CN112578027A - Method for identifying natural dye and synthetic dye and application thereof - Google Patents
Method for identifying natural dye and synthetic dye and application thereof Download PDFInfo
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- 239000000978 natural dye Substances 0.000 title claims abstract description 50
- 229930182559 Natural dye Natural products 0.000 title claims abstract description 45
- 238000000034 method Methods 0.000 title claims abstract description 32
- 239000000979 synthetic dye Substances 0.000 title claims abstract description 30
- 239000000975 dye Substances 0.000 claims abstract description 86
- 239000000203 mixture Substances 0.000 claims abstract description 73
- 238000004458 analytical method Methods 0.000 claims abstract description 26
- 238000012360 testing method Methods 0.000 claims abstract description 15
- 238000005194 fractionation Methods 0.000 claims abstract description 8
- 241000123069 Ocyurus chrysurus Species 0.000 claims abstract 16
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 62
- 229910052799 carbon Inorganic materials 0.000 claims description 62
- 239000000126 substance Substances 0.000 claims description 27
- 238000005103 elemental analyser isotope ratio mass spectroscopy Methods 0.000 claims description 15
- 239000007789 gas Substances 0.000 claims description 11
- 230000000155 isotopic effect Effects 0.000 claims description 8
- WHUUTDBJXJRKMK-VKHMYHEASA-N L-glutamic acid Chemical compound OC(=O)[C@@H](N)CCC(O)=O WHUUTDBJXJRKMK-VKHMYHEASA-N 0.000 claims description 6
- 238000002485 combustion reaction Methods 0.000 claims description 5
- 238000005259 measurement Methods 0.000 claims description 5
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 claims description 4
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 4
- 238000012937 correction Methods 0.000 claims description 4
- 229910052760 oxygen Inorganic materials 0.000 claims description 4
- 239000001301 oxygen Substances 0.000 claims description 4
- 239000000843 powder Substances 0.000 claims description 4
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 claims description 3
- 229910002092 carbon dioxide Inorganic materials 0.000 claims description 3
- 229960002989 glutamic acid Drugs 0.000 claims description 3
- 239000001569 carbon dioxide Substances 0.000 claims description 2
- 239000012159 carrier gas Substances 0.000 claims description 2
- 238000001514 detection method Methods 0.000 claims description 2
- 238000010926 purge Methods 0.000 claims description 2
- 239000012898 sample dilution Substances 0.000 claims description 2
- 238000005507 spraying Methods 0.000 claims description 2
- 230000035945 sensitivity Effects 0.000 abstract description 3
- COHYTHOBJLSHDF-BUHFOSPRSA-N indigo dye Chemical compound N\1C2=CC=CC=C2C(=O)C/1=C1/C(=O)C2=CC=CC=C2N1 COHYTHOBJLSHDF-BUHFOSPRSA-N 0.000 abstract description 2
- COHYTHOBJLSHDF-UHFFFAOYSA-N indigo powder Natural products N1C2=CC=CC=C2C(=O)C1=C1C(=O)C2=CC=CC=C2N1 COHYTHOBJLSHDF-UHFFFAOYSA-N 0.000 abstract description 2
- 239000001044 red dye Substances 0.000 abstract description 2
- 238000011160 research Methods 0.000 abstract description 2
- RGCKGOZRHPZPFP-UHFFFAOYSA-N alizarin Chemical group C1=CC=C2C(=O)C3=C(O)C(O)=CC=C3C(=O)C2=C1 RGCKGOZRHPZPFP-UHFFFAOYSA-N 0.000 description 33
- 241001149655 Rubia tinctorum Species 0.000 description 31
- 241000196324 Embryophyta Species 0.000 description 11
- 239000003208 petroleum Substances 0.000 description 5
- 238000004043 dyeing Methods 0.000 description 4
- 238000005516 engineering process Methods 0.000 description 4
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 3
- 241000282414 Homo sapiens Species 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- 241001103643 Rubia Species 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 230000007613 environmental effect Effects 0.000 description 3
- 238000010672 photosynthesis Methods 0.000 description 3
- 239000004753 textile Substances 0.000 description 3
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 2
- 241001465754 Metazoa Species 0.000 description 2
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 2
- MWPLVEDNUUSJAV-UHFFFAOYSA-N anthracene Chemical compound C1=CC=CC2=CC3=CC=CC=C3C=C21 MWPLVEDNUUSJAV-UHFFFAOYSA-N 0.000 description 2
- 230000000844 anti-bacterial effect Effects 0.000 description 2
- 235000019646 color tone Nutrition 0.000 description 2
- 238000009826 distribution Methods 0.000 description 2
- 239000004744 fabric Substances 0.000 description 2
- 230000036541 health Effects 0.000 description 2
- 239000010985 leather Substances 0.000 description 2
- 230000004060 metabolic process Effects 0.000 description 2
- 230000029553 photosynthesis Effects 0.000 description 2
- FGIUAXJPYTZDNR-UHFFFAOYSA-N potassium nitrate Chemical compound [K+].[O-][N+]([O-])=O FGIUAXJPYTZDNR-UHFFFAOYSA-N 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- 244000025254 Cannabis sativa Species 0.000 description 1
- 235000012766 Cannabis sativa ssp. sativa var. sativa Nutrition 0.000 description 1
- 235000012765 Cannabis sativa ssp. sativa var. spontanea Nutrition 0.000 description 1
- 229920000742 Cotton Polymers 0.000 description 1
- 229920002943 EPDM rubber Polymers 0.000 description 1
- 241001107098 Rubiaceae Species 0.000 description 1
- 229960000583 acetic acid Drugs 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- PYKYMHQGRFAEBM-UHFFFAOYSA-N anthraquinone Natural products CCC(=O)c1c(O)c2C(=O)C3C(C=CC=C3O)C(=O)c2cc1CC(=O)OC PYKYMHQGRFAEBM-UHFFFAOYSA-N 0.000 description 1
- 150000004056 anthraquinones Chemical class 0.000 description 1
- 150000004982 aromatic amines Chemical class 0.000 description 1
- 238000003556 assay Methods 0.000 description 1
- 239000000987 azo dye Substances 0.000 description 1
- 230000006399 behavior Effects 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000003851 biochemical process Effects 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 238000004364 calculation method Methods 0.000 description 1
- 235000009120 camo Nutrition 0.000 description 1
- 230000000711 cancerogenic effect Effects 0.000 description 1
- 238000004177 carbon cycle Methods 0.000 description 1
- 231100000315 carcinogenic Toxicity 0.000 description 1
- 235000005607 chanvre indien Nutrition 0.000 description 1
- 239000011280 coal tar Substances 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 238000007405 data analysis Methods 0.000 description 1
- 239000000835 fiber Substances 0.000 description 1
- 235000013305 food Nutrition 0.000 description 1
- 239000012362 glacial acetic acid Substances 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 239000011487 hemp Substances 0.000 description 1
- 238000001727 in vivo Methods 0.000 description 1
- 238000002347 injection Methods 0.000 description 1
- 239000007924 injection Substances 0.000 description 1
- 229910052500 inorganic mineral Inorganic materials 0.000 description 1
- 238000002307 isotope ratio mass spectrometry Methods 0.000 description 1
- 238000009533 lab test Methods 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 230000002503 metabolic effect Effects 0.000 description 1
- 239000011707 mineral Substances 0.000 description 1
- 235000010755 mineral Nutrition 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 231100000252 nontoxic Toxicity 0.000 description 1
- 230000003000 nontoxic effect Effects 0.000 description 1
- 150000002894 organic compounds Chemical class 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 230000008520 organization Effects 0.000 description 1
- 239000000419 plant extract Substances 0.000 description 1
- 239000002861 polymer material Substances 0.000 description 1
- VKJKEPKFPUWCAS-UHFFFAOYSA-M potassium chlorate Chemical compound [K+].[O-]Cl(=O)=O VKJKEPKFPUWCAS-UHFFFAOYSA-M 0.000 description 1
- 239000004323 potassium nitrate Substances 0.000 description 1
- 235000010333 potassium nitrate Nutrition 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 1
- 235000011121 sodium hydroxide Nutrition 0.000 description 1
- 238000001546 stable isotope ratio mass spectrometry Methods 0.000 description 1
- 230000001954 sterilising effect Effects 0.000 description 1
- 238000004659 sterilization and disinfection Methods 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 230000002195 synergetic effect Effects 0.000 description 1
- 239000002351 wastewater Substances 0.000 description 1
- 210000002268 wool Anatomy 0.000 description 1
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- 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
- G01N30/0005—Field flow fractionation
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- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N1/00—Sampling; Preparing specimens for investigation
- G01N1/28—Preparing specimens for investigation including physical details of (bio-)chemical methods covered elsewhere, e.g. G01N33/50, C12Q
- G01N1/286—Preparing specimens for investigation including physical details of (bio-)chemical methods covered elsewhere, e.g. G01N33/50, C12Q involving mechanical work, e.g. chopping, disintegrating, compacting, homogenising
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- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N27/00—Investigating or analysing materials by the use of electric, electrochemical, or magnetic means
- G01N27/62—Investigating or analysing materials by the use of electric, electrochemical, or magnetic means by investigating the ionisation of gases, e.g. aerosols; by investigating electric discharges, e.g. emission of cathode
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Abstract
The invention belongs to the technical field of dye component research, and provides a method for identifying natural dye and synthetic dye, which uses a stable isotope fractionation method, uses a C stable isotope composition as a test analysis object, identifies whether a dye sample is the natural dye by obtaining the C stable isotope composition in the dye sample and analyzing the difference between the C stable isotope composition in the dye sample and the C stable isotope composition in the corresponding natural dye. The method has the advantages of rapidness, high efficiency, high sensitivity, high precision and the like, and can be used for identifying various source samples such as madder dye, lac-red dye, indigo dye and the like.
Description
Technical Field
The invention relates to the technical field of dyes in general, in particular to a method for identifying natural dyes and synthetic dyes and application thereof.
Background
The dye is a colored organic compound which can dye a dyed object through a medium such as water and an organic solvent and is combined with the medium in a certain way so as to obtain a bright, uniform and firm color of the dyed object, and is mainly used for dyeing various textile fibers and can also be used for dyeing leather, paper, high polymer materials, ink, food and the like. Dyes can be divided into natural and synthetic dyes.
Along with the increasing health care consciousness of people, the public demands for the fabrics for clothes are increasingly rigorous, and green, natural, safe and high-grade products are more favored by people. The natural dye has faint scent and soft color tone, a plurality of dyes have the sterilization effect, and textiles dyed by the natural dye are more and more popular. And plant, animal and mineral resources in the nature are main sources of the natural dye, the natural dye is obtained from the nature and finally returns to the nature, and the natural dye is environment-friendly and conforms to the rule of ecological cycle. Many natural dyes have excellent properties, are non-toxic and harmless, have no pollution to the environment, are antibacterial and mothproof, are convenient to use, are beneficial to storage and the like.
Since the introduction of synthetic dyes into the market, it has been found that there are many problems with synthetic dyes, mainly in the following three areas: 1. the synthetic dye is mainly extracted and produced from petroleum resources, and petroleum energy is seriously consumed in developed automobiles, shipping and the like, so that the synthetic dye taking the petroleum resources as raw materials is seriously threatened; 2. many azo dyes can decompose carcinogenic substances such as aromatic amine and the like in use, and are regarded as forbidden dyes by European organization, so that unknown synthetic dyes exist certainly and can pose potential threats to human health; 3. most synthetic dyes are difficult to degrade, and the dyed waste water and the discarded textiles cannot be biologically or chemically degraded, thereby polluting the environment. Due to the above disadvantages of synthetic dyes, research workers have been working on developing biodegradable, renewable, and health-care natural environmentally-friendly dyes.
Compared with synthetic dyes, natural dyes are natural, have good biodegradability and environmental adaptability, have antibacterial and health-care functions on human bodies, and the dyed fabrics have fresh, natural and elegant color tones and make people feel comfortable, and the advantages are all lacked by the synthetic dyes.
At present, there are counterfeiting behaviors in the market that synthetic dyes are used to impersonate natural dyes, natural dyes are doped with synthetic dyes, etc. to earn high profits, which not only seriously impairs the interests of consumers, but also seriously threatens brand protection of natural dyes. In order to standardize the market order of dye products and protect the legal rights and interests of consumers, a perfect natural dye anti-counterfeiting discrimination system is established, and the source of tracing counterfeit and shoddy dye products is very important.
In order to establish a once-for-all tracing system, the characteristics of the dye itself must be used, the characteristics can reflect the difference conditions of dyes from different sources to a certain extent, a huge database is established by using the characteristics, and the characteristic information of unknown dyes is compared and matched with a database system, so that the authenticity of the unknown dyes is judged.
The stable isotope technology has three important functions of tracing (Tracers), indicating (Indicators) and integrating (Integrators), can effectively explain the difficult problems of 'from where' and the like due to the traceability characteristic of the stable isotope technology, and provides a powerful analysis means for the authenticity identification of the natural dye.
The stable isotope composition of the substance is a natural attribute, and as a natural label of the organism, the stable isotope composition can not only be related to objective conditions such as climate and environment where the organism is located, but also be related to the metabolism type of the organism, is information of atomic level, cannot be changed along with the addition of exogenous chemical additives, and cannot be changed in a thought way. The natural fractionation of stable isotopes in vivo is affected by the same external environmental conditions, such as geographical features and climatic conditions, and different metabolic patterns of animals and plants (the distribution of different isotopes of an element between two or more substances (phases) has different isotope ratios during physical, chemical and biochemical processes due to different isotope masses). The difference of natural abundance of stable isotopes in organisms from different sources is caused, which is the theoretical basis of stable isotope source tracing and technical identification.
Two types of stable isotopes of carbon element occur in nature:12C、13c, the content of the C accounts for 98.89 percent and 1.11 percent respectively; despite the stability of carbon isotopes in the inorganic carbon cycle13C/12The ratio of C varies little but can still be accurately determined by stable Isotope Ratio Mass Spectrometry (IRMS). Plants need to absorb CO from the atmosphere during their growth2Gas, CO of plants and atmosphere during photosynthesis2The carbon isotope composition of the plants is obviously lower than that of atmospheric CO2Carbon isotope composition of (a). The stable carbon isotope distribution rule of the plant is closely related to the photosynthesis metabolism type of the plant and is influenced by other external environmental factors, so that the delta of the plant body13The C value is the result of the synergistic effect of the plant photosynthesis type and the growth environment.
The stable isotope fractionation effect is the basic theoretical basis for evaluating the authenticity of natural dyes. The natural dye is mainly derived from natural organisms, the synthetic dye is mainly derived from petroleum resources, and due to the fractionation effect of isotopes, the isotope composition of natural organisms and petroleum is greatly different, so that the isotope composition of dyes from different sources may also be greatly different, and the authenticity identification of the natural dye can be carried out on the basis of the isotope composition.
Disclosure of Invention
The invention aims to provide a method for identifying natural dye and synthetic dye, which is used for carrying out stable isotope composition analysis on the same sample from other sources based on the stable isotope composition analysis of the natural dye from known sources so as to judge whether the sample is the natural dye, and simultaneously researching the component composition analysis of the same sample from other sources by means of the stable isotope composition analysis of the dyes from two known sources.
The invention adopts the technical scheme that a stable isotope fractionation method is used for identifying natural dye and synthetic dye, C stable isotope composition is used as a test analysis object, and on the basis of determining the known C stable isotope composition of the natural dye, the C stable isotope composition in a dye sample is determined and is compared with the C stable isotope composition of the natural dye for analysis so as to judge whether the dye sample is the natural dye.
Further, the stable isotope fractionation method uses an isotope ratio mass spectrometer EA-IRMS and adopts a rapid combustion principle to perform C stable isotope composition analysis.
Further, the C-stable isotope composition of the above sample is represented by [ delta ]spl-STExpressed as the carbon isotope content ratio R of the sampleSplCarbon isotope content ratio R relative to international standard STSTThe difference in micrometers of (A) is as shown in the following formula (1):
still further, the invention uses the isotope ratio mass spectrometer EA-IRMS to test and analyze the carbon stable isotope composition delta of the samplespl-STThe carbon isotope content ratio of the sample is measured by the amesdial difference of the carbon isotope content ratio of the working standard gas WG, and the measured value is deltaspl-WGRepresents; simultaneously unifying the carbon isotope content ratio of the working standard gas WG to be relativeThousandths of the carbon isotope content ratio in the international standard ST, the unity being δWG-STRepresents; the carbon stable isotopic composition of the sample δspl-STThe formula (2) is shown as follows:
δspl-ST=δspl-WG+δWG-ST+δspl-WG×δWG-ST×10-3… … … type (2)
Wherein deltaWG-STThe standard substance Std with known carbon isotope composition is adopted for calibration, as shown in formula (3):
delta in the formulastd-STThe thousandths of the ratio of the carbon isotope contents of the standard substance Std of known isotope composition to the ratio of the carbon isotope contents of the international standard ST, δstd-WGThe thousandths of the ratio of the carbon isotope content of Std, a standard substance of known isotope composition, relative to the ratio of the carbon isotope content of ST, an international standard.
Still further, the standard substance Std is USGS40, namely L-glutamic acid, delta thereof13CVPDBSetting the value to be-26.39 per mill; the working standard gas WG adopts carbon dioxide.
Still further, in order to eliminate measurement errors caused by time drift of the EA-IRMS, the invention inserts a standard substance Std with known isotope composition into a sample analysis sequence for calibration, and the carbon stable isotope composition of the sample after time drift correction is usedExpressed, the correction formula is shown in formula (4):
wherein the content of the first and second substances,is a measure of the isotopic composition of the sample;the calibration value of the carbon isotope content ratio of the standard substance Std with known isotope composition relative to the carbon isotope content ratio thousandth difference of the international standard ST,is a measure of the carbon isotope content ratio of Std, a standard substance of known isotope composition, relative to the carbon isotope content ratio of ST, an international standard.
The natural madder dye is one of the earliest plant dyes in ancient literature records in China, is also the earliest red plant dye used by human beings, and is widely applied to dyeing of wool, cotton, hemp, leather and silk. The natural madder dye is a natural plant extract extracted from the root of madder (botanical classification: rubiaceae, rubia), and the main dyeing component of the natural madder dye is alizarin (also called alizarin), and the physical characteristics of the natural madder dye are as follows:
the name of Chinese: alizarin
The name of English: alizarin
The alternative name is as follows: 1, 2-dihydroxy-9, 10-anthraquinones
The chemical formula is as follows: c14H8O4
Molecular weight: 240.23
Melting point: 289-290 deg.C
Boiling point: 430 deg.C (806 deg.F; 703K)
Solubility: easily soluble in hot methanol and diethyl ether at 25 deg.C, soluble in benzene, glacial acetic acid, and pyridine, and slightly insoluble in water
Density: 1.540g/cm3
Appearance: orange crystal or brown yellow powder
Structure of alizarin:
the synthesized alizarin has the same molecular structure, but is different from natural alizarin dye, and belongs to chemical industry and finished products of non-natural sources. In 1868, German chemists Graebe (Carl Graebe) and Liberman (Carl Liebermann) used anthracene extracted from coal tar as a raw material to prepare anthraquinone, and then sulfonated and alkali-melted to obtain the synthetic alizarin. It is industrially prepared by heating anthraquinone-beta-sulfonic acid, caustic soda and potassium chlorate or potassium nitrate together.
Based on different sources of carbon elements in natural madder dye and synthetic madder dye and difference of respective carbon isotope compositions, the respective delta of the natural madder dye and the synthetic madder dye are subjected to respective delta by means of an EA-IRMS (ethylene-propylene-diene monomer) online system13And C, measuring, selecting a representative sample, and establishing a proper model to finally distinguish the difference of the two.
On the basis of the method, the natural madder dye and the synthetic madder dye are respectively used as two test samples, and are dried, ground into powder, weighed and wrapped by a tin bag to be used as a test sample for carbon stable isotope analysis; the identification method provided by the invention is used for respectively testing the carbon stable isotope composition of the obtained natural dye and the madder dye to be analyzed, and the carbon stable isotope composition of the madder dye to be analyzed is comparedAnd of natural dyesTo determine whether the madder dye to be analyzed is a natural madder dye.
The stable isotope composition of the main component alizarin of the natural alizarin dye is relatively stable, and an interval range of the stable isotope composition of the alizarin in the statistical sense can be obtained through experimental tests and data statistics, the alizarin dye to be analyzed in the interval can be identified as the natural alizarin dye, and a sample of the stable isotope composition outside the interval range is the synthetic alizarin dye or a mixture of the synthetic alizarin dye and the natural alizarin dye.
The invention also provides a method for determining the source of the commercial madder dye, and the method for identifying the natural dye and the synthetic dye is used for respectively testing the carbon stable isotope compositions of the natural dye and the synthetic madderAndthen testing the carbon stable isotope composition of the obtained commercial madder dyeAnd finally, calculating the respective proportions of the natural madder dye and the synthetic madder dye in the commercial madder dye according to the isotope mass conservation principle.
Further, when the differential analysis is carried out by using an isotope ratio mass spectrometer EA-IRMS, the set working parameters are as follows: flow rate of carrier gas: 100 ml/min; purging flow rate of the sample inlet; 200 ml/min; oxygen flow rate: 250 ml/min; oxygen spraying time: 3 seconds; sample introduction delay: 10 seconds; temperature of the combustion furnace: 980 ℃; the GC temperature was 55 ℃; reference gas signal: CO 22: 6V; sample dilution: CO 22: 0; and (3) starting and stopping peak detection: CO 22: 0.2/0.4 mV/s; background value: BGD 44: 10 mV; background value deduction method: calc Mean BGD, i.e., the average value of BGD signals 5 seconds before the peak is taken; analysis duration: sample introduction is carried out for 1 time, and delta is finished within 6min13And C, analyzing.
The element analyzer and isotope ratio mass spectrometer combined system, namely an EA-IRMS online system, can accurately analyze the composition of the carbon (C) stable isotope in the dye sample only by microgram-grade (microgram) sample volume, further evaluate the difference of dyes from different sources (natural and synthetic) on the composition of the C stable isotope, and estimate the proportion of natural and synthetic components in commercial dyes.
The method of the present invention can be used to determine the delta by analyzing various dye samples13C identifying natural and synthetic dyesThe method has the advantages of rapidness, high efficiency, high sensitivity, high precision and the like. Meanwhile, the authenticity of the natural madder dye is quickly discriminated by analyzing the delta 13C of the madder dyes from different sources and utilizing a carbon (13C) stable isotope technology. Therefore, the stable isotope composition analysis method provides a powerful criterion for the authenticity identification of the natural dye.
Detailed Description
The present invention will be described in further detail below with reference to specific embodiments in order to make the present invention better understood by those skilled in the art.
Example 1
A method for identifying a natural madder dye and a synthetic madder dye, comprising the steps of:
experimental part:
sample preparation: the madder dye sample was dried, ground into a powder, and weighed to about 100 μ g, and tightly wrapped with a tin sac for carbon (C) stable isotope analysis.
The instrument parameters are as follows: the experimental EA-IRMS online system mainly comprises 3 parts, namely an EA IsoLink element analysis unit, a ConFlo IV continuous flow interface device and a Delta V advanced stable isotope ratio mass spectrometer, which are all produced by Sammerfoil corporation. Applying fast combustion principle to dye sample delta13C, analysis was performed, and the main parameters are listed in Table 1.
TABLE 1 determination of dye sample delta based on fast burning EA-IRMS13C main parameters
And (3) data analysis:
the carbon (C) stable isotope composition is expressed in thousandths per thousand relative to the international standard (RST, e.g., VPDB) and is denoted by the δ symbol:
by EA-IRMSFor machine system analysis, the C stable isotope composition of the sample is determined by using a standard gas (WG, such as CO) relative to the working standard gas2) The assay was performed, with a uniform traceability to international Standards (ST): the carbon stable isotopic composition of the sample δspl-STThe formula (2) is shown as follows:
δspl-ST=δspl-WG+δWG-ST+δspl-WG×δWG-ST×10-3… … … type (2)
Working standard gas (WG) is prepared from standard substance (Std, such as USGS40 delta of L-glutamic acid) with known isotope composition13CVPDBGiven value of-26.39 ‰) is calibrated as shown in equation (3):
to eliminate measurement errors caused by the time drift of the EA-IRMS online system, a standard substance (Std) of known isotopic composition was inserted in the sample analysis sequence for further calibration, as shown in equation (4):
is a measure of the isotopic composition of the sample;the calibration value of the carbon isotope content ratio of the standard substance Std with known isotope composition relative to the carbon isotope content ratio thousandth difference of the international standard ST,is a measure of the carbon isotope content ratio of Std, a standard substance of known isotope composition, relative to the carbon isotope content ratio of ST, an international standard.
In this example, known natural madder dye and industrial synthetic madder dye were used as control samples to determine the respective delta13C, carrying out respective stable isotope composition analysis, and carrying out delta analysis on the purchased madder dye according to the same method13C, measuring and analyzing to obtain the ratio of natural components to synthetic components in the mixture.
Table 2 shows the natural and synthetic rubia dye delta13Significant variability of C (p)<0.05) and further analyzing the proportion of natural and synthetic components in the commercial madder dye according to the isotope mass conservation principle. The natural component of the madder dye of the experimental commodity accounts for 76.2 percent, and the synthetic component accounts for 23.8 percent.
TABLE 2 Delta of rubia dye from different sources13C measurement and component calculation
Note: at least 3 replicates per dye sample, delta13C is expressed as mean. + -. 1 SD.
It can be seen that carbon (A), (B) is used13C) The stable isotope technology can quickly discriminate the authenticity of the natural madder dye.
The invention also analyzes the delta of the lac red dye and the indigo dye by utilizing a Saimer Fei EA-IRMS online system13C, testing samples of unknown sources based on the data of the natural dyes and the industrial synthetic dyes to analyze the natural dyes and the synthetic dye components and judge whether the natural dyes or the industrial synthetic dyes are pure natural dyes or pure industrial synthetic dyes
The invention uses the EA-IRMS online system for testing, analyzing and identifying, and has the characteristics of high analyzing speed, high sensitivity, high precision and the like. The delta can be completed within 6min after 1 sample injection13And C, analyzing. The amount of each sample was only 100. mu.g, giving. delta13The C measurement precision is better than 0.2 per mill, and the laboratory test requirements are met.
Having described embodiments of the present invention, the foregoing description is intended to be exemplary, not exhaustive, and not limited to the embodiments disclosed. Many modifications and variations will be apparent to those of ordinary skill in the art without departing from the scope and spirit of the described embodiments. Therefore, the protection scope of the present invention shall be subject to the protection scope of the claims.
Claims (9)
1. A method for discriminating natural dye from synthetic dye, characterized in that it uses stable isotope fractionation method, using C stable isotope composition as test analysis object, on the basis of determining C stable isotope composition known as natural dye, by determining C stable isotope composition in dye sample and comparing it with C stable isotope composition of natural dye to analyze, to determine whether dye sample is natural dye.
2. The method for distinguishing natural and synthetic dyes according to claim 1 wherein the stable isotope fractionation method uses an isotope ratio mass spectrometer EA-IRMS for C-stable isotope composition analysis using the fast combustion principle.
3. The method of identifying natural and synthetic dyes of claim 2 wherein the C-stable isotopic composition of said sample is δspl-STExpressed as the carbon isotope content ratio R of the sampleSplCarbon isotope content ratio R relative to international standard STSTThe difference in micrometers of (A) is as shown in the following formula (1):
4. the method of identifying natural dyes and synthetic dyes according to claim 3,
carbon stable isotope composition delta of sample when tested and analyzed using isotope ratio mass spectrometer EA-IRMSspl-STBy usingThe thousandth difference of the carbon isotope content ratio of the sample relative to the carbon isotope content ratio of the working standard gas WG is measured, and the measured value is deltaspl-WGRepresents; simultaneously unifying the carbon isotope content ratio of the working standard gas WG to the thousandth difference of the carbon isotope content ratio relative to the international standard ST, and unifying the value by deltaWG-STRepresents; the carbon stable isotopic composition of the sample δspl-STThe formula (2) is shown as follows:
δspl-ST=δspl-WG+δWG-ST+δspl-WG×δWG-ST×10-3..
Wherein deltaWG-STThe standard substance Std with known carbon isotope composition is adopted for calibration, as shown in formula (3):
delta in the formulastd-STThe thousandths of the ratio of the carbon isotope contents of the standard substance Std of known isotope composition to the ratio of the carbon isotope contents of the international standard ST, δstd-WGThe thousandths of the ratio of the carbon isotope content of Std, a standard substance of known isotope composition, relative to the ratio of the carbon isotope content of ST, an international standard.
5. The method for discriminating natural dyes from synthetic dyes according to claim 4 wherein the standard substance Std is USGS40, L-glutamic acid, delta thereof13CVPDBSetting the value to be-26.39 per mill; the working standard gas WG adopts carbon dioxide.
6. The method of identifying natural dyes and synthetic dyes according to claim 4,
in order to eliminate measurement errors caused by time drift of the EA-IRMS, a standard substance Std with known isotope composition is inserted into a sample analysis sequence for calibration, and the carbon stable isotope composition of the sample after time drift correction is usedExpressed, the correction formula is shown in formula (4):
wherein the content of the first and second substances,is a measure of the isotopic composition of the sample;the calibration value of the carbon isotope content ratio of the standard substance Std with known isotope composition relative to the carbon isotope content ratio thousandth difference of the international standard ST,is a measure of the carbon isotope content ratio of Std, a standard substance of known isotope composition, relative to the carbon isotope content ratio of ST, an international standard.
7. A method for identifying natural madder dye and synthetic madder dye is characterized in that the natural madder dye and the madder dye to be analyzed are respectively used as two test samples, are dried and then ground into powder, and are weighed and then wrapped by a tin bag to be used as test samples for carbon stable isotope analysis; the carbon stable isotope compositions of the natural dye obtained and of the madder dye to be analyzed are tested separately using the method as claimed in any of claims 1 to 6 by comparing the compositions of the madder dyes to be analyzedAnd of natural dyesTo determine whether the madder dye to be analyzed is a natural madder dye.
8. A method for determining the origin of a commercial madder dye, characterized in that the carbon stable isotope compositions of the natural dye obtained and of the synthetic madder are measured separately by the method according to any one of claims 1 to 6Andthen testing the carbon stable isotope composition of the obtained commercial madder dyeAnd finally, calculating the respective proportions of the natural madder dye and the synthetic madder dye in the commercial madder dye according to the isotope mass conservation principle.
9. The method for determining the source of madder dye available from commercial industries according to claim 8, wherein the operating parameters of said EA-IRMS are as follows: flow rate of carrier gas: 100 ml/min; purging flow rate of the sample inlet; 200 ml/min; oxygen flow rate: 250 ml/min; oxygen spraying time: 3 seconds; sample introduction delay: 10 seconds; temperature of the combustion furnace: 980 ℃; the GC temperature was 55 ℃; reference gas signal: CO 22: 6V; sample dilution: CO 22: 0; and (3) starting and stopping peak detection: CO 22: 0.2/0.4 mV/s; background value: BGD 44: 10 mV; background value deduction method: calc Mean BGD, i.e., the average value of BGD signals 5 seconds before the peak is taken; analysis duration: sample introduction is carried out for 1 time, and delta is finished within 6min13And C, analyzing.
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