Color indicator for assessing the freshness of meat and fish products

Abstract

FIELD: food industry.SUBSTANCE: color indicator for monitoring the freshness of meat and fish products. The proposed color indicator for assessing the freshness of meat and fish products is made on a carrier and consists of genipin and a carrier material. The color indicator is a polysaccharide gel. The carrier material is cellulose fiber in the form of fabric or paper. In the first embodiment, the polysaccharide gel includes polysaccharide in a concentration of 1–5 wt.% and genipin in a concentration of 0.001–0.025 wt.%, the rest is water up to 100 wt.%. Preferably, the polysaccharide is any of the polysaccharides selected from the group: carrageenan, pectin, alginate. In the second embodiment, the polysaccharide gel includes agarose at a concentration of 2–5 wt.% and genipin at a concentration of 0.001–025 wt.%, the rest is water up to 100 wt.%.EFFECT: creating a color indicator that is resistant to erosion in an aqueous environment, does not migrate in a humid environment, and also provides guaranteed color indication of biogenic amines in food products at concentrations characteristic of spoilage processes.3 cl, 1 tbl, 1 ex

Description

[0001] The invention relates to the food industry, specifically to freshness control sensors for food products. More specifically, the present invention relates to a color indicator for monitoring the freshness of meat and fish products.

[0002] Food safety is a global issue and a priority area for scientific research and practical work in the food industry. Food safety systems are more effectively implemented in developed countries. This explains the large number of food crises in developing countries, especially in Asia. Meat continues to play an important role in the human diet, providing high-quality protein, healthy fatty acids, and trace elements essential for maintaining human health.

[0003] Basic foods included in the daily diet can contain many types of biogenic amines (hereinafter BA) in varying concentrations. Excessive consumption of foods containing BAs is hazardous to health, as their excess in the human body can cause various diseases associated with their effects on the nervous and digestive systems, as well as blood pressure. Amines are known to cause cancer due to their ability to react with nitrite salts, resulting in the formation of carcinogenic organic compounds (nitrosamines). These effects include psychoactive, vasodilatory, and hypertensive effects, as well as respiratory and neurological disorders. The number of cases of poisoning associated with BAs in food has increased, increasing the need for BA detection to ensure food safety.

[0004] Since there are no regulations regarding the permissible content of 1,4-diaminobutane (putrescine) in food products, meat and fish quality assessment is crucial to ensuring product safety and meeting consumer expectations. A thorough understanding of the presence of AB in food is essential for many food industries. The development of a simple and effective method for on-site meat freshness determination is clearly needed.

[0005] Biogenic amines (BAs) are low-molecular-weight biomolecules with organic basic functional groups (amino groups) that are formed through microbial decarboxylation of amino acids in fermented foods and beverages. Putrescine can be considered an indicator of food freshness and quality, as its levels increase as food spoils.

[0006] The toxicity of BAs is closely linked to histamine and tyramine. Phenylethylamine, putrescine, and cadaverine are important because they can enhance the negative effects of histamine. BAs are generally considered hazardous to health, and monitoring their levels in food is critical; high concentrations can lead to health problems.

[0007] The high microbial counts typical of fermented foods lead to a significant accumulation of biogenic amines. However, within the same type of product, amine content can vary significantly. These differences depend on many factors: the qualitative and quantitative composition of the microbial flora, chemical and physical parameters, hygienic procedures used during production, and the presence of precursors.

[0008] Traditional methods used to assess biogenic amine content in food products are typically time-consuming and resource-intensive, and lack the ability to perform on-site analysis. Currently, one of the most popular methods is the "electronic nose," which uses metal oxide-based semiconductor sensors.

[0009] Methods that have replaced colorimetry are used to measure BA concentrations. These include high-performance liquid chromatography (HPLC) with fluorescence, electrochemical, and mass spectrometric detection, and gas chromatography (GC) with mass spectrometric detection. These methods provide high sensitivity, specificity, and measurement accuracy; however, their use requires expensive equipment and reagents, as well as highly qualified personnel. The capillary isotachophoretic method is also frequently used in scientific papers (European food research & technology. Volume 235, Issue 3, Pagination 563–572, ISSN 1438-2377).

[0010] A new fluorescent probe based on rhodol RSMA (formyl-rhodol Schiff base with methoxyaniline) was developed for the detection of putrescine. Although RSMA is moderately reactive to some aliphatic diamines, its selectivity for putrescine is among the best (Talanta, Volume 270, 1 April 2024, Page 125615).

[0011] Disposable chemiluminescent biosensors are proposed and compared with HPLC combined with pre-column derivatization. The biosensors are based on enzymatic oxidation to 4-aminobutyraldehyde using putrescine oxidase or diamine oxidase as catalysts.

[0012] The closest analogue of the invention can be chosen to be the colorimetric paper sensor described in the article by Maria Maddalena Calabretta, Denise Gregucci, etc. “Colorimetric Paper Sensor for Food Spoilage Based on Biogenic Amine Monitoring”, Biosensors 2023, 13, https: / / doi.org / 10.3390 / bios13010126.

[0013] However, this analogue has the following disadvantages:

[0014] - the 1.5% agarose used in the analogue is not enough to retain genipin, and when water drops get in or when the sensor gets into an aqueous medium, the agarose-genipin indicator system is washed out, as a result of which the sensor fails;

[0015] - agarose-genipin system, where the agarose concentration is 1.5% - it is quite mobile in a humid environment and can migrate to meat, coloring it blue.

[0016] Thus, existing methods for detecting asthma lack simple, informative, and convenient on-site methods. The claimed invention aims to address these shortcomings.

[0017] The objective of the present invention is to develop a product that is free from the aforementioned disadvantages, specifically, to develop a design for a color indicator for placement inside food packaging, which, by changing color, signals the onset of spoilage processes in meat, fish, meat and fish products.

[0018] For the purposes of this invention, meat products are understood to mean products obtained from the processing of meat from slaughtered animals (domestic, commercial) and poultry, as well as those manufactured using (according to the recipe) a mass fraction of meat exceeding 60%. These include sausages and sausage products; semi-finished products; meat delicacies;

[0019] canned meat.

[0020] Also, within the scope of the present invention, fish products are understood to mean products of processing of objects of the fishing industry: fish, mammals, invertebrates and algae.

[0021] The claimed technical effect is achieved by combining an indicator test system based on genipin (methyl (1S, 2R, 6S) -2-hydroxy-9- (hydroxymethyl) -3-oxabicyclo [4.3.0] nona-4,8-diene-5-carboxylate) and a carrier material, where:

[0022] - indicator test system is a polysaccharide gel, including polysaccharide at a concentration of 1-5 mass% and genipin at a concentration of 0.001-0.025 mass%, the rest is water.

[0023] - the carrier material is cellulose fiber in the form of fabric or paper.

[0024] In one embodiment of the claimed invention, the polysaccharide is agarose at a concentration of 2-5 mass%.

[0025] According to the present invention, a color indicator for assessing the freshness of meat and fish products is also proposed, made on a carrier and consisting of genipin and a carrier material, characterized in that the color indicator is a polysaccharide gel including agarose at a concentration of 2-5 mass% and genipin at a concentration of 0.001-0.025 mass%, the rest is water, and the carrier material is cellulose fiber in the form of fabric or paper.

[0026] The carrier material is immersed in the indicator test system for impregnation, and then dried at a temperature of 18-22°C for 12-24 hours until solidification (loss of at least 70% water).

[0027] The technical result of the invention consists of creating a color indicator that is resistant to leaching in an aqueous environment and does not migrate in a humid environment. It also provides guaranteed color indication of biologically active substances in food products at concentrations characteristic of spoilage processes. This technical result is achieved by the entire set of features presented in the claims.

[0028] The technical result is achieved through the use of gelling polysaccharides that form “ion-crosslinked” gels in the presence of Ca ions 2+At concentrations starting from 1%. The structure of these hydrogels was found to be less susceptible to genipin migration from the gel to the outside, compared to agarose gels at concentrations of 1 to 2%. At the same time, increasing the agarose concentration to 2% eliminates genipin migration to the outside, as well as the washout by the aqueous medium characteristic of the known solution. On the other hand, the maximum concentration of all gel types is limited to 5%, since at higher concentrations, the gel does not penetrate the fibers of the substrates used.

[0029] The claimed invention is illustrated by the following example. It is understood by those skilled in the art that this example is not limiting but is provided to better understand the essence of this invention.

[0030] Example 1

[0031] The experiment was conducted using test systems based on various polysaccharides capable of forming hydrogels. For this, a solution containing genipin and a polysaccharide solution was prepared at 60°C. The solutions were then mixed in proportions until the required concentrations were achieved and cooled to room temperature. The resulting gel was applied to a fibrous material, which was dried at room temperature. The resulting composite reacted with putrescine and cadaverine, changing color from white to blue.

[0032] The performance of the indicator material was assessed using samples of fresh ground chicken, where concentrations ranging from 2 mg / kg (initial stages of spoilage) to 20 mg / kg (advanced spoilage) were added to simulate the spoilage process. Sensor performance was assessed using two criteria:

[0033] 1. Color change from white to blue in the putrescine and / or cadaverine concentration range from 2 to 20 mg / kg. If color appears at 2 mg / kg of putrescine and / or cadaverine and subsequently increases to 20 mg / kg, the result is considered positive and marked with a "+" sign; otherwise, the result is considered negative and marked with a "-" sign.

[0034] 2. Ability to adhere to fibrous materials such as fabric or paper. The adhesion and penetration properties were assessed as the uniformity of genipin distribution throughout the fibrous material. If the distribution was uniform, the result was considered positive and marked with a "+" sign; otherwise, the result was considered negative and marked with a "-" sign.

[0035] 3. No migration of the dyed test system. Migration was assessed by the transition of the blue color from the fibrous material to the ground chicken. If there was no color, the result was considered positive and marked with a "+" sign; otherwise, the result was considered negative and marked with a "-" sign.

[0036] Concentration, wt% Type of polysaccharide Concentration mg / kg Result Comment Genipin Polysaccharide Putrescine Cadaverine 0,0005 0,5 Agarose - - (-) The gel is unable to adhere to fibrous materials due to its high fluidity. 0,0005 1 Agarose 3 - 20 - (-) Minor change in the color of the test system 0,001 1 Agarose 3 - 20 - (-) Migration of the test system in a humid environment onto the product. 0,001 1 Agarose - 3 - 20 (-) Migration of the test system in a humid environment onto the product. 0,001 1 Agarose 3 - 10 3 - 10 (-) Migration of the test system in a humid environment onto the product. 0,01 1 Agarose 2 - 10 2 - 10 (-) Migration of the test system in a humid environment onto the product. 0,1 1 Agarose 2 - 10 2 - 10 (-) Migration of the test system in a humid environment onto the product. 0,5 1 Agarose 2 - 10 2 - 10 (-) Migration of the test system in a humid environment onto the product. 1 1 Agarose 2 - 10 2 - 10 (-) Hypersensitivity, unable to detect increases in amine concentrations. 0,001 1,5 Agarose 2 - 10 2 - 10 (-) Analogue. Migration of the test system in a humid environment onto the product. 0,001 2 Agarose 2 - 10 2 - 10 (+) 0,5 2 Agarose 2 - 10 2 - 10 (+) 0,001 3 Agarose 2 - 10 2 - 10 (+) 0,5 3 Agarose 2 - 10 2 - 10 (+) 0,001 4 Agarose 2 - 10 2 - 10 (+) 0,5 4 Agarose 2 - 10 2 - 10 (+) 0,001 5 Agarose 2 - 10 2 - 10 (+) 0,5 5 Agarose 2 - 10 2 - 10 (+) 0,001 6 Agarose 2 - 10 2 - 10 (-) The gel is unable to impregnate the fibrous material due to low fluidity. 0,001 0,5 Pectin - - (-) The gel is unable to adhere to fibrous materials due to its high fluidity. 0,001 1 Pectin 2 - 10 2 - 10 (+) 0,5 1 Pectin 2 - 10 2 - 10 (+) 0,001 2 Pectin 2 - 10 2 - 10 (+) 0,5 2 Pectin 2 - 10 2 - 10 (+) 0,001 3 Pectin 2 - 10 2 - 10 (+) 0,5 3 Pectin 2 - 10 2 - 10 (+) 0,001 4 Pectin 2 - 10 2 - 10 (+) 0,5 4 Pectin 2 - 10 2 - 10 (+) 0,001 5 Pectin 2 - 10 2 - 10 (+) 0,5 5 Pectin 2 - 10 2 - 10 (+) 0,001 6 Pectin 2 - 10 2 - 10 (-) The gel is unable to impregnate the fibrous material due to low fluidity. 0,001 0,5 Carrageenan (iota) - - (-) The gel is unable to adhere to fibrous materials due to its high fluidity. 0,001 1 Carrageenan (iota) 2 - 10 2 - 10 (+) 0,5 1 Carrageenan (iota) 2 - 10 2 - 10 (+) 0,001 2 Carrageenan (iota) 2 - 10 2 - 10 (+) 0,5 2 Carrageenan (iota) 2 - 10 2 - 10 (+) 0,001 3 Carrageenan (iota) 2 - 10 2 - 10 (+) 0,5 3 Carrageenan (iota) 2 - 10 2 - 10 (+) 0,001 4 Carrageenan (iota) 2 - 10 2 - 10 (+) 0,5 4 Carrageenan (iota) 2 - 10 2 - 10 (+) 0,001 5 Carrageenan (iota) 2 - 10 2 - 10 (+) 0,5 5 Carrageenan (iota) 2 - 10 2 - 10 (+) 0,001 6 Carrageenan (iota) 2 - 10 2 - 10 (-) The gel is unable to impregnate the fibrous material due to low fluidity. 0,001 1 Carrageenan (kappa) 2 - 10 2 - 10 (+) 0,001 5 Carrageenan (kappa) 2 - 10 2 - 10 (+) 0,001 1 Carrageenan (lambda) 2 - 10 2 - 10 (+) 0,001 5 Carrageenan (lambda) 2 - 10 2 - 10 (+) 0,001 0,5 Alginate (sodium) - - (-) The gel is unable to adhere to fibrous materials due to its high fluidity. 0,001 1 Alginate (sodium) 2 - 10 2 - 10 (+) 0,5 1 Alginate (sodium) 2 - 10 2 - 10 (+) 0,001 2 Alginate (sodium) 2 - 10 2 - 10 (+) 0,5 2 Alginate (sodium) 2 - 10 2 - 10 (+) 0,001 3 Alginate (sodium) 2 - 10 2 - 10 (+) 0,5 3 Alginate (sodium) 2 - 10 2 - 10 (+) 0,001 4 Alginate (sodium) 2 - 10 2 - 10 (+) 0,5 4 Alginate (sodium) 2 - 10 2 - 10 (+) 0,001 5 Alginate (sodium) 2 - 10 2 - 10 (+) 0,5 5 Alginate (sodium) 2 - 10 2 - 10 (+) 0,001 6 Alginate (sodium) 2 - 10 2 - 10 (-) The gel is unable to impregnate the fibrous material due to low fluidity. 0,001 1 Alginate (potassium) 2 - 10 2 - 10 (+) 0,001 5 Alginate (potassium) 2 - 10 2 - 10 (+) 0,001 1 Alginate (calcium) 2 - 10 2 - 10 (+) 0,001 5 Alginate (calcium) 2 - 10 2 - 10 (+)

[0037] As can be seen from the results presented in the table, the best results are shown by the composition of genipin with polysaccharide with the following ratio of components:

[0038] polysaccharide: 1-5 wt.%,

[0039] genipin: 0.001-0.5 wt%,

[0040] the rest is water up to 100 wt.%,

[0041] and also the composition:

[0042] agarose: 2-5 wt%,

[0043] genipin: 0.001-0.5 wt%,

[0044] the rest is water up to 100 wt%.

Claims

1. A color indicator for assessing the freshness of meat and fish products, made on a carrier and consisting of genipin and a carrier material, characterized in that the color indicator is a polysaccharide gel including a polysaccharide in a concentration of 1-5 wt.% and genipin in a concentration of 0.001-0.025 wt.%, the rest is water up to 100 wt.%, and the carrier material is cellulose fiber in the form of fabric or paper.

2. A color indicator according to claim 1, characterized in that the polysaccharide is any of the polysaccharides selected from the group: carrageenan, pectin, alginate.

3. A color indicator for assessing the freshness of meat and fish products, made on a carrier and consisting of genipin and a carrier material, characterized in that the color indicator is a polysaccharide gel including agarose at a concentration of 2-5 wt.% and genipin at a concentration of 0.001-0.025 wt.%, the rest is water up to 100 wt.%, and the carrier material is cellulose fiber in the form of fabric or paper.