CN115047127B - Method for identifying NFC and FC orange juice by utilizing volatile metabonomics technology - Google Patents
Method for identifying NFC and FC orange juice by utilizing volatile metabonomics technology Download PDFInfo
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- 238000000034 method Methods 0.000 title claims abstract description 37
- 238000005516 engineering process Methods 0.000 title claims abstract description 17
- 238000004458 analytical method Methods 0.000 claims abstract description 33
- 239000000203 mixture Substances 0.000 claims abstract description 31
- 238000010238 partial least squares regression Methods 0.000 claims abstract description 20
- 239000003550 marker Substances 0.000 claims abstract description 18
- 238000001319 headspace solid-phase micro-extraction Methods 0.000 claims abstract description 14
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- 238000001819 mass spectrum Methods 0.000 claims abstract description 7
- 238000012549 training Methods 0.000 claims abstract description 4
- 150000001875 compounds Chemical class 0.000 claims description 42
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 claims description 18
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- 239000003039 volatile agent Substances 0.000 claims description 13
- GRWFGVWFFZKLTI-IUCAKERBSA-N (-)-α-pinene Chemical compound CC1=CC[C@@H]2C(C)(C)[C@H]1C2 GRWFGVWFFZKLTI-IUCAKERBSA-N 0.000 claims description 12
- 238000000605 extraction Methods 0.000 claims description 12
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- OBNCKNCVKJNDBV-UHFFFAOYSA-N butanoic acid ethyl ester Natural products CCCC(=O)OCC OBNCKNCVKJNDBV-UHFFFAOYSA-N 0.000 claims description 10
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- HNAGHMKIPMKKBB-UHFFFAOYSA-N 1-benzylpyrrolidine-3-carboxamide Chemical compound C1C(C(=O)N)CCN1CC1=CC=CC=C1 HNAGHMKIPMKKBB-UHFFFAOYSA-N 0.000 claims description 8
- WRYLYDPHFGVWKC-SNVBAGLBSA-N 4-Terpineol Natural products CC(C)[C@]1(O)CCC(C)=CC1 WRYLYDPHFGVWKC-SNVBAGLBSA-N 0.000 claims description 8
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- OVKDFILSBMEKLT-UHFFFAOYSA-N alpha-Terpineol Natural products CC(=C)C1(O)CCC(C)=CC1 OVKDFILSBMEKLT-UHFFFAOYSA-N 0.000 claims description 8
- MVNCAPSFBDBCGF-UHFFFAOYSA-N alpha-pinene Natural products CC1=CCC23C1CC2C3(C)C MVNCAPSFBDBCGF-UHFFFAOYSA-N 0.000 claims description 8
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- PWLNAUNEAKQYLH-UHFFFAOYSA-N butyric acid octyl ester Natural products CCCCCCCCOC(=O)CCC PWLNAUNEAKQYLH-UHFFFAOYSA-N 0.000 claims description 8
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- 229930007744 linalool Natural products 0.000 claims description 8
- UUIQMZJEGPQKFD-UHFFFAOYSA-N n-butyric acid methyl ester Natural products CCCC(=O)OC UUIQMZJEGPQKFD-UHFFFAOYSA-N 0.000 claims description 8
- XAPCMTMQBXLDBB-UHFFFAOYSA-N butanoic acid hexyl ester Natural products CCCCCCOC(=O)CCC XAPCMTMQBXLDBB-UHFFFAOYSA-N 0.000 claims description 7
- DILOFCBIBDMHAY-UHFFFAOYSA-N methyl 2-(3,4-dimethoxyphenyl)acetate Chemical compound COC(=O)CC1=CC=C(OC)C(OC)=C1 DILOFCBIBDMHAY-UHFFFAOYSA-N 0.000 claims description 7
- 238000000513 principal component analysis Methods 0.000 claims description 7
- 238000012216 screening Methods 0.000 claims description 7
- OGLDWXZKYODSOB-SNVBAGLBSA-N alpha-phellandrene Natural products CC(C)[C@H]1CC=C(C)C=C1 OGLDWXZKYODSOB-SNVBAGLBSA-N 0.000 claims description 6
- 239000012159 carrier gas Substances 0.000 claims description 6
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- 229910052734 helium Inorganic materials 0.000 claims description 6
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- CXQXSVUQTKDNFP-UHFFFAOYSA-N octamethyltrisiloxane Chemical compound C[Si](C)(C)O[Si](C)(C)O[Si](C)(C)C CXQXSVUQTKDNFP-UHFFFAOYSA-N 0.000 claims description 6
- 238000004987 plasma desorption mass spectroscopy Methods 0.000 claims description 6
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- HNZUNIKWNYHEJJ-XFXZXTDPSA-N geranylacetone Chemical compound CC(C)=CCC\C(C)=C/CCC(C)=O HNZUNIKWNYHEJJ-XFXZXTDPSA-N 0.000 claims description 5
- VGWUJHSTGYCXQQ-UHFFFAOYSA-N ethyl 3-hydroxyoctanoate Chemical compound CCCCCC(O)CC(=O)OCC VGWUJHSTGYCXQQ-UHFFFAOYSA-N 0.000 claims description 4
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Classifications
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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
- G01N30/02—Column chromatography
- G01N30/86—Signal analysis
-
- 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
- G01N30/62—Detectors specially adapted therefor
- G01N30/72—Mass spectrometers
- G01N30/7206—Mass spectrometers interfaced to gas chromatograph
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- Physics & Mathematics (AREA)
- Health & Medical Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Chemical & Material Sciences (AREA)
- Analytical Chemistry (AREA)
- Biochemistry (AREA)
- General Health & Medical Sciences (AREA)
- General Physics & Mathematics (AREA)
- Immunology (AREA)
- Pathology (AREA)
- Other Investigation Or Analysis Of Materials By Electrical Means (AREA)
Abstract
The invention relates to a method for identifying NFC and FC orange juice, which comprises the following steps of (1) taking NFC orange juice and FC orange juice as training sets, and establishing a partial least squares regression analysis model based on data of a characteristic marker composition; (2) Extracting volatile components from commercial orange juice samples by adopting a headspace solid-phase microextraction technology; (3) Analyzing the extracted volatile components by adopting a gas chromatography-quadrupole/electrostatic field orbitrap high-resolution mass spectrum; (4) Qualitative and quantitative identification is carried out on characteristic markers in the commercial orange juice; (5) And (5) importing the data into a partial least squares regression model to obtain the identification result of the commercial orange juice. The identification method has the advantages of simple operation and accurate identification result, and is not only suitable for the identification of NFC and FC orange juice prepared by adopting the process of the invention, but also suitable for the identification of hot concentrated FC orange juice and NFC orange juice prepared by other sterilization modes.
Description
Technical Field
The invention relates to the field of food detection, in particular to a method for screening characteristic markers for identifying NFC and FC orange juice.
Background
Along with the improvement of the living standard and the enhancement of health consciousness of people, the pure fruit juice is favored by consumers because of the characteristics of nutrition, health and pure nature. Pure juice is classified into two major categories, that is, reconstituted juice (FC) and non-reconstituted juice (not from concentrate, NFC). The national standard GB/T31121-2014 indicates that juice products which are directly prepared by a mechanical method and can be fermented but not fermented are original juice, namely non-recovered juice; the concentrated juice is recovered by adding the same amount of water removed during processing. Among them, NFC orange juice audience scope is wide, and consumer's favorability is high, and industry development is also comparatively rapid. NFC orange juice has increasingly demonstrated competitive advantages over FC orange juice due to its closer quality to the original fruit of sweet oranges. The statistics show that the FC juice sales in the European Union juice market is reduced by 2.6% and the NFC juice sales is increased by 2.1% in 2017-2018. According to the data published by the society of orange juice exporters in Brazil, 7-10 months in 2019, the output of the orange juice of Brazil FC was 293107 tons, and the output of the orange juice of NFC was 474924 tons, wherein the output of the orange juice to China is increased by 109% in a comparable way. Currently, the price of NFC orange juice is about 2-3 times the price of FC orange juice. Under the drive of economic benefits, the low-price FC orange juice is utilized by the illegal vendors to impersonate the high-price NFC orange juice for sale, and the benefits of consumers are greatly damaged. Therefore, the research of the authenticity identification method of the NFC orange juice and the FC orange juice is developed, and the method has important significance for protecting the benefits of consumers and maintaining the market order of the juice.
Regarding authentication of NFC and FC juice, there have been recent researches on the use of techniques such as isotope ratio mass spectrometry, electronic nose, and liquid chromatography-mass spectrometry (LC-MS). The existing identification method mainly depends on non-targeted analysis and chemometric models to realize the distinction of two types of fruit juice. The non-targeted analysis method is not easy to popularize and form standard, and the practical application is difficult. Furthermore, existing methods do not address the specific differences between the two types of juice and the root cause of these differences. As juice processing technology continues to develop, it is still unknown whether previous methods are applicable to current products. Thus, there is a need to explore the differences between NFC and FC juice by means of modern technology and to create the root cause of these differences.
Aiming at the urgency of effectively identifying NFC and FC orange juice requirements and the limitations of the existing methods for identifying NFC and FC orange juice, the method for effectively and simply identifying two types of orange juice is provided and becomes a technical problem to be solved in the field.
Disclosure of Invention
In order to solve the technical problems, the invention comprises the following aspects:
according to a first aspect of the present invention there is provided a signature marker composition for use in the identification of NFC and FC orange juice, the signature marker composition comprising component (a) and/or component (B), the component (a) being a signature volatile compound differing between NFC and FC orange juice, selected from (a-1) 4-terpineol, (a-2) linalool, (a-3) alpha-terpineol, (a-4) gamma-terpinene, (a-5) alpha-terpinene, (a-6) beta-myrcene, (a-7) limonene, (a-8) 3-hydroxyethyl octoate, (a-9) alpha-pinene, (a-10) 1,3, 8-p-menthatriene, (a-11) ethyl octoate, (a-12) methyl butyrate, (a-13) alpha-phellandrene, (a-14) alpha-ylarene, (a-15) p-cymene, (a-16) hexanol, (a-17) alpha-terpinene, (a-18) alpha-cymene, and (B) ethyl butyrate, the two being present in the juice, or both of which are not present in the group of NFC and FC orange juice, the component (B) being a signature volatile compound selected from ethyl butyrate, the two of which is present in the juice, (B-4) two or more of 1-octanol, (B-5) trans-isomenthol, (B-6) limonone, and (B-7) p-mentha-1, 5, 8-ene.
Preferably, the component (A) is selected from three, four, five, six, seven, eight, nine, ten, eleven, twelve, thirteen, fourteen, fifteen, sixteen, seventeen or eighteen of the above-mentioned characteristic volatile compounds (A-1) to (A-18).
Preferably, the component (B) is selected from three, four, five, six or seven of the above-mentioned characteristic volatile compounds (B-1) to (B-7).
More preferably, the component (A) is a composition characterized by volatile compounds (A-1) to (A-3).
More preferably, the component (A) is a composition of the characteristic volatile compounds (A-1) to (A-18), and the component (B) is a composition of the characteristic volatile compounds (B-1) to (B-7).
Preferably, the component (a) is selected from two or more of the volatile compounds based on the orthorhombic partial least squares regression analysis model VIP > 1.4. More preferably, the component (a) is selected from two or more of volatile compounds based on an orthorhombic partial least squares regression analysis model VIP > 1.6. Most preferably, the component (a) is selected from two or more of the volatile compounds based on the orthorhombic partial least squares regression analysis model VIP > 2.
In a second aspect, the present invention provides a method of screening for a marker composition for identification of NFC and FC orange juice characteristics, the method comprising the steps of:
(1) Preparing NFC and FC orange juice samples;
(2) Taking the orange juice sample prepared in the step (1), adding sodium chloride and 2-octanol, and extracting volatile components in the orange juice sample by adopting a headspace solid-phase microextraction technology;
(3) Analyzing the extracted volatile components by adopting a gas chromatograph-quadrupole/electrostatic field orbit trap high-resolution mass spectrum to obtain a mass spectrogram;
(4) Carrying out qualitative and quantitative identification on volatile compounds in orange juice;
(5) And screening characteristic marker compositions of NFC or FC orange juice by adopting qualitative and quantitative results of principal component analysis and orthogonal partial least squares regression analysis of NFC and FC orange juice volatile compounds.
Preferably, the feature marker composition comprises component (A) and/or component (B), wherein the component (A) is a feature volatile compound which is different in NFC and FC orange juice and is selected from two or more of (A-1) 4-terpineol, (A-2) linalool, (A-3) alpha-terpineol, (A-4) gamma-terpinene, (A-5) alpha-terpinene, (A-6) beta-myrcene, (A-7) limonene, (A-8) 3-ethyl hydroxyoctanoate, (A-9) alpha-pinene, (A-10) 1,3, 8-p-menthatriene, (A-11) ethyl octanoate, (A-12) methyl butyrate, (A-13) alpha-phellandrene, (A-14) alpha-ylarene, (A-15) p-cymene, (A-16) hexanol, (A-17) alpha-terpinolene, (A-18) orange-flowering acetone, the component (B) is a characteristic volatile compound which exists only in NFC orange juice and does not exist in FC orange juice, and is selected from (B-1) ethyl butyrate, (B-2) butyl butyrate, (B-3) hexyl butyrate, (B-4) 1-octanol, (B-5) trans-isomenthol, (B-6) limonone, (B-7) p-mentha-1, 5, 8-ene.
Preferably, the component (A) is selected from three, four, five, six, seven, eight, nine, ten, eleven, twelve, thirteen, fourteen, fifteen, sixteen, seventeen or eighteen of the above-mentioned characteristic volatile compounds (A-1) to (A-18).
Preferably, the component (B) is selected from three, four, five, six or seven of the above-mentioned characteristic volatile compounds (B-1) to (B-7).
More preferably, the component (A) is a composition characterized by volatile compounds (A-1) to (A-3).
More preferably, the component (A) is a composition of the characteristic volatile compounds (A-1) to (A-18), and the component (B) is a composition of the characteristic volatile compounds (B-1) to (B-7).
Preferably, the component (a) is selected from two or more of the volatile compounds based on the orthorhombic partial least squares regression analysis model VIP > 1.4. More preferably, the component (a) is selected from two or more of volatile compounds based on an orthorhombic partial least squares regression analysis model VIP > 1.6. Most preferably, the component (a) is selected from two or more of the volatile compounds based on the orthorhombic partial least squares regression analysis model VIP > 2.
Preferably, the sweet orange for preparing NFC and FC orange juice in step (1) is selected from one or more of hamlin, pineapple, terluvista, citrus aurantium and neotame varieties.
Preferably, the preparation method of the NFC orange juice in the step (1) comprises the following steps: selecting fresh and mildew-free orange fruits, washing stains on the surfaces of the orange peels by running water, cutting the orange peels into halves, and squeezing the orange peels to obtain freshly squeezed orange juice; and uniformly dividing the mixture into four parts, and respectively carrying out pasteurization, high-temperature short-time sterilization, ultra-high-temperature instantaneous sterilization and ultra-high pressure sterilization treatment to obtain the NFC orange juice.
Preferably, the preparation method of the FC orange juice in the step (1) comprises the following steps: selecting fresh and mildew-free orange fruits, washing stains on the surfaces of the orange peels by running water, cutting the orange peels into halves, and squeezing the orange peels to obtain freshly squeezed orange juice; pre-sterilizing fresh orange juice at 80deg.C for 10min, and concentrating the preheated orange juice to soluble solids content of 65 ° Brix by thin film evaporation device; adding water removed in the concentration process to restore the content of soluble solids to 11.2 degrees Brix, dividing the obtained compound orange juice into three parts, and respectively carrying out pasteurization, high-temperature short-time sterilization and ultrahigh-temperature instantaneous sterilization to obtain the FC orange juice.
Preferably, 2g of sodium chloride and 60. Mu.L of 2-octanol are added in said step (2).
Preferably, the headspace solid-phase microextraction conditions in step (2) are as follows: balancing at 40deg.C for 20min; inserting a 50/30 mu m DVB/CAR/PDMS extraction head into a sample bottle for adsorption for 15min, and then inserting a GC sample inlet for analysis for 5min; to prevent sample contamination, the extraction head was aged at 280℃for 10min between each two samples tested.
Preferably, the gas chromatography conditions in step (3) are as follows: TG-5MS quartz capillary column (60 m. Times.0.25 mm. Times.0.25 μm); adopting a split-flow sample injection mode, wherein the sample injection ratio is 50:1; heating program: the initial temperature is 40 ℃ and kept for 2.5min; raising the temperature to 70 ℃ at 7 ℃/min, and keeping for 0min; raising the temperature to 120 ℃ at 2 ℃/min, keeping the temperature for 1min, and finally raising the temperature to 280 ℃ at 20 ℃/min, and keeping the temperature for 5min; the carrier gas is high-purity helium; column flow rate: 1.2mL/min.
Preferably, the mass spectrometry conditions in the step (3) are as follows: an electron bombardment (EI) ion source, voltage 70eV; the temperature of the ion source is 250 ℃; the scanning quality range is 35-500m/z; a full scan mode; mass resolution 60000FWHM.
A third aspect of the present invention provides a method of identifying NFC and FC orange juice, the method comprising the steps of:
(1) NFC orange juice and FC orange juice of different varieties and different preparation processes are used as training sets, and a partial least squares regression analysis model is established based on data of the characteristic marker composition;
(2) Taking a commercially available orange juice sample, adding sodium chloride and 2-octanol, and extracting volatile components in the orange juice sample by adopting a headspace solid-phase microextraction technology;
(3) Analyzing the extracted volatile components by adopting a gas chromatograph-quadrupole/electrostatic field orbit trap high-resolution mass spectrum to obtain a mass spectrogram;
(4) Qualitative and quantitative identification is carried out on characteristic markers in the commercial orange juice;
(5) The data is imported into a partial least square regression model to obtain the identification result of the commercial orange juice; the NFC orange juice group is judged as NFC orange juice, and the FC orange juice group is judged as FC orange juice.
Preferably, the feature marker composition comprises component (A) and/or component (B), wherein the component (A) is a feature volatile compound which is different in NFC and FC orange juice and is selected from two or more of (A-1) 4-terpineol, (A-2) linalool, (A-3) alpha-terpineol, (A-4) gamma-terpinene, (A-5) alpha-terpinene, (A-6) beta-myrcene, (A-7) limonene, (A-8) 3-ethyl hydroxyoctanoate, (A-9) alpha-pinene, (A-10) 1,3, 8-p-menthatriene, (A-11) ethyl octanoate, (A-12) methyl butyrate, (A-13) alpha-phellandrene, (A-14) alpha-ylarene, (A-15) p-cymene, (A-16) hexanol, (A-17) alpha-terpinolene, (A-18) orange-flowering acetone, the component (B) is a characteristic volatile compound which exists only in NFC orange juice and does not exist in FC orange juice, and is selected from (B-1) ethyl butyrate, (B-2) butyl butyrate, (B-3) hexyl butyrate, (B-4) 1-octanol, (B-5) trans-isomenthol, (B-6) limonone, (B-7) p-mentha-1, 5, 8-ene.
Preferably, the component (A) is selected from three, four, five, six, seven, eight, nine, ten, eleven, twelve, thirteen, fourteen, fifteen, sixteen, seventeen or eighteen of the above-mentioned characteristic volatile compounds (A-1) to (A-18).
Preferably, the component (B) is selected from three, four, five, six or seven of the above-mentioned characteristic volatile compounds (B-1) to (B-7).
More preferably, the component (A) is a composition characterized by volatile compounds (A-1) to (A-3).
Further preferably, the component (A) is a composition of characteristic volatile compounds (A-1) to (A-18), and the component (B) is a composition of characteristic volatile compounds (B-1) to (B-7).
Preferably, the component (a) is selected from two or more of the volatile compounds based on the orthorhombic partial least squares regression analysis model VIP > 1.4. More preferably, the component (a) is selected from two or more of volatile compounds based on an orthorhombic partial least squares regression analysis model VIP > 1.6. Most preferably, the component (a) is selected from two or more of the volatile compounds based on the orthorhombic partial least squares regression analysis model VIP > 2.
Preferably, the sweet orange for preparing NFC and FC orange juice in step (1) is selected from one or more of hamlin, pineapple, terluvista, citrus aurantium and neotame varieties.
Preferably, the preparation method of the NFC orange juice in the step (1) comprises the following steps: selecting fresh and mildew-free orange fruits, washing stains on the surfaces of the orange peels by running water, cutting the orange peels into halves, and squeezing the orange peels to obtain freshly squeezed orange juice; and uniformly dividing the mixture into four parts, and respectively carrying out pasteurization, high-temperature short-time sterilization, ultra-high-temperature instantaneous sterilization and ultra-high pressure sterilization treatment to obtain the NFC orange juice.
Preferably, the preparation method of the FC orange juice in the step (1) comprises the following steps: selecting fresh and mildew-free orange fruits, washing stains on the surfaces of the orange peels by running water, cutting the orange peels into halves, and squeezing the orange peels to obtain freshly squeezed orange juice; pre-sterilizing fresh orange juice at 80deg.C for 10min, and concentrating the preheated orange juice to soluble solids content of 65 ° Brix by thin film evaporation device; adding water removed in the concentration process to restore the content of soluble solids to 11.2 degrees Brix, dividing the obtained compound orange juice into three parts, and respectively carrying out pasteurization, high-temperature short-time sterilization and ultrahigh-temperature instantaneous sterilization to obtain the FC orange juice.
Preferably, 2g of sodium chloride and 60. Mu.L of 2-octanol are added in said step (2).
Preferably, the headspace solid-phase microextraction conditions in step (2) are as follows: balancing at 40deg.C for 20min; inserting a 50/30 mu m DVB/CAR/PDMS extraction head into a sample bottle for adsorption for 15min, and then inserting a GC sample inlet for analysis for 5min; to prevent sample contamination, the extraction head was aged at 280℃for 10min between each two samples tested.
Preferably, the gas chromatography conditions in step (3) are as follows: TG-5MS quartz capillary column (60 m. Times.0.25 mm. Times.0.25 μm); adopting a split-flow sample injection mode, wherein the sample injection ratio is 50:1; heating program: the initial temperature is 40 ℃ and kept for 2.5min; raising the temperature to 70 ℃ at 7 ℃/min, and keeping for 0min; raising the temperature to 120 ℃ at 2 ℃/min, keeping the temperature for 1min, and finally raising the temperature to 280 ℃ at 20 ℃/min, and keeping the temperature for 5min; the carrier gas is high-purity helium; column flow rate: 1.2mL/min.
Preferably, the mass spectrometry conditions in the step (3) are as follows: an electron bombardment (EI) ion source, voltage 70eV; the temperature of the ion source is 250 ℃; the scanning quality range is 35-500m/z; a full scan mode; mass resolution 60000FWHM.
The invention has the beneficial effects that:
(1) The characteristic markers selected by the invention are derived from orange juice samples of different varieties and different sterilization modes, are obtained by means of gas chromatography-quadrupole/electrostatic field orbitrap high-resolution mass spectrum, and have the advantages of comprehensiveness and high accuracy.
(2) According to the NFC and FC orange juice identification method provided by the invention, the non-targeting and targeting analysis technologies are combined, the characteristic markers are searched from the full spectrogram of the orange juice sample through non-targeting analysis, the characteristic markers are determined more objectively, comprehensively and accurately, and the screened characteristic markers are more convincing. Secondly, establishing an NFC and FC orange juice identification method based on the screened characteristic markers by a targeted analysis technology. The identification method not only solves the problems that the non-targeted analysis method is not easy to popularize, difficult to form a standard and difficult to apply in practice, but also has the advantages of simplicity and convenience and more accurate identification result.
(3) The invention further combines with the orange juice processing technology, explores the forming reason of the characteristic marker, and clarifies that the characteristic marker is not only suitable for identifying the NFC and the FC orange juice prepared by the technology, but also can be used for identifying the thermally concentrated FC orange juice and the NFC orange juice prepared by other sterilization modes.
(4) Ultrahigh pressure sterilization orange juice is one of the high-end NFC orange juice commonly found in the juice market today. According to the invention, based on the existing research, the sweet orange variety and the sterilization process (ultrahigh pressure sterilization technology) for preparing NFC and FC orange juice samples are added, and when the characteristic markers for identifying NFC and FC orange juice are screened, the actual production conditions of NFC and FC orange juice are fully considered, and the commercial process is simulated, so that the obtained characteristic markers are more objective and more representative.
Drawings
Fig. 1 is a processing flow diagram of NFC and FC orange juice (NFC 1: pasteurized NFC orange juice; NFC2: high temperature short time sterilized NFC orange juice; NFC3: ultra high temperature short time sterilized NFC orange juice; NFC4: ultra high pressure sterilized NFC orange juice; FC1: pasteurized FC orange juice; FC2: high temperature short time sterilized FC orange juice; FC3: ultra high temperature short time sterilized FC orange juice);
fig. 2 is a graph of the results of multivariate statistical analysis of NFC and FC orange juice (a: graph of principal component analysis scores of NFC and FC orange juice; B-S: concentration of 18 signature markers in NFC and FC orange juice screened based on VIP values);
FIG. 3 is a graph of the results of identifying commercially available orange juice based on a partial least squares regression analysis model (3A: a partial least squares regression analysis model established based on a self-made sample; 3B: the results of identifying commercially available orange juice).
Detailed Description
The present invention will be further described by way of test examples, but the present invention is not limited to the following test examples.
Test example 1 screening of characteristic markers for identification of NFC and FC orange juice
1. Test method
(1) NFC and FC orange juice samples were prepared. 5 single-variety oranges (Hamlin, pineapple, terluvista, orange, newhol) and 1 mixed-variety oranges (mixing of Hamlin, pineapple, terluvista, orange, newhol and the like in proportion) are selected, and 4 sterilization modes (pasteurization, high-temperature short-time sterilization, ultra-high-temperature instantaneous sterilization and ultra-high-pressure sterilization) are used for preparing orange juice, wherein the specific process is as follows:
NFC orange juice: fresh and mildew-free orange fruits are selected, stains on the surfaces of the orange peels are washed by running water, and juice is extracted after half cutting and peeling are performed, so that freshly extracted orange juice is obtained. Dividing into four parts, and respectively performing three heat sterilization (pasteurization, high-temperature short-time sterilization and ultrahigh-temperature instantaneous sterilization) and one non-heat sterilization (ultrahigh-pressure sterilization) treatments to obtain NFC orange juice.
FC orange juice: fresh and mildew-free orange fruits are selected, stains on the surfaces of the orange peels are washed by running water, and juice is extracted after half cutting and peeling are performed, so that freshly extracted orange juice is obtained. The freshly squeezed orange juice is placed at 80 ℃ for pre-sterilization for 10min, and the preheated orange juice is concentrated to the content of soluble solids of 65 DEG Brix by a thin film evaporation device. Adding water removed in the concentration process to restore the content of soluble solids to 11.2 degrees Brix, dividing the obtained compound orange juice into three parts, and respectively performing three heat sterilization (pasteurization, high-temperature short-time sterilization and ultra-high-temperature instantaneous sterilization) treatments to obtain FC orange juice (the orange processing technological process is referred to in figure 1).
(2) Taking the orange juice sample prepared in the step (1), adding 2g of sodium chloride and 60 mu L of 2-octanol, and extracting volatile components in the orange juice sample by adopting a headspace solid-phase microextraction technology; the volatile components extracted are analyzed by adopting gas chromatography-quadrupole/electrostatic field orbit trap high-resolution mass spectrometry, and the analysis conditions are as follows: the headspace solid-phase microextraction condition is balanced for 20min at 40 ℃; the sample bottle was inserted with a 50/30 μm DVB/CAR/PDMS extraction head for 15min, followed by 5min of analysis by GC injection port. To prevent sample contamination, the extraction head was aged at 280℃for 10min between each two samples tested. The gas chromatography conditions were TG-5MS quartz capillary column (60 m. Times.0.25 mm. Times.0.25 μm); adopting a split-flow sample injection mode, wherein the sample injection ratio is 50:1; heating program: the initial temperature is 40 ℃ and kept for 2.5min; raising the temperature to 70 ℃ at 7 ℃/min, and keeping for 0min; then raising the temperature to 120 ℃ at 2 ℃/min, keeping the temperature for 1min, and finally raising the temperature to 280 ℃ at 20 ℃/min, and keeping the temperature for 5min. The carrier gas is high-purity helium; column flow rate: 1.2mL/min. The mass spectrometry conditions were electron bombardment (EI) ion source, voltage 70eV; the temperature of the ion source is 250 ℃; the scanning quality range is 35-500m/z; a full scan mode; mass resolution 60000FWHM.
(3) And (5) carrying out qualitative and quantitative identification on volatile compounds in the orange juice.
(4) And screening characteristic markers of NFC or FC orange juice by adopting qualitative and quantitative results of principal component analysis and orthogonal partial least squares regression analysis of NFC and FC orange juice volatile compounds.
2. Test results
Based on 5 varieties, 4 processes, 24 NFC and 18 FC orange juice samples were prepared. The quantitative results of volatile compounds of 24 NFC and 18 FC orange juices were analyzed using a principal component analysis, which showed (FIG. 2A) that NFC juice and FC orange juice were able to be completely separated, indicating significant differences in the volatile compound composition of the two types of orange juice. Further using the orthogonal partial least squares regression analysis model, 18 different volatile compounds that contributed significantly to the differentiation of NFC and FC orange juice, including 4-terpineol, linalool, α -terpineol, γ -terpinene, α -terpinene, β -myrcene, limonene, ethyl 3-hydroxyoctoate, α -pinene, 1,3, 8-p-menthatriene, ethyl octoate, methyl butyrate, α -phellandrene, α -ylarene, p-cymene, hexanol, α -terpinolene, nerylacetone were screened based on the variable projection importance analysis Value (VIP) >1.2 (fig. 2B-S). Based on the differences, 7 characteristic volatile compounds were then identified that were present only in NFC orange juice and not in FC orange juice, including ethyl butyrate, butyl butyrate, hexyl butyrate, 1-octanol, trans-isomenthol, limonene, p-mentha-1, 5, 8-ene. In summary, 25 signature markers were identified for NFC and FC orange juice identification (table 1).
Table 1 signature markers for NFC and FC orange juice identification
Test example 2, investigation of causes of Forming characteristic markers of NFC and FC orange juice
1. Test method
(1) Taking orange juice samples of all processing units, wherein the NFC orange juice comprises freshly squeezed orange juice prepared from Hamlin orange, pasteurized NFC orange juice, high-temperature short-time sterilized NFC orange juice, ultrahigh-temperature instantaneous sterilized NFC orange juice and ultrahigh-pressure NFC orange juice; the FC orange juice comprises freshly squeezed orange juice prepared from Hamlin orange, pre-sterilized orange juice, concentrated orange juice, pasteurized FC orange juice, high-temperature short-time sterilized FC orange juice and ultrahigh-temperature instant sterilized FC orange juice.
(2) Adding 2g of sodium chloride and 60 mu L of 2-octanol, and extracting volatile components in an orange juice sample by adopting a headspace solid-phase microextraction technology; the extracted volatile components were analyzed by gas chromatography-quadrupole/electrostatic field orbitrap high resolution mass spectrometry. The headspace solid-phase microextraction condition is balanced for 20min at 40 ℃; the sample bottle was inserted with a 50/30 μm DVB/CAR/PDMS extraction head for 15min, followed by 5min of analysis by GC injection port. To prevent sample contamination, the extraction head was aged at 280℃for 10min between each two samples tested. The gas chromatography conditions were TG-5MS quartz capillary column (60 m. Times.0.25 mm. Times.0.25 μm); adopting a split-flow sample injection mode, wherein the sample injection ratio is 50:1; heating program: the initial temperature is 40 ℃ and kept for 2.5min; raising the temperature to 70 ℃ at 7 ℃/min, and keeping for 0min; then raising the temperature to 120 ℃ at 2 ℃/min, keeping the temperature for 1min, and finally raising the temperature to 280 ℃ at 20 ℃/min, and keeping the temperature for 5min. The carrier gas is high-purity helium; column flow rate: 1.2mL/min. The mass spectrometry conditions were electron bombardment (EI) ion source, voltage 70eV; the temperature of the ion source is 250 ℃; the scanning quality range is 35-500m/z; a full scan mode; mass resolution 60000FWHM.
(3) And (5) carrying out qualitative and quantitative identification on the characteristic markers in the orange juice at different processing stages.
(4) And analyzing the change condition of the characteristic markers in the orange juice at different processing stages by adopting principal component analysis.
2. Test results
Principal component analysis is used to reflect the variation of different compounds during juice processing. The results indicate that the concentration process is a critical processing step that results in differences in NFC and FC orange juice volatile compounds. The concentrations of the 25 signature markers showed significant changes during orange juice processing; after concentration treatment, the signature marker concentration was significantly reduced (table 2).
Table 225 concentration results of signature markers in orange juice at various stages of processing
Table 2 results of concentration of 25 signature markers in orange juice at various stages of processing
| Feature markers | Con | FC1 | FC2 | FC3 |
| Linalool | 16.05±0.61 e | 9.92±0.27 e | 10.21±0.53 e | 12.09±0.65 e |
| 4-terpineol | 3.28±0.06 e | 2.09±0.69 e | 2.93±0.43 e | 2.38±0.5 e |
| Alpha-terpineol | 2.41±0.75 e | 4.46±0.58 e | 5.51±0.36 e | 13.09±0.96 e |
| 1-octanol | 2.1±0.28 e | ND e | ND e | ND e |
| Hexanol | 4.22±0.4 e | ND e | ND e | ND e |
| Trans-isomenthol | ND c | ND c | ND c | ND c |
| Methyl butyrate | 2.16±0.05 f | 2.4±0.03 ef | 2.43±0.11 ef | 2.74±0.14 e |
| Butyric acid ethyl ester | ND f | ND f | ND f | ND f |
| Butyl butyrate | ND e | ND e | ND e | ND e |
| 3-Hydroxyoctanoic acid ethyl ester | 4±0.33 e | 2.67±0.16 f | 2.63±0.19 f | 2.87±0.45 ef |
| Hexyl butyrate | ND d | ND d | ND d | ND d |
| Octanoic acid ethyl ester | ND e | ND e | ND e | ND e |
| Alpha-pinene | 47.4±0.54 e | 26.09±2.13 g | 36.68±2.18 f | 43.74±0.61 ef |
| Beta-myrcene | 317.13±53.84 d | 164.85±12.76 e | 250.86±10.01 d | 280.7±7.73 d |
| Alpha-phellandrene | 16.99±2.19 ef | 10.08±0.52 g | 14.89±0.19 f | 17.08±0.43 e |
| Alpha-terpinenes | 4.53±0.31 b | 5.38±0.26 b | 9.77±0.54 b | 11.49±0.22 b |
| Limonene | 9638.31±342.49 c | 5599.68±182.74 d | 8322.21±267.44 c | 9174.23±174.61 c |
| Gamma-terpinene | 21.41±0.7 g | 19.44±0.75 g | 31.29±0.9 f | 34.7±0.75 f |
| Alpha terpinolene | 3.68±0.28 i | 5.6±0.27 h | 7.71±0.11 g | 11.64±0.27 f |
| 1,3, 8-p-menthatriene | ND e | ND e | ND e | ND e |
| Para-mentha-1, 5, 8-enes | ND d | ND d | ND d | ND d |
| Beta-ylang olefins | 1.39±0.07 d | 1.11±0.07 d | 1.35±0.03 d | 1.38±0.03 d |
| P-cymene | 7.38±0.75 i | 12.13±0.57 h | 15.79±0.18 g | 18.9±0.33 f |
| Lemon ketone | ND d | ND d | ND d | ND d |
| Neryl acetone | 1.78±0.31 d | 2.00±0.07 cd | 2.32±0.07 cd | 3.02±0.15 c |
Note that: (1) Fre: freshly squeezed orange juice, pre: pre-sterilized orange juice, NFC1: pasteurizing NFC orange juice, NFC2: high-temperature short-time sterilization NFC orange juice, NFC3: ultrahigh temperature instant sterilization NFC orange juice, NFC4: ultrahigh pressure sterilization NFC orange juice, FC1: pasteurizing FC orange juice, FC2: high-temperature short-time sterilization FC orange juice, FC3: FC orange juice is instantly sterilized at ultrahigh temperature. (2) Different lowercase letters of the same row represent difference saliency (p < 0.05). ND: not detected.
Test example 3, identification of commercially available orange juice
1. Test method
(1) 14 commercial NFC orange juices and 15 commercial FC orange juices were collected from each of the Beijing grand markets.
(2) Adding 2g of sodium chloride and 60 mu L of 2-octanol, and extracting volatile components in an orange juice sample by adopting a headspace solid-phase microextraction technology; the extracted volatile components were analyzed by gas chromatography-quadrupole/electrostatic field orbitrap high resolution mass spectrometry. The headspace solid-phase microextraction condition is balanced for 20min at 40 ℃; the sample bottle was inserted with a 50/30 μm DVB/CAR/PDMS extraction head for 15min, followed by 5min of analysis by GC injection port. To prevent sample contamination, the extraction head was aged at 280℃for 10min between each two samples tested. The gas chromatography conditions were TG-5MS quartz capillary column (60 m. Times.0.25 mm. Times.0.25 μm); adopting a split-flow sample injection mode, wherein the sample injection ratio is 50:1; heating program: the initial temperature is 40 ℃ and kept for 2.5min; raising the temperature to 70 ℃ at 7 ℃/min, and keeping for 0min; then raising the temperature to 120 ℃ at 2 ℃/min, keeping the temperature for 1min, and finally raising the temperature to 280 ℃ at 20 ℃/min, and keeping the temperature for 5min. The carrier gas is high-purity helium; column flow rate: 1.2mL/min. The mass spectrometry conditions were electron bombardment (EI) ion source, voltage 70eV; the temperature of the ion source is 250 ℃; the scanning quality range is 35-500m/z; a full scan mode; mass resolution 60000FWHM.
(3) And (5) carrying out qualitative and quantitative identification on the characteristic markers in different commercial orange juices.
(4) Qualitative and quantitative data of characteristic markers of 24 NFC and 18 FC orange juices are used for establishing a partial least squares regression analysis model for identifying the commercial NFC and FC orange juices.
2. Test results
Qualitative and quantitative data of the characteristic markers of 24 NFC and 18 FC orange juices prepared by self are taken as training sets, and a least squares regression analysis model is established and can be successfully used for identifying the commercial orange juices (figure 3).
Although specific embodiments of the invention have been described, those skilled in the art will recognize that many changes and modifications may be made thereto without departing from the scope or spirit of the invention. Accordingly, the present invention is intended to embrace all such alterations and modifications that fall within the scope of the appended claims and equivalents thereof.
Claims (8)
1. A signature composition for use in identifying NFC and FC orange juice, characterized in that the signature composition comprises a component a and a component B, the component a being a characteristic volatile compound that differs between NFC and FC orange juice, selected from A1: 4-terpineol, A2: linalool, A3:αterpineol, A4:γterpinene, A5:αterpinene, A6:β-myrcene, A7: limonene, A8: 3-hydroxyoctanoic acid ethyl ester, A9:α-pinene, a10:1,3, 8-p-menthatriene, a11: ethyl octanoate, a12: methyl butyrate, a13:α-cressAlkene, a14:αylanene, a15: p-cymene, a16: hexanol, a17:αterpinolene, a18: two or more of the nerylacetone, the component B is a characteristic volatile compound which exists only in NFC orange juice and does not exist in FC orange juice, and the component B is selected from the group consisting of B1: ethyl butyrate, B2: butyl butyrate, B3: hexyl butyrate, B4: 1-octanol, B5: trans-isomenthol, B6: limonone, B7: two or more of p-mentha-1, 5, 8-ene.
2. The signature marker composition according to claim 1, wherein the component a is selected from three, four, five, six, seven, eight, nine, ten, eleven, twelve, thirteen, fourteen, fifteen, sixteen, seventeen or eighteen of the above-mentioned signature volatile compounds A1 to a 18; the component B is selected from three, four, five, six or seven of the above-mentioned characteristic volatile compounds B1 to B7.
3. The signature marker composition according to claim 1, wherein the component a is a composition of signature volatile compounds A1 to a18 and the component B is a composition of signature volatile compounds B1 to B7.
4. A method of screening for a marker composition for identification of NFC and FC orange juice characteristics, the method comprising the steps of:
(1) Preparing NFC and FC orange juice samples;
(2) Taking the orange juice sample prepared in the step (1), adding sodium chloride and 2-octanol, and extracting volatile components in the orange juice sample by adopting a headspace solid-phase microextraction technology;
(3) Analyzing the extracted volatile components by adopting a gas chromatograph-quadrupole/electrostatic field orbit trap high-resolution mass spectrum to obtain a mass spectrogram;
(4) Carrying out qualitative and quantitative identification on volatile compounds in orange juice;
(5) Screening characteristic marker compositions of NFC or FC orange juice by adopting qualitative and quantitative results of principal component analysis and orthogonal partial least squares regression analysis of NFC and FC orange juice volatile compounds;
the signature marker composition comprises a component a and a component B, the component a being a signature volatile compound that differs between NFC and FC orange juice, selected from A1: 4-terpineol, A2: linalool, A3:αterpineol, A4:γterpinene, A5:αterpinene, A6:β-myrcene, A7: limonene, A8: 3-hydroxyoctanoic acid ethyl ester, A9:α-pinene, a10:1,3, 8-p-menthatriene, a11: ethyl octanoate, a12: methyl butyrate, a13:αphellandrene, a14:αylanene, a15: p-cymene, a16: hexanol, a17:αterpinolene, a18: two or more of the nerylacetone, the component B is a characteristic volatile compound which exists only in NFC orange juice and does not exist in FC orange juice, and the component B is selected from the group consisting of B1: ethyl butyrate, B2: butyl butyrate, B3: hexyl butyrate, B4: 1-octanol, B5: trans-isomenthol, B6: limonone, B7: two or more of p-mentha-1, 5, 8-ene.
5. The method according to claim 4, wherein the headspace solid phase microextraction conditions in step (2) are as follows: balancing at 40deg.C for 20min; inserting a 50/30 mu m DVB/CAR/PDMS extraction head into a sample bottle for adsorption for 15min, and then inserting a GC sample inlet for analysis for 5min; to prevent sample contamination, the extraction head was aged at 280℃for 10min between each two samples tested.
6. The method according to claim 4, wherein the gas chromatography conditions in step (3) are as follows: TG-5MS quartz capillary column; adopting a split-flow sample injection mode, wherein the sample injection ratio is 50:1; heating program: the initial temperature is 40 ℃ and kept for 2.5min; raising the temperature to 70 ℃ at 7 ℃/min, and keeping for 0min; raising the temperature to 120 ℃ at 2 ℃/min, keeping the temperature for 1min, and finally raising the temperature to 280 ℃ at 20 ℃/min, and keeping the temperature for 5min; the carrier gas is high-purity helium; column flow rate: 1.2mL/min.
7. According to claim 4The method is characterized in that the mass spectrum conditions in the step (3) are as follows: electron bombardment EI ion source, voltage 70eV; the temperature of the ion source is 250 ℃; scanning quality range is 35-500m/zThe method comprises the steps of carrying out a first treatment on the surface of the A full scan mode; mass resolution 60000FWHM.
8. A method of identifying NFC and FC orange juice, the method comprising the steps of:
(1) NFC orange juice and FC orange juice of different varieties and different preparation processes are used as training sets, and a partial least squares regression analysis model is established based on data of the characteristic marker composition;
(2) Taking a commercially available orange juice sample, adding sodium chloride and 2-octanol, and extracting volatile components in the orange juice sample by adopting a headspace solid-phase microextraction technology;
(3) Analyzing the extracted volatile components by adopting a gas chromatograph-quadrupole/electrostatic field orbit trap high-resolution mass spectrum to obtain a mass spectrogram;
(4) Qualitative and quantitative identification is carried out on characteristic markers in the commercial orange juice;
(5) The data is imported into a partial least square regression model to obtain the identification result of the commercial orange juice; the NFC orange juice is classified into NFC orange juice groups, and the FC orange juice is classified into FC orange juice groups;
the signature marker composition comprises a component a and a component B, the component a being a signature volatile compound that differs between NFC and FC orange juice, selected from A1: 4-terpineol, A2: linalool, A3:αterpineol, A4:γterpinene, A5:αterpinene, A6:β-myrcene, A7: limonene, A8: 3-hydroxyoctanoic acid ethyl ester, A9:α-pinene, a10:1,3, 8-p-menthatriene, a11: ethyl octanoate, a12: methyl butyrate, a13:αphellandrene, a14:αylanene, a15: p-cymene, a16: hexanol, a17:αterpinolene, a18: two or more of the nerylacetone, the component B is a characteristic volatile compound which exists only in NFC orange juice and does not exist in FC orange juice, and the component B is selected from the group consisting of B1: ethyl butyrate, B2: butyl butyrate, B3: hexyl butyrate, B4: 1-octanol, B5: trans-isomenthol, B6: limonone, B7: two or more of p-mentha-1, 5, 8-ene.
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| CN202210444448.7A CN115047127B (en) | 2022-04-25 | 2022-04-25 | Method for identifying NFC and FC orange juice by utilizing volatile metabonomics technology |
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