阅读说明：本技术 一种利用精油降低烤黄花鱼中杂环胺含量的方法 (Method for reducing heterocyclic amine content in baked yellow croaker by using essential oil ) 是由 张思敏 王睿纯 王新艳 林松毅 姜鹏飞 于 2021-09-22 设计创作，主要内容包括：本发明公开了一种利用精油降低烤黄花鱼中杂环胺含量的方法,属于食品加工技术领域。本发明所述的方法包括如下步骤：(1)将精油与食用油混合均匀,制成精油混合油,备用；其中,精油为牛至精油、丁香精油中的一种；(2)将鱼糜和步骤(1)所述的精油混合油混合均匀,放入模具加工成鱼制品；(3)将步骤(2)的鱼制品进行熟化,得到成品鱼制品。本发明采用的精油均为天然提取物,对人体无任何毒副作用,完全符合天然、绿色、健康的发展趋势。本发明解决了现有技术中烤黄花鱼中杂环胺含量高等技术问题,具有原料廉价易得、工艺条件易于控制、对于杂环胺的抑制效果显著等优点,使烤鱼制品食用更安全,可应用于大规模生产。(The invention discloses a method for reducing heterocyclic amine content in grilled yellow croaker by using essential oil, and belongs to the technical field of food processing. The method comprises the following steps: (1) mixing the essential oil and edible oil uniformly to obtain essential oil mixed oil for later use; wherein the essential oil is one of oregano essential oil and clove essential oil; (2) uniformly mixing minced fillet and the essential oil mixed oil in the step (1), and putting the mixture into a mould to process into a fish product; (3) and (3) curing the fish product obtained in the step (2) to obtain a finished fish product. The essential oil adopted by the invention is a natural extract, has no toxic or side effect on human body, and completely accords with the development trend of nature, green and health. The invention solves the technical problems of high heterocyclic amine content in the grilled yellow croaker in the prior art, has the advantages of cheap and easily-obtained raw materials, easily-controlled process conditions, obvious inhibition effect on the heterocyclic amine and the like, ensures that grilled fish products are safer to eat, and can be applied to large-scale production.)

1. A method for reducing the content of heterocyclic amines in grilled yellow croakers by using essential oil is characterized by comprising the following steps:

(1) mixing the essential oil and edible oil uniformly to obtain essential oil mixed oil for later use; wherein the essential oil is one of oregano essential oil and clove essential oil;

(2) uniformly mixing minced fillet and the essential oil mixed oil in the step (1), and putting the mixture into a mould to process into a fish product;

(3) and (3) curing the fish product obtained in the step (2) to obtain a finished fish product.

2. The method according to claim 1, wherein the essential oil added in the step (1) is 4 to 20 wt% of the essential oil mixture oil.

3. The method according to claim 1 or 2, wherein the edible oil of step (1) comprises soybean oil, sunflower oil, rapeseed oil, peanut oil.

4. The method according to any one of claims 1 to 3, wherein the minced fillet in the step (2) comprises minced yellow croaker fillet, minced mackerel fillet and minced mateiid fillet.

5. The method according to any one of claims 1 to 4, wherein the mass ratio of the essential oil to the surimi in the step (2) is 0.16 to 0.8: 100.

6. the method according to any one of claims 1 to 5, wherein the curing in the step (3) comprises baking, and specifically, the baking temperature is 230 to 250 ℃, the humidity is 45 to 55%, and the baking time is 15 to 25min per side and is 30 to 50min in total.

7. The method according to any one of claims 1 to 6, wherein the heterocyclic amine comprises 2-amino-3-methylimidazo [4,5-f ] quinoline, 2-amino-3-methylimidazo [4,5-f ] quinoxaline, 2-amino-3, 4-dimethylimidazo [4,5-f ] quinoline, 2-amino-3, 8-dimethylimidazo [4,5-f ] quinoxaline, 2-amino-3, 4, 8-trimethyl-3H-imidazo [4,5-f ] quinoxaline, 2-amino-3, 7, 8-trimethylimidazo [4,5-f ] quinoline, 2-amino-1-methyl-6-phenylimidazo [4, 5-b ] pyridine, 3-amino-1, 4-dimethyl-5H pyrido [4, 3-b ] indole, 3-amino-1-methyl-5H-pyrido [4, 3-b ] indole, 2-amino-9H-pyrido [2, 3-6] indole, 2-amino-3-methyl-9H-pyrido [2, 3-6] indole, 9H-pyrido [3,4-b ] indole, 1-methyl-9H-pyrido [3,4-b ] indole.

8. A method according to any one of claims 1 to 7, wherein the fish product of step (2) comprises a fish cake.

9. A finished fish product prepared by the method of claims 1-8.

10. Use of the method according to claims 1 to 8 in the field of food processing.

Technical Field

The invention relates to a method for reducing heterocyclic amine content in grilled yellow croaker by using essential oil, belonging to the technical field of food processing.

Background

Heterocyclic amine is a compound with a heterocyclic aromatic structure and composed of carbon, hydrogen and nitrogen atoms, and is a carcinogenic mutation-causing compound formed by further reacting Maillard reaction products (Amadori compound, Strecker degraded aldehyde, pyridine and pyrazine) of free amino acid, creatine and reducing sugar in the high-temperature heat processing process of high-protein food such as fish and meat. Scientists have now isolated over 30 heterocyclic amines from high temperature cooked foods, mainly including the two main classes of aminoimidazole azaarenes and aminocarbolines. In the society today, as people have increasingly higher health requirements, the formation and control of heterocyclic amines in foods has become a current research hotspot.

The yellow croaker is mainly distributed in sea areas such as the east sea, the yellow sea and the Bohai sea in China, is an important economic fish in China, has tender meat quality and rich nutrition, and is a common food on a dining table of common people in China. Frying, frying and roasting are common processing and cooking modes of yellow croakers, and commercially available yellow croaker finished products such as yellow croaker cans, dried yellow croakers and the like are all finished products prepared by thermally processing fish. Because the yellow croaker is rich in amino acid and protein, heterocyclic amines are easily generated in the thermal processing process. In view of the potential safety hazard, the key technical problem to be solved urgently is to develop a natural, safe and healthy method for effectively reducing the content of heterocyclic amine in the process of roasting the yellow croakers.

Liliana Rounds et al (centralized-dependent inhibition of Escherichia coli O157: H7and heterocyclic amines in hydrated ground meat pads by applets and olive extracts, on powder and pork bulb oil) disclose the use of essential oils for the preparation of beef patties to reduce the heterocyclic amine content, but belong to white meat, beef to red meat, differ in the amino acid content and type between them, differ in the amount and type of heterocyclic amine produced, and also differ in the inhibitory effect of the essential oils on the heterocyclic amines in them; there are also some documents (Association of the antibiotic proteins on the formation of heterocyclic amines in meat) disclosing the use of certain oregano extracts to inhibit the production of heterocyclic amines in beef, but the inhibitory effect is not ideal because the purity of the active ingredients contained in the extract is not high.

So far, no research on the formation and control of heterocyclic amine in the roasting process of yellow croakers exists, and reports on the utilization of essential oil to reduce the content of the heterocyclic amine in fish and meat products are not found. Therefore, how to reduce the content of heterocyclic amine in the heat processing process of the yellow croakers becomes one of the hot focuses of the food safety field.

Disclosure of Invention

[ problem ] to

Heterocyclic amine is formed in the roasting process of the yellow croakers; the existence of heterocyclic amine is a great hidden trouble of food safety. However, at present, the research on the formation and control of heterocyclic amine in the roasting process of the yellow croakers does not exist.

[ solution ]

In order to solve the problems, the invention provides a method for reducing the content of heterocyclic amine in the roasted yellow croaker based on oregano essential oil or clove essential oil, and provides a new way for the quality safety of aquatic products, particularly the control of the content of the heterocyclic amine in the roasted fish meat products.

The first object of the present invention is to provide a method for reducing the content of heterocyclic amines in baked yellow croakers by using essential oil, comprising the steps of:

(1) mixing the essential oil and edible oil uniformly to obtain essential oil mixed oil for later use; wherein the essential oil is one of oregano essential oil and clove essential oil;

(2) uniformly mixing minced fillet and the essential oil mixed oil in the step (1), and putting the mixture into a mould to process into a fish product;

(3) and (3) curing the fish product obtained in the step (2) to obtain a finished fish product.

In one embodiment of the invention, the heterocyclic amine comprises IQ (2-amino-3-methylimidazo [4,5-f ] quinoline), IQx (2-amino-3-methylimidazo [4,5-f ] quinoxaline), MeIQ (2-amino-3, 4-dimethylimidazo [4,5-f ] quinoline), 8-MeIQx (2-amino-3, 8-dimethylimidazo [4,5-f ] quinoxaline), 4,8-DiMeIQx (2-amino-3, 4, 8-trimethyl-3H-imidazo [4,5-f ] quinoxaline), 7,8-DiMeIQx (2-amino-3, 7, 8-trimethylimidazo [4,5-f ] quinoline), PhIP (2-amino-1-methyl-6-phenylimidazo [4, 5-b ] pyridine), Trp-P-1 (3-amino-1, 4-dimethyl-5H-pyrido [4, 3-b ] indole), Trp-P-2 (3-amino-1-methyl-5H-pyrido [4, 3-b ] indole), AaC (2-amino-9H-pyrido [2, 3-6] indole), MeAaC (2-amino-3-methyl-9H-pyrido [2, 3-6] indole), Norharman (9H-pyrido [3,4-b ] indole), and Harman (1-methyl-9H-pyrido [3,4-b ] indole).

In one embodiment of the invention, the essential oil added in the step (1) is 4 to 20 wt% of the essential oil mixed oil.

In one embodiment of the present invention, the edible oil in step (1) comprises soybean oil, sunflower oil, rapeseed oil, peanut oil, and the like.

In one embodiment of the invention, the minced fillet in the step (2) comprises minced yellow croaker, minced mackerel, minced friendship and the like.

In one embodiment of the invention, the mass ratio of the essential oil mixed oil to the surimi in the step (2) is 4: 100, respectively; the mass ratio of the essential oil to the minced fillet is 0.16-0.8: 100.

in one embodiment of the invention, the fish product of step (2) comprises fish cake, the size of the fish cake is phi 9cm x 1 cm.

In an embodiment of the invention, the curing in the step (3) includes baking, specifically, the baking temperature is 230 to 250 ℃, the humidity is 45 to 55%, the baking time is 15 to 25min per side for 30 to 50min, more preferably the baking temperature is 240 ℃, the humidity is 50%, and the baking time is 20min per side for 40 min.

The second object of the invention is the finished fish product obtained by the method of the invention.

A third object of the invention is the use of the method according to the invention in the field of food processing.

[ advantageous effects ]

(1) The essential oil of origanum vulgaris adopted by the invention is volatile oil extracted from origanum vulgaris of origanum of Labiatae, is yellowish red or brownish red essential oil, has spicy aromatic smell of thyme, and has carvacrol-like main components; thymol; for aragonite hydrocarbons; a-caryophyllene and other more than 30 polyphenol compounds and organic compounds, and the oregano essential oil is a safe, efficient and green additive with high pure natural active ingredients; the flos Caryophylli essential oil is volatile aromatic substance extracted from flos Caryophylli of Syzygium of Myrtaceae, wherein the components are eugenol, acetyl eugenol, and dianthus caryophyllus phenol substances. The phenols in the two essential oils are both natural and safe plant sources, and have good free radical scavenging ability.

(2) The essential oil added in the invention is a natural plant extract, has no toxic or side effect on human health, completely accords with the development trend of nature, green and health, and has cheap and easily obtained raw materials.

(3) The processing and baking process conditions of the baked yellow croaker in the method are easy to achieve, and the production and production cost of the product is low.

(4) The method can effectively reduce the content of the heterocyclic amine in the baked yellow croaker, has the inhibition rate of the heterocyclic amine in the yellow croaker of not less than 97.74 percent, has obvious inhibition effect on the heterocyclic amine in the baked yellow croaker, and is suitable for large-scale production. In addition, the degree of fatylation in the finished fish product obtained by the method is between 0.8 and 1.25mg MDA/kg, and the content of carbonyl is between 0.1 and 0.27nmol/mg protein.

Drawings

FIG. 1 is a heterocyclic amine test spectrum of yellow croaker patties obtained in example 1; wherein a is a liquid phase spectrum of the sample in the example 1, and b, c and d are respectively quantitative analysis of Norharman, Harman and PhIP in the sample in the example 1.

FIG. 2 is a heterocyclic amine test spectrum of yellow croaker patties measured in example 2; wherein a is a liquid phase spectrum of the sample of example 2 and b is a quantitative analysis of Norharman in the sample of example 2.

FIG. 3 is a heterocyclic amine test spectrum of yellow croaker patties obtained in example 3; wherein a is a liquid phase spectrum of the sample in the example 3, and b, c and d are respectively quantitative analysis of Norharman, Harman and PhIP in the sample in the example 3.

FIG. 4 is a heterocyclic amine test spectrum of yellow croaker patties obtained in example 4; wherein a is a liquid phase spectrum of the sample of the example 4, and b and c are respectively quantitative analysis of PhIP and Norharman in the sample of the example 4.

FIG. 5 is a heterocyclic amine test spectrum of a yellow croaker cake measured in comparative example 1; wherein a is a liquid phase spectrogram of the sample of the comparative example 1, and b, c and d are quantitative analysis of IQ, 8-MeIQx and Norharman in the sample of the comparative example 1 respectively.

FIG. 6 is a heterocyclic amine test spectrum of a yellow croaker cake measured in comparative example 1; wherein a, b and c are respectively the quantitative analysis of 4,8-DiMeIQx, Harman and PhIP in the sample of comparative example 1.

FIG. 7 is a top view comparison of the GC-IMS three-dimensional spectra of the VOC of comparative example 1 and the VOC of examples 1-4.

Detailed Description

The following description of the preferred embodiments of the present invention is provided for the purpose of better illustrating the invention and is not intended to limit the invention thereto.

The test method comprises the following steps:

testing of heterocyclic amine content:

smashing the finished fish cake (15 parts, numbered 1-15, 2g each), adding 1mL of deionized water, and shaking and mixing for 10 min; adding 9mL acetonitrile solution (containing 1% acetic acid), and shaking for 10 min; adding extraction bag (4g anhydrous magnesium sulfate and 1g anhydrous sodium acetate), and shaking vigorously by hand for 1 min; centrifuging at 6000r/min for 10min, adding 6mL of supernatant into a centrifuge tube containing 900mg of anhydrous magnesium sulfate, 300mg of PSA and 300mg of C18EC, and oscillating for 1 min; centrifuging at 6000r/min for 5min, taking 1mL of supernatant, drying by using a nitrogen blowing instrument, adding 1mL of methanol solution, performing vortex redissolution, filtering by using a 0.22-micron filter membrane, and determining the content of heterocyclic amine in the fish cake by using an Aglient1290-6460 liquid chromatography mass spectrometer; wherein, the chromatographic conditions of the high performance liquid chromatography-mass spectrometry combined method are that a chromatographic column: agilent C18 column (2.1mm x 100mm, 1.8 μm); injecting sample of 5uL at room temperature; mobile phase A: 5mmol/L aqueous ammonium acetate solution (containing 0.1% formic acid), mobile phase B: acetonitrile; performing gradient elution at the column temperature of 30 ℃ and the flow rate of 0.3 mL/min; an acquisition mode: ESI +.

Method for measuring fat oxidation:

the lipid oxidation of the baked fish cake is measured by adopting a TBA method; wherein the used thiobarbituric acid solution consists of 0.375 percent of 2-thiobarbituric acid, 15 percent of trichloroacetic acid and 0.25mol/L hydrochloric acid solution. The specific method comprises the following steps: adding 1g of smashed fish cake into 5mL of thiobarbituric acid solution, heating in a boiling water bath for 20 minutes, cooling with flowing water, centrifuging at 8000r/min for 15 minutes at 4 ℃, and measuring the absorbance of the supernatant at 532 nm; the TBARS value of the degree of fat oxidation is calculated as shown in the following formula (1):

TBARS(mg/kg)＝A₅₃₂×2.77 (1)

wherein A532 is the absorbance of the supernatant at 532 nm.

Protein oxidation assay method:

the oxidation of the baked yellow croaker protein was determined by calculating the carbonyl content using a protein carbonyl content detection kit (Beijing Solarbio technologies, Ltd.). The method comprises the following steps: adding 1mL of the extractive solution (acidic buffer solution) in the kit into 0.1g of the grilled yellow croaker sample, homogenizing, and centrifuging at 4 deg.C at 5000r/min for 10 min; taking the supernatant to 0.1mL of reagent 1 in the kit, standing at room temperature for 10 minutes, and centrifuging at 4 ℃ for 10 minutes at the speed of 12000 r/min; the supernatant was used as a sample and the assay was performed according to the procedure in the kit instructions.

Flavor change determination method:

the flavor comparison of the baked fish cake before and after adding the essential oil is measured by adopting a GC-IMS method. The method comprises the following steps: weighing 1g of sample, adding into a 20mL headspace bottle, and culturing at 80 ℃ for 15 minutes before injection; then injecting 500 mul of incubation sample at 85 ℃ by using a sample injection needle, wherein the gas chromatographic column is FS-SE-54-CB-115 m ID:0.53mm, and the column temperature is set to be 60 ℃; the gas chromatography conditions were set as follows: 2mL/min, 2min, 10mL/min, 8min, 100mL/min, 10min, 150mL/min, and finally 10 min. The drift gas flow rate is set to 150 ml/min; end useThe fish cake flavor was analyzed.

Example 1

A method for reducing the heterocyclic amine content in grilled yellow croaker using oregano essential oil, comprising the steps of:

(1) mincing wild large yellow croaker to obtain minced yellow croaker, and refrigerating for later use;

(2) mixing 0.4g oregano essential oil and 9.6g soybean oil uniformly to obtain essential oil mixed oil for later use; wherein the addition amount of the essential oil is 4 wt% of the essential oil mixed oil;

(3) uniformly mixing 50g of the yellow croaker surimi obtained in the step (1) and 2g of the essential oil mixed oil obtained in the step (2), putting into a phi 9cm mould for shaping, and processing into phi 9cm multiplied by 1cm yellow croaker cakes;

(4) and (4) placing the yellow croaker cakes obtained in the step (3) in an oven, and baking each side for 20min at the temperature of 240 ℃ and the humidity of 50% for 40min to obtain finished product fish cakes.

Example 2

Adjusting the addition amount of the essential oil in the step (2) of the example 1 to be 20 wt% of the essential oil mixed oil; the rest is kept the same as example 1 to obtain the finished fish cake.

Example 3

The oregano essential oil in example 1 was adjusted to clove essential oil, and the rest was kept the same as example 1, to obtain the final fish cake.

Example 4

Adjusting the addition amount of the essential oil in the step (2) of the example 1 to be 20 wt% of the essential oil mixed oil and adjusting the oregano essential oil to be clove essential oil; the rest is kept the same as example 1 to obtain the finished fish cake.

Comparative example 1 omitting addition of oregano essential oil

A method for preparing a finished fish cake comprises the following steps:

(1) mincing wild large yellow croaker to obtain minced yellow croaker, and refrigerating for later use;

(2) uniformly mixing 50g of the yellow croaker surimi obtained in the step (1) with 2g of soybean oil, shaping in a phi 9cm mould, and processing into phi 9cm multiplied by 1cm yellow croaker cakes;

(3) and (3) placing the yellow croaker cakes obtained in the step (2) in an oven, and baking each side for 20min at the temperature of 240 ℃ and the humidity of 50% for 40min to obtain finished product fish cakes.

The fish cakes obtained in examples 1-4 and comparative example 1 are subjected to performance tests, and the test results are shown in tables 1 and 2:

table 1 shows the results of the test for the content of hybrid amine. As can be seen from table 1: after the yellow croaker cake treated by the essential oil is baked, the content of generated hybrid amine is greatly reduced, wherein the effect of the embodiment 2 is most obvious.

TABLE 1 test results of examples 1-4 and comparative example 1

Heterocyclic amines	Comparative example 1	Example 1	Example 2	Example 3	Example 4
						IQ	0.6073±0.0065b	NDa	NDa	NDa	NDa
IQX	NDa	NDa	NDa	NDa	NDa
						MeIQ	NDa	NDa	NDa	NDa	NDa
Trp-p-1	NDa	NDa	NDa	NDa	NDa
						8-MeIQX	0.7590±0.0121b	NDa	NDa	NDa	NDa
Norharman	876.3333±11.8462c	19.8643±0.0739b	0.2927±0.0038a	1.9427±0.0107a	0.9173±0.0135a
						4,8-DiMeIQX	0.5417±0.0202b	NDa	NDa	NDa	NDa
7,8-DiMeIQX	NDa	NDa	NDa	NDa	NDa
						Harman	13.2667±0.1528c	0.9393±0.0055b	NDa	0.0783±0.0021a	NDa
PhIP	37.4333±0.2082d	0.1983±0.0032b	NDa	0.0193±0.0006ab	0.3750±0.0072c
						AaC	NDa	NDa	NDa	NDa	NDa
MeAaC	NDa	NDa	NDa	NDa	NDa
						Trp-p-2	NDa	NDa	NDa	NDa	NDa
Total heterocyclic amines	928.9413±6.8492c	21.0020±0.0817b	0.2927±0.0037a	2.0707±0.0131a	1.2924±0.0210a
						Total inhibition rate	—	97.74％	99.97％	99.78％	99.86％

Note: "ND" means not detected.

Table 2 shows the results of the oxidation degree test. As can be seen from table 2: after the yellow croaker cake treated by the essential oil is baked, the oxidation degree of fat is greatly reduced, wherein the effects of the examples 2 and 4 are most obvious, and the oxidation degree of the yellow croaker cake is not obviously different from that of the unroasted yellow croaker; the oxidation degree of protein of the yellow croaker cake treated by the essential oil is reduced after baking, wherein the examples 2, 3 and 4 have better inhibition effect compared with the comparative example 1, and have no significant difference, while the comparative example 1 has a certain degree of increase compared with the comparative example.

TABLE 2 results of oxidation degree test of samples in examples 1 to 4 and comparative example 1

Example (b)	TBARS(mg MDA/kg)	Carbonyl content (nmol/mg protein)
			Raw meat	0.8287±0.0032e	0.3430±0.0107a
Comparative example 1	2.0951±0.0076a	0.1830±0.0127c
			Example 1	1.2233±0.0229b	0.2637±0.0110b
Example 2	0.8792±0.0078d	0.1183±0.0057d
			Example 3	0.1245±0.0102c	0.1075±0.0019d
Example 4	0.8543±0.0058de	0.1060±0.0041d

Note: the raw meat is uncooked yellow croaker.

FIG. 7 is a top view comparison of the GC-IMS three-dimensional spectra of the VOC of comparative example 1 and the VOC of examples 1-4. As can be seen from fig. 7: the croaker cakes of examples 1 to 4 were baked to have a different degree of flavor change compared with comparative example 1, wherein examples 1 and 3 were slightly different from comparative example 1, and examples 2 and 4 were greatly different from comparative example 1, indicating that the effect on flavor was excessive.

Comparative example 2

Adjusting the content of the essential oil of example 2 to be evening primrose essential oil; other conditions were kept the same as in example 2 to obtain a finished fish cake.

The obtained finished fish cake is subjected to a fat oxidation test, and the test result is as follows:

the fish cake fat oxidation degree of comparative example 2 was 1.965 + -0.048 mg MDA/kg, with no significant difference compared to 2.095 + -0.076 mg MDA/kg of comparative example 1.