Method for preparing hydrogen-rich water pickled fish

Abstract

The application belongs to the technical field of food processing, and particularly relates to a preparation method of hydrogen-rich water pickled fish. The method comprises the following steps: removing the internal organs, scales and gills of raw fish, cleaning and arranging the fish, and draining the fish to obtain pretreated fish meat; preparing a salt water pickling solution; using a pre-hydrogenation or process hydrogenation method to make the dissolved hydrogen concentration in the pickling system reach 0.1-2.1 ppm; mixing the fish meat with the pickling solution, and sealing and pickling the mixture at 0-8 DEG C for 1-24 h to obtain a pickled fish product. The hydrogen-rich water has the characteristics of low viscosity, high permeability and selective free radical scavenging, which can promote the rapid and uniform penetration of salt, inhibit lipid oxidation and excessive protein cross-linking, maintain stable color and improve tenderness, and can reduce the TBARS value by 10%-20%. The hydrogen-rich water is natural, safe and residue-free, and does not need to add chemical antioxidants. The method realizes the synergistic effect of efficient pickling promotion and quality regulation, and provides a new technical path for green processing of aquatic products.

Description

Technical Field

[0001] This invention belongs to the field of food processing technology, and specifically relates to a method for preparing fish pickled in hydrogen-rich water. Background Technology

[0002] Traditional fish curing typically uses liquid or dry curing, which suffers from long curing cycles and uneven salt penetration, leading to salt accumulation on the surface of the fish meat and uneven salt penetration throughout. During curing and subsequent storage, lipids and proteins in the fish meat are prone to oxidation, causing browning, texture deterioration, and flavor loss, thus affecting product acceptability. To address the low curing efficiency and lipid oxidation issues of traditional curing methods, physical aids such as vacuum, ultrasound, and high pressure are commonly used. However, these techniques are expensive, complex, and can damage the muscle fiber structure of the fish meat, resulting in a soft and inelastic texture. Furthermore, while the addition of antioxidants, such as ascorbic acid, tea polyphenols, or butylated hydroxyanisole (BHA), can delay oxidation to some extent, their widespread application in high-quality seafood curing products is limited by high raw material costs and consumer demands for clean labels and natural, additive-free products. Therefore, there is an urgent need to develop a fish curing method that combines low cost, high efficiency, and quality preservation.

[0003] Hydrogen (H2) is a gas with a small molecular weight and strong diffusivity. When dissolved in water, it forms hydrogen-rich water, giving the pickling solution the potential to both promote mass transfer and provide antioxidant protection. Previous studies have shown that hydrogen-rich water has low surface tension and high diffusivity, which can improve the wetting, penetration, and migration behavior of aqueous media on the surface and within the pores of materials. Research by Özcan et al. found that hydrogen-rich water can enhance the solvent's permeability in the pores of materials, thereby increasing the extraction rate of target components. [1] Alwazeer et al. found that hydrogen-rich water can significantly improve the leaching efficiency of olive leaf polyphenols by improving the solvent diffusion rate. [2]The above research indicates that hydrogen-rich water can not only be used as a common aqueous medium, but may also promote the mass transfer of solutes in biological tissues by reducing interfacial resistance, improving diffusion efficiency, and enhancing pore permeability. In traditional fish pickling, salt and flavor compounds in the pickling mixture mainly diffuse into the fish meat through a concentration gradient. However, the dense structure of fish muscle fibers and relatively narrow interstitial spaces result in slow penetration of the pickling solution, easily leading to uneven local salt concentration distribution, tissue dehydration, and textural degradation. Introducing hydrogen-rich water into the pickling system, its lower surface tension and stronger permeability help improve the flow and diffusion of the pickling solution on the surface of the fish meat and in the micropores, promoting faster and more uniform entry of salt and flavor compounds into the tissue, thereby improving pickling efficiency without the addition of chemical penetration enhancers. Simultaneously, hydrogen has certain antioxidant activity, which can alleviate lipid and protein oxidation caused by salt stress, oxygen pressure changes, and enzymatic reactions during the pickling process, reducing color deterioration, flavor loss, and nutrient loss. Compared to methods like vacuum pickling, ultrasonic-assisted pickling, and high-pressure treatment, which rely on specialized equipment and complex parameter control, hydrogen-rich water pickling has relatively lower equipment requirements and a simpler process flow, thus possessing the potential to reduce process complexity and control overall processing costs. Based on this advantage, hydrogen-rich water, as a pickling medium for fish, can accelerate salt penetration, shorten pickling time, and inhibit oxidative deterioration, achieving synergistic effects in multiple aspects. However, current research on hydrogen-rich water mainly focuses on aquatic product preservation, conventional soaking treatment, and extraction of plant active ingredients. In the context of fish pickling, there is still a lack of technical solutions that use hydrogen-rich water as a pickling medium to simultaneously improve pickling efficiency and maintain quality. Therefore, it is necessary to develop or improve a method for preparing fish pickled with hydrogen-rich water. Summary of the Invention

[0004] Based on this, in order to solve the problems of low efficiency in fish marinating and lipid oxidation, the present invention provides a method for preparing fish marinated in hydrogen-rich water.

[0005] This invention is achieved through the following technical solution: A method for preparing fish pickled in hydrogen-rich water includes the following steps: (1) Raw material pretreatment: Remove the internal organs, scales and gills from the raw fish, clean it and shape it as needed, drain the surface water to obtain pre-treated fish meat. (2) Preparation of pickling solution: Salt and water are mixed evenly to form a brine pickling solution; (3) Low-temperature sealed pickling: The pretreated fish meat is mixed with the marinade and then sealed and marinated at 0-8°C. After marinating, the marinated fish product is obtained.

[0006] Furthermore, the fish mentioned in step (1) include one or more of freshwater fish and saltwater fish.

[0007] Furthermore, the salt concentration of the brine in step (2) is 2% to 18%.

[0008] Furthermore, the mass ratio of the pretreated fish meat to the marinade in step (3) is 1:(1~6).

[0009] Furthermore, the marinating time for the sealed marinating process described in step (3) is 1 to 24 hours.

[0010] Furthermore, it also includes hydrogen permeation treatment: The dissolved hydrogen concentration in the pickling system is achieved to be 0.1–2.1 ppm by at least one of the following methods: (a) Pre-hydrogenation: Before the mixing in the low-temperature sealed pickling step, hydrogen gas is introduced into the pickling liquid to obtain hydrogen-rich brine; (b) Hydrogen introduction in the process: Hydrogen gas is introduced into the pickling system during the pickling process after the mixing in the low-temperature sealed pickling step.

[0011] Furthermore, when using pre-hydrogen purging, the hydrogen purging time is 1~60 min, the hydrogen flow rate is 10~3000 mL / min, the hydrogen purity is not less than 99.9%, and the hydrogen purging is stopped when the dissolved hydrogen concentration reaches 0.1~2.1 ppm.

[0012] Furthermore, when hydrogen is introduced during the pickling process, continuous or intermittent aeration is adopted, with a single aeration time of 1 to 60 minutes and a total aeration time of not less than 1 / 4 of the pickling time, and the dissolved hydrogen concentration of the system is controlled to be stable at 0.1 to 2.1 ppm.

[0013] Furthermore, the pickling process is carried out using sealed bags, airtight containers, or vacuum packaging containers.

[0014] The present invention has the following advantages over the prior art: (1) Effectively promotes salt penetration: The molecular weight of H2 in hydrogen-rich water is extremely small, which can effectively reduce the viscosity of the pickling solution, weaken the steric hindrance of salt diffusion, and promote the penetration of Na+. + With Cl - It migrates quickly, deeply, and evenly into the fish meat, thus achieving efficient and uniform flavor penetration.

[0015] (2) Maintain color stability: Hydrogen-rich water has a low oxidation-reduction potential. H2 can selectively neutralize strong oxidizing reactive oxygen species such as hydroxyl radicals (·OH), inhibit myoglobin oxidation to methemoglobin, slow down browning and discoloration, and maintain the color and surface gloss of fish meat.

[0016] (3) Improve the tenderness of fish meat: H2 penetrates into the muscle fibers, removes reactive oxygen species induced by salt stress, reduces carbonylation modification and disulfide bond formation of myofibril proteins, inhibits excessive cross-linking of proteins and irreversible contraction of muscle fibers, thereby reducing the hardness of fish meat and improving tenderness.

[0017] (4) Inhibition of lipid oxidation: H2 penetrates the cell membrane and enters the lipid bilayer, specifically neutralizing ·OH and blocking the chain reaction of lipid peroxidation. During the pickling process, H2 continuously accumulates in the interstitial space, forming a dynamic "hydrogen-rich microenvironment," maintaining a local low redox potential, and inhibiting the formation of lipid hydroperoxides and malondialdehyde. Experimental results show that pickling in hydrogen-rich brine can reduce the TBARS value (thiobarbituric acid reaction product) by 10%~20%, effectively delaying the deterioration of quality during storage.

[0018] (5) Natural, green and safe: Hydrogen-rich water is a natural, green, safe and residue-free treatment medium. No chemical antioxidants need to be added. Hydrogen can be naturally released during pickling and storage without producing harmful residues. While improving the quality of fish and meat and storage stability, it is more in line with the development trend of clean label, natural health and food inherent safety. Detailed Implementation

[0019] To further explain the present invention, the following specific embodiments are described.

[0020] Example 1: A method for preparing fish pickled in hydrogen-rich water, comprising the following steps: Raw material pretreatment: Remove the internal organs, scales and gills from fresh spotted catfish (freshwater fish), wash and remove the bones to obtain fish fillets, drain the surface water to obtain pretreated fish meat.

[0021] Preparation of pickling solution: Mix salt and water to form a brine pickling solution, wherein the salt concentration is 2% by mass.

[0022] Hydrogen purging treatment: Hydrogen gas is introduced into the pickling solution, and the hydrogen concentration is measured with a hydrogen pen to make the dissolved hydrogen concentration in the brine reach 0.4 ppm, thus obtaining hydrogen-rich brine; Low-temperature sealed marinating: The pretreated fish meat and hydrogen-rich brine are mixed at a mass ratio of 1:1 and sealed and marinated at 4°C for 24 hours. Example 2: Basically the same as Example 1, except that the dissolved hydrogen concentration was measured and controlled to be 0.5 ppm using a hydrogen pen during the hydrogen treatment.

[0023] Example 3: Basically the same as Example 1, except that the dissolved hydrogen concentration was measured and controlled to be 0.6 ppm using a hydrogen pen during the hydrogen treatment.

[0024] Example 4: Basically the same as Example 1, except that the dissolved hydrogen concentration was measured and controlled to be 0.7 ppm using a hydrogen pen during the hydrogen treatment.

[0025] Example 5: Basically the same as Example 1, except that the dissolved hydrogen concentration was measured and controlled to be 0.8 ppm using a hydrogen pen during the hydrogen treatment.

[0026] Comparative Example 1: Basically the same as Example 1, except that the pickling solution is pure water (without added salt) and no hydrogen treatment is performed.

[0027] Comparative Example 2: Basically the same as Example 1, except that: no hydrogen treatment was performed (i.e., pickling was done with ordinary brine, with a dissolved hydrogen concentration of 0 ppm).

[0028] Comparative Example 3: It is basically the same as Example 1, except that hydrogen treatment is not performed, but tea polyphenols with a mass concentration of 0.05% are added as an antioxidant in the preparation of the pickling solution.

[0029] Comparative Example 4: Basically the same as Example 1, except that: no hydrogen treatment was performed, and the packaging container was vacuum-sealed during the sealed pickling process.

[0030] The following examples use the spotted catfish as an example. The technical solution of the present invention is also applicable to all freshwater fish, marine fish and various fish processed products that include pickling processes, including but not limited to raw pickled fish, fermented fish, drunken fish, etc.

[0031] Detection methods (1) Salt permeability measurement A portable salinity meter was used to insert a probe 1 cm into the back of the fish to measure the penetration of salt into the inner layer.

[0032] (2) Color difference measurement Measurements are taken using a high-precision colorimeter, which needs to be calibrated before use.

[0033] (3) Texture determination The fish meat was cut into 2 cm × 2 cm × 2 cm pieces. Elasticity was tested using a cylindrical probe of model P / 50. The speed before the test was 1 mm / s, the test speed was 1 mm / s, and the speed after the test was 1 mm / s. The compression ratio was 50%, the trigger force was 5.0 g, the interval between two compressions was 5 s, and the number of repetitions was ≥3.

[0034] (4) Malondialdehyde determination Refer to GB 5009.181-2016 "Determination of malondialdehyde in food".

[0035] Table 1 Internal salt permeation of each embodiment and comparative example ; Table 2 Color difference between each embodiment and the comparative example ; Table 3. Texture of each embodiment and comparative example ; Table 4. Malondialdehyde content (mg / kg) in each example and comparative example ; In summary, based on the data in Tables 1-4, it can be seen that the hydrogen-rich water pickling treatment used in this invention can simultaneously improve the pickling efficiency of fish and enhance product quality. Regarding salt penetration, the inner layer salt content of Examples 1-5 at 2 h, 12 h, and 24 h was significantly higher than that of the ordinary brine pickling group (Comparative Example 2). Specifically, Example 1 achieved a salt penetration value of 0.65±0.01 at 24 h, significantly higher than the 0.48±0.02 of Comparative Example 2, indicating that the hydrogen-rich system can promote the diffusion and uniform distribution of salt into the fish meat, thus improving pickling efficiency. In terms of color indicators, the example groups generally exhibited higher L values ​​and lower a* values, indicating that hydrogen-rich treatment can effectively slow down browning and oxidative discoloration of the fish meat. Example 3 showed the closest overall color difference index to the fresh state, demonstrating that appropriate concentrations of hydrogen-rich treatment have a positive effect on maintaining the overall color stability of the fish meat. Regarding textural properties, the hardness, elasticity, and chewiness of the example groups remained within a reasonable range. Example 3 exhibited the best elasticity (0.70±0.01 N) and chewiness (11.59±1.33 N) among the example groups, indicating that hydrogen-rich treatment helps maintain muscle tissue structural stability and reduces damage to myofibril proteins caused by salt stress and oxidation. Comparative Examples 1 and 3 showed hardness values ​​of 34.33±1.31 N and 36.18±1.02 N, respectively, significantly higher than the example groups, suggesting that tissue shrinkage and textural degradation are more likely to occur under ordinary treatment conditions. In terms of lipid oxidation control, the malondialdehyde (MDA) content in the example groups after 5 days of refrigeration was lower than that in the comparative examples. Examples 2 and 3 showed the lowest levels at 0.94±0.02 mg / kg, significantly lower than the 1.19±0.01 mg / kg in the ordinary brine-cured group, indicating that hydrogen-rich treatment effectively inhibits lipid peroxidation and delays quality decline during storage. Considering all indicators, Example 3 demonstrates superior performance in terms of color, texture, and lipid oxidation control, making it the optimal implementation scheme of this invention. This invention achieves a comprehensive effect of promoting salt penetration, maintaining color stability, improving texture quality, and inhibiting lipid oxidation through the synergistic regulation of mass transfer performance and oxidative environment of the pickling system by hydrogen-rich brine. This method is simple, requires no complex equipment, and can improve the quality of pickled fish products, demonstrating good industrial application value and promising prospects for promotion.

[0036] The specific embodiments described above further illustrate the purpose, technical solution, and beneficial effects of the present invention. It should be understood that the above description is only a specific embodiment of the present invention and is not intended to limit the scope of protection of the present invention. Any modifications, equivalent substitutions, improvements, etc., made within the spirit and principles of the present invention should be included within the scope of protection of the present invention.

Claims

1. A method for preparing fish pickled in hydrogen-rich water, characterized in that, Includes the following steps: (1) Raw material pretreatment: Remove the internal organs, scales and gills from the raw fish, clean it and shape it as needed, drain the surface water to obtain pre-treated fish meat. (2) Preparation of pickling solution: Salt and water are mixed evenly to form a brine pickling solution; (3) Low-temperature sealed pickling: The pretreated fish meat is mixed with the marinade and then sealed and marinated at 0-8°C. After marinating, the marinated fish product is obtained.

2. The method for preparing hydrogen-rich water-marinated fish according to claim 1, characterized in that, The fish mentioned in step (1) include one or more of freshwater fish and saltwater fish.

3. The method for preparing hydrogen-rich water-marinated fish according to claim 1, characterized in that, The salt concentration of the brine in step (2) is 2% to 18%.

4. The method for preparing hydrogen-rich water-marinated fish according to claim 1, characterized in that, The mass ratio of the pretreated fish meat to the marinade in step (3) is 1:(1~6).

5. The method for preparing hydrogen-rich water-marinated fish according to claim 1, characterized in that, The marinating time for the sealed marinating process described in step (3) is 1 to 24 hours.

6. The method for preparing hydrogen-rich water-marinated fish according to claim 1, characterized in that, It also includes hydrogen permeation treatment: The dissolved hydrogen concentration in the pickling system is achieved to be 0.1–2.1 ppm by at least one of the following methods: (a) Pre-hydrogenation: Before the mixing in the low-temperature sealed pickling step, hydrogen gas is introduced into the pickling liquid to obtain hydrogen-rich brine; (b) Hydrogen introduction in the process: Hydrogen gas is introduced into the pickling system during the pickling process after the mixing in the low-temperature sealed pickling step.

7. The method for preparing hydrogen-rich water-marinated fish according to claim 6, characterized in that, When using pre-hydrogen purging, the hydrogen purging time is 1~60 min, the hydrogen flow rate is 10~3000 mL / min, the hydrogen purity is not less than 99.9%, and the hydrogen purging is stopped when the dissolved hydrogen concentration reaches 0.1~2.1 ppm.

8. The method for preparing hydrogen-rich water-marinated fish according to claim 6, characterized in that, When hydrogen is introduced during the pickling process, continuous or intermittent aeration is adopted, with a single aeration time of 1 to 60 minutes and a total aeration time of not less than 1 / 4 of the pickling time. The dissolved hydrogen concentration in the system is controlled to be stable at 0.1 to 2.1 ppm.

9. The method for preparing hydrogen-rich water-marinated fish according to claim 1, characterized in that, The pickling process is carried out using sealed bags, airtight containers, or vacuum-packed containers.