generally 5~10 DEG C/min, for example, 6 DEG C/min；
MS analysis conditions are in mode two：Mass spectrographic ion source is the sources EI；Scanning of the mass spectrum range (m/z) be 35~ 600amu。
The further improvements in methods for differentiating fresh cocoon/dried cocoon raw silk based on GC or GC-MS technologies as the present invention：
In the mode one of step 3), composed with the retention time of the maximum chemical composition of GC middle peak of spectrogram areas and NIST Library searching result is foundation；It is determined as that the necessary condition of dried cocoon raw silk is：The maximum ingredient warp of GC middle peak of spectrogram areas of sample NIST library searchings, the highest result of matching degree are 1- acetic acid hexacosane base esters (C28H56O2)；Otherwise, it is determined that sample to be tested is Raw silks of fresh cocoons.
The further improvements in methods for differentiating fresh cocoon/dried cocoon raw silk based on GC or GC-MS technologies as the present invention：
In the mode two of step 3), it is determined as that the necessary condition of dried cocoon raw silk is：The GC middle peak of spectrogram areas of sample to be tested Retention time (retention time close with the retention time of 1- acetic acid hexacosane base ester standard items corresponding to maximum chromatographic peak Gap absolute value≤1min), judge the sample to be tested for dried cocoon raw silk；Otherwise, it is determined that sample is raw silks of fresh cocoons.
In the process of the present invention, the method for the invention is used to establish the standard drawing of raw silks of fresh cocoons and dried cocoon raw silk first Spectrum；Take the foundation of the raw silks of fresh cocoons and dried cocoon raw silk in the different village mouthful for standard diagram.
The organic solvent of step 1) and step 2) can be same object, also can not be same object.
The GC analysis conditions of step 3) are preferably：Chromatographic column specification is 30m × 0.25mm × 0.25 μm quartz capillary column； Carrier gas is helium；Flow velocity is 1.0mL/min；Injector temperature is 200~300 DEG C；Temperature programming：With 6 DEG C/min from initial temperature 20~60 DEG C of degree is warming up to 200~350 DEG C；Sample size is 1 μ L；
MS Mass Spectrometry Conditions are preferably：Ion source is the sources EI；Electron energy is 70eV；Mass scan range is 35~600am μ；Acquisition mode is scan patterns.
The present invention is realized particular by following technical scheme：
(1) standard diagram of raw silks of fresh cocoons and dried cocoon raw silk is established
A, the raw silks of fresh cocoons and dried cocoon raw silk for taking the different village mouthful, raw silk is shredded or is crushed, and addition solvent extracts (super Sound wave assisted extraction).Obtained extracting solution is concentrated to dryness, extract is obtained.
B, solvent is added to re-dissolve extract, filter, filtrate is as test solution.
C, test liquid is analyzed with GC-MS combined instruments, obtains the gas chromatogram and mass spectrogram of sample.
D, by standard items 1- acetic acid hexacosane base esters (C28H56O2, CAS#822-32-2) with solvent it is made into 0.1 μ g/mL The standard solution of~1mg/mL.
E, 1- acetic acid hexacosane base ester standard solution is analyzed with GC instrument, obtains 1- acetic acid hexacosane base ester standard items GC spectrograms.
In the above technical solution, the Extraction solvent described in step a is organic solvent (petroleum ether, n-hexane, acetic acid second Ester, ethyl alcohol etc.).
In the above technical solution, the solvent described in step b and d and the solvent described in step a can be same object, also may not be used For same object.
The GC-MS of the step c is analyzed:Chromatographic column specification is 30m × 0.25mm × 0.25 μm quartz capillary column；Carrier gas For helium；Flow velocity is 1.0mL/min；Injector temperature is 200~300 DEG C；Temperature programming：With 6 DEG C/min from initial temperature 20 DEG C it is warming up to 200~350 DEG C；Sample size is 1 μ L；Mass Spectrometry Conditions are：Ion source is the sources EI；Electron energy is 70eV；Quality is swept Retouch ranging from 35-600am μ；Acquisition mode is scan patterns.
(2) when analyzing sample using GC-MS combined instruments (GC-MS methods), raw silk to be measured is obtained in the identical methods of step c The GC-MS collection of illustrative plates of sample.The standard diagram of the GC-MS collection of illustrative plates of sample to be tested and raw silks of fresh cocoons and dried cocoon raw silk is compared, is judged Sample to be tested is that raw silks of fresh cocoons are still dried cocoon raw silk.
Judgment method is：When the chemical composition corresponding to the maximum chromatographic peak of peak area in the gas chromatogram of sample to be tested When the structural information provided by online NIST databases is 1- acetic acid hexacosane base esters, judge that the sample to be tested is given birth to for dried cocoon Silk.Otherwise, sample is raw silks of fresh cocoons.
(3) it when analyzing sample using GC instrument (GC methods), with the GC condition analysis samples to be tested in step c, obtains to be measured The GC spectrograms of sample.The GC collection of illustrative plates of sample to be tested and the GC collection of illustrative plates of 1- acetic acid hexacosane base ester standard items are compared, sentenced Disconnected sample to be tested is that raw silks of fresh cocoons are still dried cocoon raw silk.
Judgment method is：Retention time corresponding to the maximum chromatographic peak of GC middle peak of spectrogram areas of sample to be tested and 1- When the retention time of acetic acid hexacosane base ester standard items is close (within difference 1min), judge that the sample to be tested is given birth to for dried cocoon Silk.Otherwise, it is determined that sample is raw silks of fresh cocoons.
The present invention has following technical advantage：
1, the present invention for the first time identifies raw silks of fresh cocoons and dried cocoon raw silk using GC GC-MS technologies.What is used carries Take solvent selectivity wide, extracting method is succinctly, conveniently；
2, the present invention is based on the detection method of silk volatile chemical component, and method is reliable, and discrimination is high.
It is detection object that the present invention, which is with the volatile small molecule chemical composition in silk, is given birth to according to raw silks of fresh cocoons and dried cocoon The difference of these small molecule components differentiates that sample is fresh cocoon or dried cocoon raw silk in silk.
In conclusion the present invention selects GC GC-MS technologies to analyze volatile chemical component in raw silk, solve Difficult problem is differentiated to raw silks of fresh cocoons and dried cocoon raw silk；The method of the present invention is easy to operate, rapid, and experimental result intuitively may be used It leans on, accuracy rate is high, can be used for the quality control and evaluation of raw silk product.
Description of the drawings
The specific implementation mode of the present invention is described in further detail below in conjunction with the accompanying drawings.
Fig. 1 is the GC standard diagrams of raw silks of fresh cocoons and dried cocoon raw silk when using ethyl alcohol as Extraction solvent.
Fig. 2 be using ethyl acetate be Extraction solvent when raw silks of fresh cocoons and dried cocoon raw silk GC standard diagrams.
Fig. 3 is the GC standard diagrams of raw silks of fresh cocoons and dried cocoon raw silk when using n-hexane as Extraction solvent.
Fig. 4 is the GC standard diagrams of raw silks of fresh cocoons and dried cocoon raw silk when using petroleum ether as Extraction solvent.
Fig. 5 is that (retention time is 30min or so, 1- acetic acid 20 to the maximum component of dried cocoon raw silk GC middle peak of spectrogram areas Six Arrcostabs) MS figure.
Fig. 6 is the GC spectrograms of 1- acetic acid hexacosane base ester standard items.
Specific implementation mode
With reference to specific embodiment, the present invention is described further, but protection scope of the present invention is not limited in This.
Embodiment 1：The blind examination identification of two raw silk samples (1# and 2# samples) of nutrient elements in Huzhou area of Zhejiang Province production：
Above-mentioned two raw silk sample is proceeded as follows respectively：
Sample is shredded respectively to 1cm hereinafter, the sample of 5g or so is taken to be placed in 250mL beakers, addition 80mL ethyl alcohol surpasses Sound wave (frequency 23KHz, power 100W) assisted extraction 90min.Obtained extracting solution is concentrated to dryness at 50 DEG C, obtains ethyl alcohol Extract.
Extract is re-dissolved with 1mL ethyl alcohol, is filtered solution with the syringe filter in 0.22 μm of aperture.
Then following 2 kinds of modes are carried out respectively：
Mode one, GC-MS methods：Filtrate is analyzed with GC-MS combined instruments, analysis condition is Agilent 7890B-5977A gas Phase chromatography-mass spectroscopy instrument；Chromatographic column specification is 30m × 0.25mm × 0.25 μm quartz capillary column；Carrier gas is helium；Flow velocity is 1.0mL/min；Injector temperature is 220 DEG C；Temperature programming：It is warming up to for 20 DEG C from initial temperature with the heating rate of 6 DEG C/min 250℃；Sample size is 1 μ L；Mass Spectrometry Conditions are：Ion source is the sources EI；Electron energy is 70eV；Mass scan range be 35~ 600amμ；Acquisition mode is scan patterns.
Analysis result：The retention time of sample each component and integral area are by Agilent GC-MS chemistry works in GC spectrograms Make station to be automatically performed, relative amount is obtained by area normalization method, and chemical composition use of information NIST library searchings determine, knot Fruit is as shown in Table 1 and Table 2.
The maximum component retention time of 1# sample GC middle peak of spectrogram areas is 29.887min, is identified through NIST library searchings For 1- acetic acid hexacosanes base ester (No. CAS:822-32-2), the necessary condition for meeting the judgement of dried cocoon raw silk, therefore, it is determined that being dry Silk raw silk.The maximum component retention time of 2# sample GC middle peak of spectrogram areas is 21.001min, is identified through NIST library searchings For phthalic acid ester, the necessary condition of dried cocoon raw silk judgement is not met, therefore, it is determined that being raw silks of fresh cocoons.The above judgement result warp Sample provider (Silk Detection Centre, Zhejiang Exit-Entry Inspection and Quarantine) confirms, completely correct.
The GC-MS data of table 1,1# sample main components
The GC-MS data of table 2,2# sample main components
Mode two, GC methods：Filtrate is analyzed using GC instrument, GC analysis conditions and the GC in GC-MS methods are consistent.Analysis knot Fruit：The retention time of sample each component and integral area are automatically performed by Agilent GC-MS chem workstations in GC spectrograms, phase Content is obtained by area normalization method.
The maximum component retention time of 1# sample GC middle peak of spectrogram areas is 29.869min, 2# sample GC middle peak of spectrograms face The maximum component retention time of product is 21.015min.The retention time of 1# samples and 1- acetic acid hexacosane base ester standard items Retention time (29.764min) differs 0.105min, and gap is within 1min.The necessary item of 1# samples met dried cocoon raw silks judgement Part, therefore, it is determined that for dried cocoon silk raw silk.The 2# samples maximum component of GC middle peak of spectrogram areas and 1- acetic acid hexacosane base ester marks The retention time of quasi- product differs 8.749min, does not meet the necessary condition of dried cocoon raw silk judgement, therefore, it is determined that being raw silks of fresh cocoons.With Upper judgement result confirms through sample provider (Silk Detection Centre, Zhejiang Exit-Entry Inspection and Quarantine), completely correct.
Confirmatory experiment 1, by 10 different raw silks of fresh cocoons samples of the place of production known to realization and 10 dried cocoon raw silk samples, as 1 the method for embodiment is detected；
The testing result of each dried cocoon raw silk sample is satisfied by the following conditions：When being detected using GC-MS methods, GC middle peak of spectrograms Maximum group of lease making NIST library searching of area is accredited as 1- acetic acid hexacosane base esters.When being detected using GC methods, sample GC spectrums In figure the retention time gap of the maximum component retention time of peak area and 1- acetic acid hexacosane base ester standard items 1min with It is interior.
And 10 raw silks of fresh cocoons samples cannot meet above-mentioned condition；That is, its maximum group of lease making of GC middle peak of spectrogram areas The identification of NIST library searchings is the substance other than 1- acetic acid hexacosane base esters.Peak area is most when being detected with GC methods, in GC figures The retention time of big component is with the retention time gap of 1- acetic acid hexacosane base ester standard items in 1min or more.
Embodiment 2：The blind examination identification of two raw silk samples (3# and 4# samples) of Guangxi Yizhou area production：
Above-mentioned two raw silk sample is proceeded as follows respectively：
Sample is shredded to 1cm hereinafter, 6.7g is taken to be placed in 250mL beakers, 120mL ethyl acetate is added, ultrasonic wave is auxiliary Help extraction 2min.Obtained extracting solution is concentrated to dryness at 35 DEG C, obtains extract.
Extract is re-dissolved with 1mL n-hexanes, the syringe filter filtering in 0.45 μm of aperture is used in combination.
Then following 2 kinds of modes are carried out respectively：
Mode one, GC-MS methods：Filtrate is analyzed with GC-MS combined instruments, analysis condition is:Agilent 7890B-5977A gas Phase chromatography-mass spectroscopy instrument；Chromatographic column specification is 30m × 0.25mm × 0.25 μm quartz capillary column；Carrier gas is helium；Flow velocity is 1.0mL/min；Injector temperature is 200 DEG C；Temperature programming：It is warming up to for 60 DEG C from initial temperature with the heating rate of 6 DEG C/min 330℃；Sample size is 1 μ L；Mass Spectrometry Conditions are：Ion source is the sources EI；Electron energy is 70eV；Mass scan range be 35~ 600amμ；Acquisition mode is scan patterns.
Analysis result：The retention time of sample each component and integral area are automatically performed by work station in GC spectrograms, relatively Content is obtained by area normalization method, and chemical composition use of information NIST library searchings determine, as a result as shown in Table 3 and Table 4.
The maximum component retention time of 3# sample GC middle peak of spectrogram areas is 30.096min, is identified through NIST library searchings For 1- acetic acid hexacosane base esters, meet the necessary condition of dried cocoon raw silk judgement, therefore, it is determined that being dried cocoon raw silk.4# sample GC spectrograms The middle maximum component retention time of peak area is 21.001min, and phthalic acid ester, judgement knot are accredited as through NIST library searchings Fruit confirms through sample provider (Silk Detection Centre, Zhejiang Exit-Entry Inspection and Quarantine), completely correct.
The GC-MS data of table 3,3# sample main components
The GC-MS data of table 4,4# sample main components
Mode two, GC methods：Filtrate is analyzed using GC instrument, GC analysis conditions and the GC in GC-MS methods are consistent.Analysis knot Fruit：The retention time of sample each component and integral area are automatically performed by Agilent GC-MS chem workstations in GC spectrograms, phase Content is obtained by area normalization method.
The maximum component retention time of 3# sample GC middle peak of spectrogram areas is 30.201min, 4# sample GC middle peak of spectrograms face The maximum component retention time of product is 21.315min.The retention time of 1# samples and 1- acetic acid hexacosane base ester standard items Retention time (29.764min) differs 0.437min, and gap is within 1min.The necessary item of 3# samples met dried cocoon raw silks judgement Part, therefore, it is determined that for dried cocoon silk raw silk.The 4# samples maximum component of GC middle peak of spectrogram areas and 1- acetic acid hexacosane base ester marks The retention time of quasi- product differs 8.449min, does not meet the necessary condition of dried cocoon raw silk judgement, therefore, it is determined that being raw silks of fresh cocoons.With Upper judgement result confirms through sample provider (Silk Detection Centre, Zhejiang Exit-Entry Inspection and Quarantine), completely correct.
Confirmatory experiment 2, by 10 different raw silks of fresh cocoons samples of the place of production known to realization and 10 dried cocoon raw silk samples, as 2 the method for embodiment is detected；
The testing result of each dried cocoon raw silk sample is satisfied by the following conditions：When being detected using GC-MS methods, GC middle peak of spectrograms Maximum group of lease making NIST library searching of area is accredited as 1- acetic acid hexacosane base esters.When being detected using GC methods, sample GC spectrums In figure the retention time gap of the maximum component retention time of peak area and 1- acetic acid hexacosane base ester standard items 1min with It is interior.
And 10 raw silks of fresh cocoons samples cannot meet above-mentioned condition；That is, its maximum group of lease making of GC middle peak of spectrogram areas The identification of NIST library searchings is the substance other than 1- acetic acid hexacosane base esters.Peak area is most when being detected with GC methods, in GC figures The retention time of big component is with the retention time gap of 1- acetic acid hexacosane base ester standard items in 1min or more.
Embodiment 3：The blind examination identification of the raw silk sample (5# and 6# samples) of Dongtai area production：
Above-mentioned two raw silk sample is proceeded as follows respectively：
Sample is shredded to 1cm hereinafter, 1.06g is taken to be placed in 250mL beakers, addition 200mL n-hexanes, ultrasonic wave assists Extract 4hours.Obtained extracting solution is concentrated to dryness at 30 DEG C, obtains extract.
Extract is re-dissolved with 1mL ethyl acetate, the syringe filter filtering in 0.22 μm of aperture is used in combination.
Then following 2 kinds of modes are carried out respectively：
Mode one, GC-MS methods：Filtrate is analyzed with GC-MS combined instruments, analysis condition is:Agilent 7890B-5977A gas Phase chromatography-mass spectroscopy instrument；Chromatographic column specification is 30m × 0.25mm × 0.25 μm quartz capillary column；Carrier gas is nitrogen；Flow velocity is 1.0mL/min；Injector temperature is 300 DEG C；Temperature programming：It is warming up to for 30 DEG C from initial temperature with the heating rate of 6 DEG C/min 350℃；Sample size is 1 μ L；Mass Spectrometry Conditions are：Ion source is the sources EI；Electron energy is 70eV；Mass scan range be 35~ 600amμ；Acquisition mode is scan patterns.
Analysis result：The retention time of the sample each component and integral area are automatically performed by work station in GC spectrograms, phase Content is obtained by area normalization method, chemical composition use of information NIST library searchings determine, as a result such as 6 institute of table 5 and table Show.
The maximum component retention time of 5# sample GC middle peak of spectrogram areas is 18.031min, is identified through NIST library searchings For cedrol, the necessary condition of dried cocoon raw silk judgement is not met, therefore, it is determined that being raw silks of fresh cocoons.6# sample GC middle peak of spectrograms area is most Big component retention time is 29.935min, and 1- acetic acid hexacosane base esters are accredited as through NIST library searchings, therefore, it is determined that should Sample is dried cocoon raw silk.Judge that result confirms through sample provider (Silk Detection Centre, Zhejiang Exit-Entry Inspection and Quarantine), it is complete Total correctness.
The GC-MS data of table 5,5# sample main components
The GC-MS data of table 6,6# sample main components
Mode two, GC methods：Filtrate is analyzed using GC instrument, GC analysis conditions and the GC in GC-MS methods are consistent.Analysis knot Fruit：The retention time of sample each component and integral area are automatically performed by Agilent GC-MS chem workstations in GC spectrograms, phase Content is obtained by area normalization method.
The maximum component retention time of 5# sample GC middle peak of spectrogram areas is 18.089min, 6# sample GC middle peak of spectrograms face The maximum component retention time of product is 29.885min.The retention time of 5# samples and 1- acetic acid hexacosane base ester standard items Retention time (29.764min) differs 11.675min, and gap is in 1min or more.5# samples do not meet dried cocoon raw silk judgement must Condition is wanted, therefore, it is determined that being fresh silk raw silk.The 6# samples maximum component of GC middle peak of spectrogram areas and 1- acetic acid ceruls The retention time of ester standard items differs 0.121min, meets the necessary condition of dried cocoon raw silk judgement, therefore, it is determined that being dried cocoon raw silk. The above judgement result confirms through sample provider (Silk Detection Centre, Zhejiang Exit-Entry Inspection and Quarantine), completely correct.
Confirmatory experiment 3, by 10 different raw silks of fresh cocoons samples of the place of production known to realization and 10 dried cocoon raw silk samples, as 3 the method for embodiment is detected；
The testing result of each dried cocoon raw silk sample is satisfied by the following conditions：When being detected using GC-MS methods, GC middle peak of spectrograms Maximum group of lease making NIST library searching of area is accredited as 1- acetic acid hexacosane base esters.When being detected using GC methods, sample GC spectrums In figure the retention time gap of the maximum component retention time of peak area and 1- acetic acid hexacosane base ester standard items 1min with It is interior.
And 10 raw silks of fresh cocoons samples cannot meet above-mentioned condition；That is, its maximum group of lease making of GC middle peak of spectrogram areas The identification of NIST library searchings is the substance other than 1- acetic acid hexacosane base esters.Peak area is most when being detected with GC methods, in GC figures The retention time of big component is with the retention time gap of 1- acetic acid hexacosane base ester standard items in 1min or more.
Embodiment 4：The blind examination identification of the raw silk sample (7# and 8# samples) of Foshan area production：
Above-mentioned two raw silk sample is proceeded as follows respectively：
Sample is shredded to 1cm hereinafter, 2.3g is taken to be placed in 250mL beakers, addition 200mL petroleum ethers, ultrasonic wave assists Extract 10hours.Obtained extracting solution is concentrated to dryness at 30 DEG C, obtains extract.
Extract is re-dissolved with 1mL petroleum ethers, the syringe filter filtering in 0.22 μm of aperture is used in combination.
Then following 2 kinds of modes are carried out respectively：
Mode one, GC-MS：Filtrate is analyzed with GC-MS combined instruments, analysis condition is:Agilent 7890B-5977A gas phases Chromatography-mass spectroscopy instrument；Chromatographic column specification is 30m × 0.25mm × 0.25 μm quartz capillary column；Carrier gas is hydrogen；Flow velocity is 1.0mL/min；Injector temperature is 250 DEG C；Temperature programming：It is warming up to for 20 DEG C from initial temperature with the heating rate of 6 DEG C/min 200℃；Sample size is 1 μ L；Mass Spectrometry Conditions are：Ion source is the sources EI；Electron energy is 60eV；Mass scan range be 35~ 600amμ；Acquisition mode is scan patterns.
Analysis result：The retention time of the sample each component and integral area are automatically performed by work station in GC spectrograms, phase Content is obtained by area normalization method, chemical composition use of information NIST library searchings determine, as a result such as 8 institute of table 7 and table Show.
The maximum component retention time of 7# sample GC middle peak of spectrogram areas is 24.677min, is identified through NIST library searchings For ethyl palmitate, the necessary condition of dried cocoon raw silk judgement is not met, therefore, it is determined that being raw silks of fresh cocoons.8# sample GC middle peak of spectrograms face The maximum component retention time of product is 28.991min, is accredited as 1- acetic acid hexacosane base esters through NIST library searchings, therefore sentence The fixed sample is dried cocoon raw silk.Judge that result is true through sample provider (Silk Detection Centre, Zhejiang Exit-Entry Inspection and Quarantine) Recognize, it is completely correct.
The GC-MS data of table 7,7# sample main components
The GC-MS data of table 8,8# sample main components
Mode two, GC methods:Filtrate is analyzed using GC instrument, GC analysis conditions and the GC in method one are consistent.Analysis knot Fruit：The retention time of sample each component and integral area are automatically performed by Agilent GC-MS chem workstations in GC spectrograms, phase Content is obtained by area normalization method.
The maximum component retention time of 7# sample GC middle peak of spectrogram areas is 24.491min, 8# sample GC middle peak of spectrograms face The maximum component retention time of product is 28.801min.The retention time of 7# samples and 1- acetic acid hexacosane base ester standard items Retention time (29.764min) differs 5.273min, and gap is in 1min or more.7# samples do not meet necessity of dried cocoon raw silk judgement Condition, therefore, it is determined that being fresh silk raw silk.The 8# samples maximum component of GC middle peak of spectrogram areas and 1- acetic acid hexacosane base esters The retention time of standard items differs 0.963min, meets the necessary condition of dried cocoon raw silk judgement, therefore, it is determined that being dried cocoon raw silk.With Upper judgement result confirms through sample provider (Silk Detection Centre, Zhejiang Exit-Entry Inspection and Quarantine), completely correct.
Confirmatory experiment 4, by 10 different raw silks of fresh cocoons samples of the place of production known to realization and 10 dried cocoon raw silk samples, as 4 the method for embodiment is detected；
The testing result of each dried cocoon raw silk sample is satisfied by the following conditions：When being detected using GC-MS methods, GC middle peak of spectrograms Maximum group of lease making NIST library searching of area is accredited as 1- acetic acid hexacosane base esters.When being detected using GC methods, sample GC spectrums In figure the retention time gap of the maximum component retention time of peak area and 1- acetic acid hexacosane base ester standard items 1min with It is interior.
And 10 raw silks of fresh cocoons samples cannot meet above-mentioned condition；That is, its maximum group of lease making of GC middle peak of spectrogram areas The identification of NIST library searchings is the substance other than 1- acetic acid hexacosane base esters.Peak area is most when being detected with GC methods, in GC figures The retention time of big component is with the retention time gap of 1- acetic acid hexacosane base ester standard items in 1min or more.
Comparative example 1-1, make into " being warming up to 250 DEG C " in the GC-MS analysis conditions in embodiment 1 " be warming up to 400 DEG C ", remaining is equal to embodiment 1.
Use GC-MS methods and GC methods to the 10 raw silks of fresh cocoons samples and 10 dried cocoon raw silk samples in confirmatory experiment 1 respectively It is detected；Acquired results are：When being detected using GC-MS methods, dried cocoon raw silk sample GC maximum group of lease making of middle peak of spectrogram area NIST library searchings are identified, are not belonging to 1- acetic acid hexacosane base esters, therefore can not judge that sample is dried cocoon raw silk or fresh cocoon Raw silk.When being detected using GC methods, the retention time of the maximum component of peak area and 1- acetic acid hexacosane base ester standards in GC figures For the retention time gap of product in 1min or more, flase drop possibility is very high.
Comparative example 1-2, make into " being warming up to 250 DEG C " in the GC-MS analysis conditions in embodiment 1 " be warming up to 150 DEG C ", remaining is equal to embodiment 1.
In this way in confirmatory experiment 1 10 raw silks of fresh cocoons samples and 10 dried cocoon raw silk samples be detected；Institute Obtaining result is：When being detected using GC-MS methods, dried cocoon raw silk sample GC maximum group of lease making NIST library searching of middle peak of spectrogram area Identification, is not belonging to 1- acetic acid hexacosane base esters, can not judge that sample is dried cocoon raw silk or raw silks of fresh cocoons.It is detected using GC methods When, the retention time of the maximum component of peak area and the retention time gap of 1- acetic acid hexacosane base ester standard items are equal in GC figures In 1min or more, flase drop possibility is very high.
Comparative example 1-3, the organic solvent in embodiment 1 is made into dichloromethane or acetone by ethyl alcohol；Remaining is equal to Embodiment 1.
In this way in confirmatory experiment 1 10 raw silks of fresh cocoons samples and 10 dried cocoon raw silk samples be detected；Institute Obtaining result is：When being detected using GC-MS methods, the maximum group of lease making NIST spectrums library inspection of dried cocoon raw silk sample GC middle peak of spectrogram areas Suo Jianding is not admitted to 1- acetic acid hexacosane base esters, can not judge that sample is dried cocoon raw silk or raw silks of fresh cocoons.Use GC methods When detection, the retention time of the maximum component of peak area and the retention time of 1- acetic acid hexacosane base ester standard items are poor in GC figures Away from 1min or more, flase drop possibility is very high.
Although finally, it should also be noted that, listed above is only several specific embodiments of the present invention, On the basis of the present invention, it can also be made some modifications or improvements, this will be apparent to those skilled in the art.Cause This, all deformations for directly being exported or being associated by present disclosure belong to the scope of protection of present invention.

Claims (6)

1. differentiate the method for fresh cocoon/dried cocoon raw silk based on GC or GC-MS technologies, using raw silks of fresh cocoons, dried cocoon raw silk as waiting for test sample Product；It is characterized in that including the following steps：
1), sample to be tested is shredded or crushed, is extracted after organic solvent is added, after the extracting solution concentration of gained, must be extracted Object；
2) organic solvent, is added to re-dissolve extract, filters, gained filtrate is test liquid；
Organic solvent in the step 1) and step 2) is ethyl alcohol, ethyl acetate, n-hexane or petroleum ether；
3) any one following identification method, is selected：
Mode one, GC-MS differential methods：
Test liquid is analyzed with GC-MS combined instruments, to obtain GC the and MS spectrograms of sample to be tested；
Judgement silk is the standard of raw silks of fresh cocoons or dried cocoon raw silk：When the maximum chromatography of peak area in the GC figures of sample to be tested When chemical composition corresponding to peak is 1- acetic acid hexacosane base esters；Judge the sample to be tested for dried cocoon raw silk；Otherwise, it is determined that should Sample to be tested is raw silks of fresh cocoons；
Mode two, GC differential methods：
Test liquid and 1- acetic acid hexacosane base ester standard solutions are analyzed respectively with GC instrument；
Judgement silk is the standard of raw silks of fresh cocoons or dried cocoon raw silk：When the maximum color of GC middle peak of spectrogram areas of sample to be tested When gap absolute value≤1min of retention time and the retention time of 1- acetic acid hexacosane base ester standard items corresponding to spectral peak, Judge the sample to be tested for dried cocoon raw silk；Otherwise, it is determined that sample is raw silks of fresh cocoons；
GC conditions in mode one and mode two are：It is warming up to 200~350 DEG C from initial temperature；Carrier gas be helium, hydrogen or Person's nitrogen, flow rate of carrier gas 1ml/min；Sample size：1μL；
MS analysis conditions are in mode one：Mass spectrographic ion source is the sources EI；Scanning of the mass spectrum ranging from 35~600amu.
2. the method according to claim 1 for differentiating fresh cocoon/dried cocoon raw silk based on GC or GC-MS technologies, it is characterized in that：Institute It states in step 1), the solid-liquid ratio of sample to be tested and organic solvent is 1g/5~200mL.
3. the method according to claim 1 for differentiating fresh cocoon/dried cocoon raw silk based on GC or GC-MS technologies, it is characterized in that：Institute It states in step 1), extracting mode is ultrasonic wave assisted extraction, and extraction time is 2 minutes~10 hours.
4. the method according to claim 1 for differentiating fresh cocoon/dried cocoon raw silk based on GC or GC-MS technologies, it is characterized in that：Institute It states in step 2), the aperture of filtering is 0.22 μm~0.45 μm.
5. the method according to claim 1 for differentiating fresh cocoon/dried cocoon raw silk based on GC or GC-MS technologies, it is characterized in that：
It is with the retention time of the maximum chemical composition of GC middle peak of spectrogram areas and the library inspection of NIST spectrums in the mode one of step 3) Hitch fruit is foundation；It is determined as that the necessary condition of dried cocoon raw silk is：The maximum ingredient of GC middle peak of spectrogram areas of sample is through NIST Library searching, the highest result of matching degree are 1- acetic acid hexacosane base esters；Otherwise, it is determined that sample to be tested is raw silks of fresh cocoons.
6. the method according to claim 1 for differentiating fresh cocoon/dried cocoon raw silk based on GC or GC-MS technologies, it is characterized in that：
In the mode two of step 3), it is determined as that the necessary condition of dried cocoon raw silk is：The GC middle peak of spectrograms area of sample to be tested is maximum Chromatographic peak corresponding to retention time it is close with the retention time of 1- acetic acid hexacosane base ester standard items, judge that this waits for test sample Product are dried cocoon raw silk；Otherwise, it is determined that sample is raw silks of fresh cocoons.
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