Method for reducing heterocyclic amine in grilled fish

Abstract

The invention belongs to the technical field of aquatic product processing, and discloses a method for reducing heterocyclic amine in grilled fish. According to the invention, the mixture of onion and ginger is used as the pickling liquid, and one or more of carrageenan, xanthan gum, sodium carboxymethyl cellulose and tea polyphenol is / are used as the film forming liquid, so that the generation of heterocyclic amine in the grilled fish can be effectively inhibited; and meanwhile, the meat can be prevented from being in direct contact with grease, and the loss of water and other nutrients or flavor substances in food materials is inhibited, so that the food quality is improved. The method is simple to operate and has a wide application prospect.

Description

Technical Field

[0001] The present invention belongs to the technical field of aquatic product processing, and particularly relates to a method for reducing heterocyclic amines in roasted fish. Background Art

[0002] Heterocyclic amines (Has) are a class of heterocyclic aromatic hydrocarbon compounds with carcinogenic and mutagenic effects, which are generated by the reaction of glucose, creatine, amino acids, etc. during the thermal processing of food raw materials rich in animal-derived proteins. They especially exist in high-temperature processed foods such as grilled and fried foods. So far, more than 30 kinds of heterocyclic amines have been isolated and identified in meat products and simulation systems. According to the formation pathways and chemical structures of heterocyclic amines, they can be divided into two categories: polar and non-polar heterocyclic amines. Polar heterocyclic amines are mainly formed at 100 - 300 °C, and non-polar heterocyclic amines are generally formed at high temperatures above 300 °C, and most polar heterocyclic amines have strong mutagenicity. Therefore, it is of great significance to develop effective measures to inhibit the formation of heterocyclic amines during food cooking and processing.

[0003] Roasted fish, as a product with delicious taste and high nutritional value, is especially popular among consumers. However, during the roasting of high-protein meat, improper process control easily generates carcinogenic substances such as heterocyclic amine compounds. The main factors affecting the formation of heterocyclic amines in food are temperature, time, processing method, precursor substances, etc. The existing measures to inhibit the formation of heterocyclic amines in meat products mainly include: controlling the processing temperature and time, changing the processing method, pre-treating the raw meat, and reasonably adding ingredients and exogenous components, etc.

[0004] Among them, adding common food seasonings and film-forming liquids is an effective measure to reduce heterocyclic amines in the food system. However, in the existing methods, the addition of chili powder, star anise, etc. is likely to cover up the original flavor of the ingredients and affect the original sensory properties of the food system; the addition of the film-forming liquid is mostly in the way of adding colloidal powder and mixing it evenly in the food system before cooking, lacking a method that can be applied to the whole food system such as roasted fish. Therefore, it is particularly important to explore a method that can reduce heterocyclic amines in roasted fish.

[0005] In recent years, the control of heterocyclic amines and the improvement of the quality of fried and grilled fish and other foods have attracted much attention. The invention patent with the publication number CN 115624128 A discloses an additive for fried foods and its preparation method, which uses modified bacterial cellulose nanofibers, hibiscus flower gum powder, calcium citrate, edible oil and deionized water to form an edible colloid coating to improve the crispy taste of fried foods. However, the preparation period of this method is relatively long, and the effect of inhibiting heterocyclic amines is not obvious. The invention patent with the publication number CN114847446A discloses a method for reducing the content of heterocyclic amines and fat oxidation in grilled mackerel, which uses vegetable extracts, including celery extract, yam extract and carrot extract, etc. to reduce the content of heterocyclic amines in grilled mackerel. However, this method is applied to the fish cake system by mixing addition, and is not applicable to the whole grilled fish system. Summary of the Invention

[0006] In view of this, the ginger and onion selected in the present invention are common additives in foods, which are cheap and easy to obtain, and the antioxidant substances such as phenols contained therein can effectively scavenge free radicals and inhibit the reaction process. The film-forming solution containing carrageenan, xanthan gum, sodium carboxymethyl cellulose, tea polyphenols, etc. can play a role in cross-linking and water retention, and the combined coating application can play a better role in inhibiting the deterioration of products and the generation of heterocyclic amines.

[0007] In order to achieve the above object, the object of the present invention is to provide a method for reducing heterocyclic amines in grilled fish, and the following technical solutions are adopted:

[0008] A method for reducing heterocyclic amines in grilled fish, using a mixture of onion and ginger as a pickling solution, and using one or several of carrageenan, xanthan gum, sodium carboxymethyl cellulose, and tea polyphenols as a film-forming solution to make grilled fish.

[0009] It is worth noting that the present invention effectively prevents the generation of heterocyclic amines by wrapping the outer layer of the fish pickled with scallions and ginger with a hydrophilic colloid.

[0010] Among them, curcumin in ginger and polyphenolic compounds such as flavonoids in onion have significant antioxidant activities, which can effectively scavenge free radicals generated during the high-temperature processing of grilled fish, reduce the fat oxidation reaction and the generation of HAs active carbonyl intermediates, thereby reducing the generation of heterocyclic amines. Carrageenan, xanthan gum, sodium carboxymethyl cellulose, tea polyphenols, etc. contain rich hydrophilic groups such as carboxyl or amino groups, which can inhibit the generation of heterocyclic amines by interfering with the pyrolysis reaction of amino acids and reacting with the carbonyl compounds of the key intermediates of heterocyclic amines. In addition, the film-forming solution coated on the surface of the fish body forms a protective layer, which will also reduce the baking loss to a certain extent, thereby weakening the degree of migration of precursor substances such as creatine, sugar and free amino acids to the surface of the fish body with water, and interfering with the subsequent reaction process of heterocyclic amine precursors and key intermediates.

[0011] In addition, the raw materials of the pickling solution selected in the present invention, namely ginger and onion, are common food raw materials, and the selected film-forming solution is carrageenan, xanthan gum, sodium carboxymethyl cellulose (CMC-Na), and tea polyphenols (TP), all of which have no obvious characteristic flavors and are widely used in various foods without affecting the original flavors of the food ingredients.

[0012] Furthermore, the preparation method of the pickling solution is as follows:

[0013] (1) Prepare onion pieces and ginger pieces, and mix the onion pieces and ginger pieces in a ratio of 1:1 to obtain a mixed solid material;

[0014] (2) Add the mixed solid material obtained in step (1) to the mixed brine according to a solid-liquid ratio of 3%, and perform ultrasonic treatment at a power of 480W and a temperature of 72°C for 32 minutes to obtain a pickling solution for standby.

[0015] Even further, the mixed brine is prepared according to a weight ratio of fish: ice water: table salt = 100:100:1.5.

[0016] Furthermore, the preparation method of the film-forming solution is as follows:

[0017] Add 2.0% (w / v) glycerol to water as a co-solvent, then add one or more of carrageenan, xanthan gum, sodium carboxymethyl cellulose, and tea polyphenols, and then heat and stir in a 60°C constant temperature water bath with a overhead stirrer at 2000 r / min for 0.5 h to ensure the uniformity of the film-forming solution system. After stirring, place it in a 50°C constant temperature water bath for standby to prevent the film-forming solution from solidifying.

[0018] It should be noted that the film-forming solution disclosed in the present invention is recommended to be used immediately after preparation.

[0019] Even further, one or more of carrageenan, xanthan gum, sodium carboxymethyl cellulose, and tea polyphenols include any one of 1.0% (w / v) carrageenan, 1.0% (w / v) xanthan gum, 0.5% (w / v) sodium carboxymethyl cellulose, 1.0% (w / v) sodium carboxymethyl cellulose, 2.0% (w / v) sodium carboxymethyl cellulose, 2.0% (w / v) tea polyphenols, and 1.0% (w / v) sodium carboxymethyl cellulose + 1.0% (w / v) tea polyphenols combination.

[0020] It should be noted that under the preparation process of the pickling solution used in the present invention, the total inhibition rate of heterocyclic amines in grilled fish is 54.02%; combined with the composite coating (1.0% sodium carboxymethyl cellulose + 1.0% tea polyphenols), the total inhibition rate of heterocyclic amines in grilled fish reaches 67.93%.

[0021] Even further, the steps of the grilled fish in the method for reducing heterocyclic amines in grilled fish include:

[0022] Pretreatment: The raw fish is slaughtered, gutted, and then cleaned and cut after opening the back;

[0023] Marinating: Place the fish after opening the back and cutting into the marinating liquid and marinate for 3 hours;

[0024] Coating: Immerse the marinated fish body in the film-forming liquid for dipping coating;

[0025] Baking: Bake the coated fish body at 280 °C for 13 min.

[0026] Furthermore, the raw fish includes frozen fish or live fish, and the raw fish includes grass carp, perch, catfish or basa fish.

[0027] Furthermore, the water temperature during marinating is 8 °C - 10 °C; each time the marinating liquid is only used for marinating once, tumbling for 10 minutes at a speed of 6 rpm; after tumbling, let it stand and marinate for 3 hours, and turn it over once every half hour.

[0028] Furthermore, the specific method of coating includes: put the marinated fish body into the film-forming liquid and immerse it for 5 min, take it out and place it in a ventilated and cool place to dry.

[0029] Compared with the prior art, the present invention comprehensively utilizes the antioxidant blocking effect of ginger and scallions and the physical barrier effect of the film-forming liquid coating to inhibit the production of heterocyclic amines during the high-temperature processing of grilled fish. That is, through the antioxidant blocking inhibition effect of marinating with ginger and onion and the chemical reaction interference and physical coating barrier mechanism of the film-forming liquid coating, the generation of heterocyclic amines is synergistically inhibited. The process involved is simple, time-consuming, and low-cost, and has broad application and promotion prospects. Brief Description of the Drawings

[0030] In order to more clearly illustrate the technical solutions in the embodiments of the present invention or the prior art, the following will briefly introduce the drawings required to be used in the description of the embodiments or the prior art. Obviously, the drawings in the following description are only the embodiments of the present invention. For those of ordinary skill in the art, other drawings can be obtained according to the provided drawings without creative efforts.

[0031] Figure 1 It is a process flow chart of the method for reducing heterocyclic amines in grilled fish disclosed in the present invention.

[0032] Figure 2 It is the PCA score plot (A) and loading plot (B) of free HAs in Example 1 and Examples 2 - 4 in Experimental Example 2 of the present invention.

[0033] Figure 3 It is the PCA score plot (A) and loading plot (B) of bound HAs in Example 1 and Examples 2 - 4 in Experimental Example 2 of the present invention.

[0034] Figure 4 This is the effect of different concentrations of CMC-Na on free HAs in roasted fish in Experimental Example 3 of the present invention.

[0035] Figure 5 This is the effect of different concentrations of CMC-Na on bound HAs in roasted fish in Experimental Example 3 of the present invention. Detailed implementation manners

[0036] The technical solutions in the embodiments of the present invention will be clearly and completely described below. Obviously, the described embodiments are only a part of the embodiments of the present invention, rather than all the embodiments. All other embodiments obtained by those of ordinary skill in the art based on the embodiments of the present invention without creative efforts shall fall within the protection scope of the present invention.

[0037] The special term "embodiment" here, any embodiment described as "exemplary" does not have to be construed as superior or better than other embodiments. For the performance index tests in the embodiments of the present application, unless otherwise specified, the conventional test methods in the art are adopted. It should be understood that the terms described in the present application are only for describing specific embodiments and are not used to limit the content disclosed in the present application.

[0038] Unless otherwise specified, the technical and scientific terms used herein have the same meanings as those commonly understood by those of ordinary skill in the technical field to which the present application belongs; the test methods and technical means not specifically noted in the present application refer to the experimental methods and technical means commonly adopted by those of ordinary skill in the art.

[0039] To better illustrate the content of the present application, numerous specific details are given in the following specific embodiments. Those skilled in the art should understand that the present application can also be implemented without some specific details. In the embodiments, some methods, means, instruments, equipment, etc. well-known to those skilled in the art are not described in detail to highlight the gist of the present application.

[0040] On the premise of no conflict, the technical features disclosed in the embodiments of the present application can be combined arbitrarily, and the obtained technical solutions belong to the content disclosed in the embodiments of the present application.

[0041] The present invention discloses a method for reducing heterocyclic amines in roasted fish, belonging to the technical field of aquatic product processing. By combining the use of a mixture of onion and ginger as a pickling solution and using one or several of carrageenan, xanthan gum, sodium carboxymethyl cellulose, and tea polyphenols as a film-forming solution, the present invention can effectively inhibit the formation of heterocyclic amines in roasted fish, and at the same time can also prevent the direct contact between meat and grease, inhibit the loss of internal moisture and other nutrients or flavor substances in the food materials, thereby improving the food quality. This method is simple to operate and has broad application prospects.

[0042] To better understand the present invention, the following specific embodiments are used to further elaborate on the present invention. However, it should not be construed as a limitation of the present invention. For those skilled in the art, some non-essential improvements and adjustments made based on the above-mentioned invention content are also considered to fall within the protection scope of the present invention.

[0043] Example 1

[0044] Pretreatment: Fresh grass carp is slaughtered, opened, cleaned, and cut after cleaning;

[0045] Marinating: Prepare the marinating solution. First, prepare a brine mixed solution in the ratio of grass carp: ice water: salt = 100:100:1.5. Then, grind onions and ginger with a blender, and add the onion and ginger mixture at a ratio of 1:1 with 3% (based on the mass of the aqueous phase). Prepare the marinating solution under the conditions of a preparation time of 32 min, a temperature of 72 °C, and an ultrasonic power of 480 W. When marinating, the water temperature is 8 °C - 10 °C, and each batch of ingredients is only marinated once, with tumbling for 10 minutes at a speed of 6 rpm; after tumbling, marinate for 3 hours, and turn over once every half hour;

[0046] Baking: Bake the marinated fish body at 280 °C for 13 min.

[0047] Example 2

[0048] Pretreatment: Fresh grass carp is slaughtered, opened, cleaned, and cut after cleaning;

[0049] Marinating: Prepare the marinating solution. First, prepare a brine mixed solution in the ratio of grass carp: ice water: salt = 100:100:1.5. Then, grind onions and ginger with a blender, and add the onion and ginger mixture at a ratio of 1:1 with 3% (based on the mass of the aqueous phase). Prepare the marinating solution under the conditions of a preparation time of 32 min, a temperature of 72 °C, and an ultrasonic power of 480 W. When marinating, the water temperature is 8 °C - 10 °C, and each batch of ingredients is only marinated once, with tumbling for 10 minutes at a speed of 6 rpm; after tumbling, marinate for 3 hours, and turn over once every half hour;

[0050] Coating: First, add 2.0% (w / v) glycerol to pure water as a cosolvent, and then dissolve 1.0% CMC-Na in pure water. Heat and stir in a 60 °C constant temperature water bath with a top-mounted stirrer at 2000 r / min for about 0.5 h to ensure the uniformity of the film-forming liquid system. After stirring, place it in a 50 °C constant temperature water bath for standby to prevent the film-forming liquid from solidifying. Then, put the processed fish pieces into the coating liquid, soak for 5 min, take them out and place them in a ventilated and cool place to dry, waiting for the film-forming liquid to form a film on the surface of the fish meat;

[0051] Baking: Bake the coated fish body at 280 °C for 13 min.

[0052] Example 3

[0053] Pretreatment: Fresh grass carps are slaughtered, gutted, cleaned, and cut after opening the back;

[0054] Marination: Prepare the marinating solution. First, prepare a brine mixed solution in the ratio of grass carp: ice water: salt = 100:100:1.5. Then, grind onions and ginger with a blender, and add the onion and ginger mixture at a ratio of 1:1 by 3% (based on the mass of the aqueous phase). The marinating solution is prepared under the conditions of a preparation time of 32 min, a temperature of 72 °C, and an ultrasonic power of 480 W. The water temperature during marination is 8 °C - 10 °C, and each batch of ingredients is marinated only once, with tumbling for 10 minutes at a speed of 6 rpm; after tumbling, marinate for 3 hours and turn over once every half hour;

[0055] Coating: First, add 2.0% (w / v) glycerol to pure water as a cosolvent, and then dissolve 1.0% xanthan gum in pure water. Heat and stir in a 60 °C constant temperature water bath with a overhead stirrer at 2000 r / min for about 0.5 h to ensure the uniformity of the film-forming liquid system. After stirring, place it in a 50 °C constant temperature water bath for standby to prevent the film-forming liquid from solidifying. Then, put the processed fish pieces into the coating liquid, soak for 5 min, take them out and place them in a ventilated and cool place to dry until the film-forming liquid forms a film on the surface of the fish meat;

[0056] Baking: Bake the coated fish body at 280 °C for 13 min.

[0057] Example 4

[0058] Pretreatment: Fresh grass carps are slaughtered, gutted, cleaned, and cut after opening the back;

[0059] Marination: Prepare the marinating solution. First, prepare a brine mixed solution in the ratio of grass carp: ice water: salt = 100:100:1.5. Then, grind onions and ginger with a blender, and add the onion and ginger mixture at a ratio of 1:1 by 3% (based on the mass of the aqueous phase). The marinating solution is prepared under the conditions of a preparation time of 32 min, a temperature of 72 °C, and an ultrasonic power of 480 W. The water temperature during marination is 8 °C - 10 °C, and each batch of ingredients is marinated only once, with tumbling for 10 minutes at a speed of 6 rpm; after tumbling, marinate for 3 hours and turn over once every half hour;

[0060] Coating: First, add 2.0% (w / v) glycerol to pure water as a cosolvent, and then dissolve 1.0% carrageenan in pure water. Heat and stir in a 60 °C constant temperature water bath with a overhead stirrer at 2000 r / min for about 0.5 h to ensure the uniformity of the film-forming liquid system. After stirring, place it in a 50 °C constant temperature water bath for standby to prevent the film-forming liquid from solidifying. Then, put the processed fish pieces into the coating liquid, soak for 5 min, take them out and place them in a ventilated and cool place to dry until the film-forming liquid forms a film on the surface of the fish meat;

[0061] Baking: Bake the fish body with the coating at 280 °C for 13 min.

[0062] Example 5

[0063] Pretreatment: The fresh grass carp is slaughtered, opened, cleaned and cut after being opened;

[0064] Marinating: Prepare the marinating liquid. First, prepare a brine mixed solution in the ratio of grass carp: ice water: salt = 100:100:1.5. Then, grind the onion and ginger with a blender, and add the onion and ginger mixture at a ratio of 1:1 at 3% (based on the mass of the aqueous phase). The marinating liquid is prepared under the conditions of a preparation time of 32 min, a temperature of 72 °C, and an ultrasonic power of 480 W. The water temperature during marinating is 8 °C - 10 °C, and each batch of ingredients is marinated only once, with tumbling for 10 minutes at a speed of 6 rpm; after tumbling, marinate for 3 hours, and turn over once every half hour;

[0065] Coating: First, add 2.0% (w / v) glycerol to pure water as a cosolvent, and then dissolve 0.5% CMC-Na in pure water. Heat and stir in a 60 °C constant temperature water bath with a top-mounted stirrer at 2000 r / min for about 0.5 h to ensure the uniformity of the film-forming liquid system. After stirring, place it in a 50 °C constant temperature water bath for standby to prevent the film-forming liquid from solidifying. Then, put the processed fish pieces into the coating liquid, soak for 5 min, take them out and place them in a ventilated and cool place to dry until the film-forming liquid forms a film on the surface of the fish meat;

[0066] Baking: Bake the fish body with the coating at 280 °C for 13 min.

[0067] Example 6

[0068] Pretreatment: The fresh grass carp is slaughtered, opened, cleaned and cut after being opened;

[0069] Marinating: Prepare the marinating liquid. First, prepare a brine mixed solution in the ratio of grass carp: ice water: salt = 100:100:1.5. Then, grind the onion and ginger with a blender, and add the onion and ginger mixture at a ratio of 1:1 at 3% (based on the mass of the aqueous phase). The marinating liquid is prepared under the conditions of a preparation time of 32 min, a temperature of 72 °C, and an ultrasonic power of 480 W. The water temperature during marinating is 8 °C - 10 °C, and each batch of ingredients is marinated only once, with tumbling for 10 minutes at a speed of 6 rpm; after tumbling, marinate for 3 hours, and turn over once every half hour;

[0070] Coating: First, add 2.0% (w / v) glycerol to pure water as a cosolvent, and then dissolve 2.0% CMC-Na in pure water. Heat and stir in a 60°C constant temperature water bath with a top-mounted stirrer at 2000 r / min for about 0.5 h to ensure the uniformity of the film-forming liquid system. After stirring, place it in a 50°C constant temperature water bath for standby to prevent the film-forming liquid from solidifying. Then, put the processed fish pieces into the coating liquid, immerse them for 5 min, take them out and place them in a ventilated and cool place to dry, waiting for the film-forming liquid to form a film on the surface of the fish meat;

[0071] Baking: Bake the coated fish at 280°C for 13 min.

[0072] Example 7

[0073] Pretreatment: Fresh grass carp is slaughtered, opened, cleaned and cut after being opened;

[0074] Marinating: Prepare the marinating liquid. First, prepare a brine mixed solution in the ratio of grass carp: ice water: salt = 100:100:1.5. Then, grind onions and ginger with a blender, and add a 3% (based on the mass of the aqueous phase) mixture of onions and ginger in a 1:1 ratio, and prepare the marinating liquid under the conditions of a preparation time of 32 min, a temperature of 72°C, and an ultrasonic power of 480 W. The water temperature during marinating is 8°C - 10°C, and each batch of ingredients is marinated only once, and kneaded for 10 minutes at a speed of 6 rpm; after kneading, marinate for 3 hours and turn it over once every half hour;

[0075] Coating: First, add 2.0% (w / v) glycerol to pure water as a cosolvent, and then dissolve 2.0% TP in pure water. Heat and stir in a 60°C constant temperature water bath with a top-mounted stirrer at 2000 r / min for about 0.5 h to ensure the uniformity of the film-forming liquid system. After stirring, place it in a 50°C constant temperature water bath for standby to prevent the film-forming liquid from solidifying. Then, put the processed fish pieces into the coating liquid, immerse them for 5 min, take them out and place them in a ventilated and cool place to dry, waiting for the film-forming liquid to form a film on the surface of the fish meat;

[0076] Baking: Bake the coated fish at 280°C for 13 min.

[0077] Example 8

[0078] Pretreatment: Fresh grass carp is slaughtered, opened, cleaned and cut after being opened;

[0079] Marinating: Prepare the marinating solution. First, prepare a brine mixture solution in the ratio of grass carp: ice water: salt = 100:100:1.5. Then, grind onions and ginger with a blender, and add the onion and ginger mixture at a ratio of 1:1 with 3% (based on the mass of the aqueous phase). Prepare the marinating solution under the conditions of a preparation time of 32 min, a temperature of 72 °C, and an ultrasonic power of 480 W. During marinating, the water temperature is 8 °C - 10 °C, and each batch of ingredients is marinated only once, with tumbling for 10 minutes at a speed of 6 rpm; after tumbling, marinate for 3 hours, and turn over once every half hour;

[0080] Coating: First, add 2.0% (w / v) glycerol to pure water as a co-solvent, and then dissolve 2.0% of the composite coating raw materials (1.0% CMC-Na + 1.0% TP) in pure water. Heat and stir in a 60 °C constant temperature water bath with a top-mounted stirrer at 2000 r / min for about 0.5 h to ensure the uniformity of the film-forming liquid system. After stirring, place it in a 50 °C constant temperature water bath for standby to prevent the film-forming liquid from solidifying. Then, put the processed fish pieces into the coating liquid, soak for 5 min, take them out and place them in a ventilated and cool place to dry, waiting for the film-forming liquid to form a film on the surface of the fish meat;

[0081] Baking: Bake the coated fish body at 280 °C for 13 min.

[0082] To further prove the beneficial effects of the present invention for better understanding of the present invention, the following Comparative Example 1 and Experimental Examples 1 to 4 further clarify the properties and application performance of the method for reducing heterocyclic amines in roasted fish disclosed by the present invention. However, it should not be construed as a limitation of the present invention. For the method properties obtained by other determination experiments made by those skilled in the art according to the above-mentioned invention content and the applications based on the above properties, they are also considered to fall within the protection scope of the present invention.

[0083] Comparative Example 1

[0084] Pretreatment: Fresh grass carp is slaughtered, opened, cleaned, and cut after cleaning;

[0085] Marinating: Prepare the marinating solution in the ratio of grass carp: ice water: salt = 100:100:1.5, and the water temperature during marinating is 8 °C - 10 °C; each batch of ingredients is marinated only once, with tumbling for 10 minutes at a speed of 6 rpm; after tumbling, marinate for 3 hours, and turn over once every half hour;

[0086] Baking: Bake the marinated fish body at 280 °C for 13 min.

[0087] Comparison of Heterocyclic Amine Contents in Roasted Fish Using Different Marinating Solutions in Experimental Example 1

[0088] Determine the heterocyclic amine contents of Example 1 and Comparative Example 1, and the determination results are shown in Table 1.

[0089] Table 1

[0090]

[0091] By comparing the types and contents of free and protein-bound heterocyclic amines in the grilled fish of Example 1 and Comparative Example 1, it was found that the content changes of different types of heterocyclic amines during the baking process were different.

[0092] There are mainly 7 kinds of heterocyclic amines formed during the baking of grass carp, namely Norharman, Harman, AαC, MeAαC, IQ, MeIQ, PhIP and 4,8-DiMeIQx. Among the free heterocyclic amines, a total of 4 kinds of HAs (including α-carboline and β-carboline) were detected, and their total amount was 3.72 ng / g. Among them, the contents of Norharman and Harman accounted for a relatively large proportion, and the contents of the two free HAs were 1.18 ng / g and 1.44 ng / g respectively. The inhibition rate of free HAs was 14.48%. Seven kinds of HAs (including α-carboline, β-carboline, pyridine, quinoline and quinoxaline) were determined in the bound HAs. The total content of bound HAs was 147.04 ng / g, among which Norharman and Harman accounted for the largest proportion, and the contents of the two HAs were 33.22 ng / g and 102.37 ng / g respectively, accounting for 92.21% of the total bound amount. In Example 1, the total amount of HAs was 150.75 ng / g, and the total inhibition rate was 54.02%. Example 1 after process optimization could significantly reduce the content of heterocyclic amines.

[0093] Comparison of the Contents of Heterocyclic Amines in Grilled Fish with or without Film-Forming Solution in Experimental Example 2

[0094] The heterocyclic amine contents of Examples 2-4 were determined and compared with that of Example 1, and the measurement results are shown in Table 2.

[0095] Table 2 Effects of Film-Forming Solution on Free Heterocyclic Amines in Grilled Fish (ng / g)

[0096]

[0097] Table 2 shows the contents of free heterocyclic amines in the grilled fish of Example 1 and Examples 2-4. Five kinds of heterocyclic amines were detected and quantified in Example 1: Norharman, Harman, MeAαC, AαC and IQ. Example 1 contained 3.72 ng / g of HAs. And CMC-Na, xanthan gum and carrageenan all had inhibitory effects on free heterocyclic amines in grilled fish. The total amounts of their free HAs from high to low were: Example 4 (3.33 ng / g), Example 2 (3.25 ng / g) and Example 3 (3.21 ng / g).

[0098] The PCA (Principal Component Analysis) method was used to study the effects of different film-forming solutions on HAs. Figure 2 The PCA score plot and loading plot of free HAs in the grilled fish of Example 1 and Examples 2-4 are shown.

[0099] As Figure 2 shown in the score plot (A), PC1 = 73.7%, PC2 = 13.9%, and their cumulative contribution rate is 87.6%. Among them, in the direction of PC1, there were significant differences (p < 0.05) between Examples 2-4 and the treatment group in the generation of free heterocyclic amines in the grilled fish. However, Example 1 and Example 2 were close in position in the direction of PC1, and there was no significant difference between them (p > 0.05). Moreover, Example 4 and Example 1 were both located on the right side of the vertical axis and were close in position, indicating that the effect of carrageenan on the generation of free HAs in the grilled fish was slightly worse than that of xanthan gum and CMC-Na. From the loading plot (B), it can be seen that in the direction of PC1, Norharman, Harman, and IQ were on both sides of the vertical axis respectively with MeAαC and AαC, and the positions of Norharman and Harman corresponded to the control group, indicating that xanthan gum and CMC-Na had better inhibitory effects on free Norharman, Harman, and IQ.

[0100] Table 3 shows the contents of bound heterocyclic amines in the grilled fish of Example 1 and Examples 2-4. Seven heterocyclic amines were detected in the control group, namely: Norharman, Harman, MeAαC, AαC, IQ, PhIP, and 4,8-DiMeIQx. Example 1 contained a total of 147.04 ng / g HAs, among which the most abundant was Harman (102.37 ng / g), followed by Norharman (33.22 ng / g), PhIP (3.30 ng / g), MeAαC (2.83 ng / g), AαC (1.96 ng / g), IQ (1.92 ng / g), and 4,8-DiMeIQx (1.45 ng / g).

[0101] Table 3 Effects of film-forming solutions on bound heterocyclic amines in grilled fish (ng / g)

[0102]

[0103] PCA (Principal Component Analysis) was used to explore the effects of different film-forming solutions on the generation of protein-bound HAs. Figure 3 The PCA score plot and loading plot of bound HAs in the grilled fish of Example 1 and Examples 2-4 are shown.

[0104] As Figure 3As shown in the score plot (A), PC1 = 94.40% and PC2 = 2.49%, and their cumulative contribution rate is 96.89%. Among them, in the direction of PC1, there are significant differences (p < 0.05) between Examples 2 - 4 and the treatment group in the generation of bound heterocyclic amines in grilled fish. And Example 2 and Example 1 are the farthest apart in the direction of PC1, indicating that CMC - Na has the best inhibitory effect on the bound heterocyclic amines in grilled fish, followed by xanthan gum and carrageenan. From the loading plot (B), it can be seen that in the direction of PC1, the positions of the 7 heterocyclic amines all correspond to Example 1, indicating that both CMC - Na and xanthan gum have good inhibitory effects on the bound heterocyclic amines in grilled fish, and CMC - Na is better than xanthan gum.

[0105] Compared with the total HAs of the control group, the addition of these three kinds of film - forming solutions can all inhibit the generation of heterocyclic amines to varying degrees. And the total inhibition rates of Examples 2, 3, and 4 are 16.07%, 11.53%, and 4.42% respectively. That is, compared with xanthan gum and carrageenan, CMC - Na has a stronger inhibitory ability on the formation of Harman, Norharman, PhIP, and 4,8 - DiMeIQx in grilled fish. Thus, compared with xanthan gum and carrageenan, CMC - Na is a more effective heterocyclic amine inhibitor.

[0106] Comparison of Heterocyclic Amine Contents in Grilled Fish with Different Concentrations of Film - Forming Solutions in Experimental Example 3

[0107] The heterocyclic amine contents of Examples 2, 5, 6 and Example 1 were measured respectively, and the present invention further discloses the influence of different concentrations of CMC - Na (0.5%, 1.0%, and 2.0%) on the formation of heterocyclic amines in grilled fish. As Figure 4 shown is the influence of different concentrations of CMC - Na on the free HAs in grilled fish.

[0108] As Figure 4 shown, compared with Example 1, CMC - Na can reduce the content of free Harman in grilled fish by 1.39% - 4.17%, but there is no significant difference in the inhibitory effect of different concentrations of CMC - Na on Harman (p > 0.05). Compared with Example 1, CMC - Na can reduce the content of Norharman in grilled fish by 5.32% - 27.30%, and with the increase of the CMC - Na concentration, the inhibitory effect of CMC - Na on Norharman shows an increasing trend. Compared with Example 1, CMC - Na can slightly increase the content of free AαC in grilled fish, and there is no significant difference in the influence on MeAαC (p > 0.05). The results show that different concentrations of CMC - Na can effectively reduce the contents of free Harman and Norharman in grilled fish, and Example 6 has the best inhibitory effect on these two heterocyclic amines.

[0109] As Figure 5 shown, compared with Example 1, CMC-Na can reduce the content of bound Harman in grilled fish by 6.85% - 16.67%, and with the increase of CMC-Na concentration, the inhibitory effect of CMC-Na on Harman shows an increasing trend. Compared with Example 1, CMC-Na can reduce the content of Norharman in grilled fish by 8.34% - 35.37%, and the higher the CMC-Na concentration, the stronger the inhibitory effect of CMC-Na on Norharman (p<0.05). Compared with Example 1, CMC-Na can reduce the content of PhIP in grilled fish by 17.58% - 65.76%, and the higher the CMC-Na concentration, the stronger the inhibitory effect of CMC-Na on PhIP (p<0.05). Compared with Example 1, CMC-Na can reduce the content of 4,8-DiMeIQx in grilled fish by 19.14% - 57.15%, and the higher the CMC-Na concentration, the stronger the inhibitory effect of CMC-Na on 4,8-DiMeIQx (p<0.05). The results show that different concentrations of CMC-Na can effectively reduce the contents of bound Harman, Norharman, PhIP and 4,8-DiMeIQx in grilled fish, and Example 6 has the best inhibitory effect on these 4 kinds of heterocyclic amines.

[0110] Compared with the total HAs in Example 1, the addition of different concentrations of CMC-Na can inhibit the generation of heterocyclic amines in a dose-dependent manner, and the total inhibition rates of Example 5, Example 2 and Example 6 are 7.75%, 16.07% and 22.78% respectively. That is, the addition of different concentrations of CMC-Na can inhibit the generation of heterocyclic amines in a dose-dependent manner, and the addition of 2% CMC-Na has a strong ability to inhibit the generation of heterocyclic amines.

[0111] Comparison of heterocyclic amine contents in grilled fish with single-component and composite-component film-forming solutions in Experimental Example 4

[0112] Considering that tea polyphenols, as natural phenolic compounds, have good antioxidant and free radical scavenging abilities and can scavenge free radicals generated during the formation of heterocyclic amines. Therefore, the present invention further discloses the effects of single coatings (Examples 6 and 7) and composite coatings (Example 8) on the formation of HAs, and the results are shown in Tables 4 and 5.

[0113] Table 4 Effects of single and composite coatings on free heterocyclic amines in grilled fish

[0114]

[0115] Table 5 Effects of single and composite coatings on bound heterocyclic amines in grilled fish

[0116]

[0117]

[0118] Table 4 shows the effects of different examples on free heterocyclic amines in grilled fish. In Example 1, 5 kinds of HAs (including α-carboline, β-carboline and pyridine) were determined in the free state, and the total amount was 3.72 ng / g. In Examples 6-8, 4 kinds of heterocyclic amines were detected. This may be because CMC-Na can inhibit the production of phenylacetaldehyde intermediate of PhIP, thus interfering with the reaction process of PhIP production. Generally speaking, the inhibition rates of Examples 6-8 on free HAs in grilled fish were between 28.05% and 33.33%, and there was no significant difference (p>0.05). However, compared with the grilled fish in Example 1, the contents of HAs in the grilled fish of Examples 6-8 were significantly reduced (p<0.05).

[0119] Table 5 shows the effects of different examples on bound heterocyclic amines in grilled fish. In Example 1, 7 kinds of HAs (including α-carboline, β-carboline, quinoxaline and pyridine) were determined in the free state, and the total amount was 147.04 ng / g. In Examples 6-8, there was no significant difference in the inhibition rate of heterocyclic amines between Examples 6 and 7 (p>0.05), but both significantly inhibited the production of HAs compared with Example 1. And the inhibitory effect of Example 8 on HAs was slightly better than that of Examples 6 and 7. This may be because the encapsulation of the film-forming solution weakened the thermal degradation of TP, or there was a potential synergistic effect between the two. In summary, the inhibition rate of Example 8 on the total amount of heterocyclic amines in grilled fish was 67.93%.

[0120] The above description of the disclosed embodiments enables those skilled in the art to implement or use the present invention. Various modifications to these embodiments will be apparent to those skilled in the art, and the general principles defined herein can be implemented in other embodiments without departing from the spirit or scope of the present invention. Therefore, the present invention will not be limited to these embodiments shown herein, but rather to the widest scope consistent with the principles and novel features disclosed herein.

Claims

1. A method for reducing heterocyclic amines in grilled fish, characterized in that: The grilled fish is prepared by using a mixture of onions and ginger as a pickling liquid and one or more of carrageenan, xanthan gum, sodium carboxymethyl cellulose and tea polyphenols as a film-forming liquid.

2. The method according to claim 1, characterized in that The preparation method of the pickling liquid is: (1) preparing chopped onion and chopped ginger, and mixing the chopped onion and chopped ginger in a ratio of 1:1 to obtain a mixed solid; (2) The mixed solid material obtained in step (1) is added to the mixed brine at a solid-liquid ratio of 3%, and ultrasonically treated at a power of 480 W and 72° C. for 32 min to obtain a pickling liquid for later use.

3. The method according to claim 2, characterized in that The mixed brine is prepared according to a weight ratio of fish: ice water: salt = 100:100:1.

5.

4. The method according to claim 1, characterized in that: The preparation method of the film-forming solution is: Add 2.0% (w / v) glycerol to the water as a cosolvent, and then add one or more of carrageenan, xanthan gum, sodium carboxymethyl cellulose, and tea polyphenols. Then, heat and stir at 2000 r / min for 0.5 h in a 60°C constant temperature water bath with an overhead stirrer. After stirring, place in a 50°C constant temperature water bath for later use.

5. The method according to claim 4, characterized in that The one or more of the carrageenan, xanthan gum, sodium carboxymethyl cellulose and tea polyphenols include any one of 1.0% (w / v) carrageenan, 1.0% (w / v) xanthan gum, 0.5% (w / v) sodium carboxymethyl cellulose, 1.0% (w / v) sodium carboxymethyl cellulose, 2.0% (w / v) sodium carboxymethyl cellulose, 2.0% (w / v) tea polyphenols and a combination of 1.0% (w / v) sodium carboxymethyl cellulose and 1.0% (w / v) tea polyphenols.

6. The method according to any one of claims 1 to 5, characterized in that: The method for reducing heterocyclic amines in grilled fish comprises the following steps: Pre-treatment: the raw fish is slaughtered, cut open, cleaned and cut into pieces; Marinate: Place the fish in the marinade solution after back-cutting and marinating for 3 hours; Coating: Dip the pickled fish body into the film-forming liquid for coating; Baking: Bake the coated fish at 280°C for 13 minutes.

7. The method according to claim 6, characterized in that The raw material fish includes frozen fish or fresh fish, and the raw material fish includes grass carp, sea bass, catfish or basa fish.

8. The method according to claim 6, characterized in that The water temperature during pickling is 8° C.-10° C.; the pickling liquid is used only once each time, and the mixture is rolled and kneaded for 10 minutes at a speed of 6 rpm; after rolling and kneading, the mixture is allowed to stand and pickle for 3 hours, and is turned over once every half an hour.

9. The method according to claim 6, characterized in that The specific coating method comprises: placing the pickled fish body into the film-forming liquid and dipping it for 5 minutes, taking it out and placing it in a ventilated and cool place to dry.

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