阅读说明：本技术 一种提高硫胺素降解产物中肉香物质含量的方法及降解产物的应用 (Method for increasing content of meat flavor substances in thiamine degradation product and application of degradation product ) 是由 赵向东 何聪聪 杨贺 蒋丹丹 于 2019-09-10 设计创作，主要内容包括：本发明涉及一种提高硫胺素降解产物中肉香物质含量的方法及降解产物的应用,属于食品加工技术领域。通过将硫胺素盐酸盐、食品添加剂和溶剂加入密闭反应容器中,80-140℃下搅拌反应10-180min,反应结束后冷却,得到硫胺素降解产物。所述方法能大大提高硫胺素降解过程中肉香化合物的生成量,硫胺素降解产物可以直接用于反应香精制备中,增强肉香,降低成本。此外,通过食用油或辛癸酸甘油酯对硫胺素降解产物进行萃取分离干燥,获得肉香调味油,去除了口感中苦味物质,用于肉味反应或调香产品中,同样可起到增强肉感,降低成本作用,具有广阔的应用前景。(The invention relates to a method for improving the content of meat flavor substances in thiamine degradation products and application of the degradation products, and belongs to the technical field of food processing. Adding thiamine hydrochloride, a food additive and a solvent into a closed reaction container, stirring and reacting for 10-180min at 80-140 ℃, and cooling after the reaction is finished to obtain a thiamine degradation product. The method can greatly improve the generation amount of the meat flavor compounds in the thiamine degradation process, and the thiamine degradation products can be directly used in the preparation of reaction essences, so that the meat flavor is enhanced, and the cost is reduced. In addition, the thiamine degradation products are extracted, separated and dried through edible oil or caprylic capric glyceride to obtain the meat flavor seasoning oil, bitter substances in the taste are removed, and the meat flavor seasoning oil can be used in meat flavor reaction or flavor blending products, can also play a role in enhancing meat flavor and reducing cost, and has wide application prospects.)

1. A method for increasing the content of meat flavor substances in thiamine degradation products is characterized in that: the method comprises the following steps:

adding thiamine hydrochloride, a food additive and a solvent into a closed reaction container, stirring and reacting for 10-180min at 80-140 ℃, and cooling after the reaction is finished to obtain a thiamine degradation product;

wherein the food additive is food grade phosphate or food grade lactate;

the solvent is more than one of deionized water, glycerol and propylene glycol;

the mass ratio of the thiamine hydrochloride to the solvent is 1:1-1: 10;

the mass of the food-grade additive is 0.5-4.0% of the total mass of the thiamine hydrochloride and the solvent.

2. The method of claim 1, wherein the amount of meat flavor material in the thiamine degradation product is increased by: the food grade phosphate is more than one of disodium hydrogen phosphate, sodium dihydrogen phosphate, dipotassium hydrogen phosphate, potassium dihydrogen phosphate, sodium pyrophosphate and sodium tripolyphosphate.

3. The method of claim 1, wherein the amount of meat flavor material in the thiamine degradation product is increased by: the food grade lactate is sodium lactate or calcium lactate.

4. The method of claim 1, wherein the amount of meat flavor material in the thiamine degradation product is increased by: the mass ratio of the thiamine hydrochloride to the solvent is 1:1-1: 2.

5. The method of claim 1, wherein the amount of meat flavor material in the thiamine degradation product is increased by: the mass of the food-grade additive is 1-2% of the total mass of the thiamine hydrochloride and the solvent.

6. The method of claim 1, wherein the amount of meat flavor material in the thiamine degradation product is increased by: the reaction temperature is 100-120 ℃, and the reaction time is 60-150 min.

7. Use of a thiamine degradation product according to any one of claims 1 to 6, characterized in that: the thiamine degradation product is used as a raw material for preparing meat-flavor essence.

8. The use of a thiamine degradation product according to claim 7, wherein: extracting the thiamine degradation product by using an extracting agent, separating and drying to obtain meat-flavor seasoning oil; wherein the extracting agent is edible oil or caprylic/capric glyceride; the mass ratio of the extracting agent to the thiamine degradation product is 0.5:1-10: 1.

9. The use of a thiamine degradation product according to claim 7, wherein: the mass ratio of the extracting agent to the thiamine degradation product is 1:1-3: 1.

10. Use of a meat flavor oil according to claim 8, wherein: the meat flavor seasoning oil is used as a raw material for preparing meat flavor essence.

Technical Field

The invention relates to a method for improving the content of meat flavor substances in thiamine degradation products and application of the degradation products, and belongs to the technical field of food processing.

Background

Thiamine (vitamin B1) provides a meat flavor and is therefore commonly used to prepare savory reactive flavors. Thiamine is mainly available in the form of hydrochloride thiamine, and the price of thiamine is 300-500/Kg. Thiamine and derivatives thereof are mainly derived from chemical synthesis, have large price fluctuation due to requirements of raw materials and environmental protection, and are important raw materials in meat flavor, so that thiamine and derivatives thereof are considered as important factors influencing the cost of meat flavor.

The mechanism of thiamine degradation is shown in formula I, wherein the route 1 is that C-N connected with a methylene bridge of quaternary ammonium salt in thiamine is broken to generate thiazothiazole and pyrimidine compounds [ Journal of Food Science,1972,37 ]; route 2 is a C-N ring opening of the thiazole position 2 in thiamine, removing the functional group attached to the sulfur atom, to yield a pyrimidine compound and 5-hydroxy-3-mercapto-2-pentanone [ Annals of the New York Academy of sciences.2008,1126(1): 66-71; journal of Agricultural and Food chemistry 1990,38(3): 777-. The mercapto pentanone compound has high activity, can continue to react to form the meat flavor compound 2-methyl-3-mercapto furan, and can be further oxidized into bis (2-methyl-3-furyl) disulfide. The two compounds are important meat flavor compounds and play a main role in influencing thiamine meat flavor. The main compound generated by thiamine degradation is thiazoie, meat flavor compounds are generated rarely, and the meat flavor is changed by the trace difference of 2-methyl-3-sulfydryl furan and bis (2-methyl-3-furyl) disulfide although the usage amount of the disulfide in the meat flavor is ppm level. The two compounds are expensive in the market, usually 3000-.

In 1969, the product of thiamine hydrochloride was isolated by heating in phosphate buffered saline (pH 6.7) at 100 ℃ for 15min to obtain the formation of hydrogen sulfide, 2-methylthiophene, 2-methylfuran, and 2-methyl-4, 5-dihydrothiophene (j.agr.food Chem,1969,17, 390). In 1972, b.k.dwivedi and r.g.arnold adjusted the pH of the thiamine hydrochloride solution to 5.0, 6.0, 7.0 again by NaOH or phosphate buffer solutions and underwent thiamine degradation under three reaction conditions: 1. heating in sealed water bath at 100 deg.C for 30 min; 2. heating in water bath at 100 deg.C in air for 30 min; 3. the autoclave was heated at 121 ℃ for 30min, and then the degradation product thiazothiazole was identified and investigated for the growth rule (Journal of food science.1972,37,689). In 1973, the ratio of the thiothiazole degradation products to the total product of the thiamine degradation was investigated at different times (15min, 30min, 120min) by adjusting the pH of the thiamine hydrochloride solution to 3.5, 5.0, 6.0, 7.0, 8.0 using phosphate buffer solution (Journal of Food science.1973,37,866). In the same year, B.K.Dwivedi and R.G.Arnold were further adjusted to pH 5.0, 6.0, 7.0 and 8.4 by NaOH, left for 2 hours and then heated at 120 ℃ for 1 hour to investigate the formation of thiazoes, and the 2-acetyltetrahydrothiophenes produced by the degradation of thiamine were analyzed, while thiophenes were summarized (Journal of Food science.1973,38,450). Morfe, B.J.Liska adjusted various concentrations of thiamine hydrochloride solutions to 5.9, 7.4 by phosphate buffer followed by heating at 121 ℃ for 40min, and elemental sulfur was found to be generated (Journal of Dairy Science,1972,55, 123). In 1979, Joseph w.bell et al used phosphate-citrate buffer to adjust the pH of thiamine solution to 6.60 and studied the effect of different reactor materials on thiamine degradation at different reaction temperatures (70-90 ℃), and found that thiamine degradation occurred mainly in a homogeneous phase and was not greatly affected by reactor wall materials (j.agr.food chem.,1979,27, 384). In 2018, Adrienne Voelker et al studied the trends in the changes of thiamine hydrochloride and thiamine nitrate upon storage at 25, 40, 60, 70, 80 ℃ for 6 months and gave an explanation by the solubility of the two solutions, the pH of the solutions and their corresponding activation energies (Food research International,2018,112,443). In 2004, Shejechuan et al heated thiamine in 1, 2-propanediol by medium and high fire in a microwave oven for 5min, identified 26 kinds of sulfur compounds including thiophene, thiazole, sulfur substituted furan, aliphatic sulfur compounds, and carbonyl sulfur compounds, etc., wherein 2-methyl-3-furanthiol, 2-acetylthiophene compound has a characteristic structural unit of meat flavor compounds (food science, 2004,25, 241).

Although researchers have studied the above reaction rules, the reported methods for degrading thiamine by heating or adjusting pH (adjustment with NaOH solution or phosphate buffer solution) have only studied the effect of a specific pH on the major substances produced such as thiazoles and thiophenes, and have not studied the effect on the production of 2-methyl-3-mercaptofuran and bis (2-methyl-3-furyl) disulfide. Because of competitive reaction in the degradation process of thiamine, only by increasing the generation amount of two meat flavor compounds of 2-methyl-3-sulfydryl furan and bis (2-methyl-3-furyl) disulfide, the meat flavor essence can play a more important role in the production of the essence, the cost of the reactive essence is reduced, and meanwhile, the meat flavor of the reactive essence is improved.

Disclosure of Invention

In view of the above, an object of the present invention is to provide a method for increasing the content of meat-flavor substances in thiamine degradation products, which has the advantages of low production cost, high yield of meat-flavor compounds, stable process, simple operation, and suitability for mass production. The invention also aims to provide the application of the thiamine degradation product, the thiamine degradation product can be directly used as a semi-finished product raw material to be added into a reaction to prepare essence, the meat flavor of the product is improved, and high-concentration meat flavor seasoning oil can be obtained through extraction and separation of edible oil or caprylic-capric glyceride.

In order to achieve the above object, the technical solution of the present invention is as follows.

A method for increasing the content of meat-flavor substances in thiamine degradation products comprises the following steps:

adding thiamine hydrochloride, a food additive and a solvent into a closed reaction container, stirring and reacting for 10-180min at 80-140 ℃, and cooling after the reaction is finished to obtain a thiamine degradation product;

wherein the food additive is food grade phosphate or food grade lactate;

the solvent is more than one of deionized water, glycerol and propylene glycol;

the mass ratio of the thiamine hydrochloride to the solvent is 1:1-1: 10;

the mass of the food-grade additive is 0.5-4.0% of the total mass of the thiamine hydrochloride and the solvent.

Preferably, the food-grade phosphate is more than one of disodium hydrogen phosphate, sodium dihydrogen phosphate, dipotassium hydrogen phosphate, potassium dihydrogen phosphate, sodium pyrophosphate and sodium tripolyphosphate.

Preferably, the food grade lactate salt is sodium lactate or calcium lactate.

Preferably, the mass ratio of the thiamine hydrochloride to the solvent is 1:1-1: 2.

Preferably, the mass of the food-grade additive is 1-2% of the total mass of the thiamine hydrochloride and the solvent.

Preferably, the reaction temperature is 100-120 ℃, and the reaction time is 60-150 min.

The application of a thiamine degradation product which is used as a raw material for preparing meat-flavor essence.

The application of the thiamine degradation product comprises the steps of extracting the thiamine degradation product with an extracting agent, separating and drying to obtain meat flavor seasoning oil; wherein the extracting agent is edible oil or caprylic/capric glyceride; the mass ratio of the extracting agent to the thiamine degradation product is 0.5:1-10: 1. The edible oil comprises sunflower seed oil, rapeseed oil, rice oil, corn oil, linseed oil, peanut oil, soybean oil and the like.

Preferably, the mass ratio of the extracting agent to the thiamine degradation product is 1:1-3: 1.

The application of the meat flavor seasoning oil is used as a raw material for preparing meat flavor essence.

Has the advantages that:

the method can greatly improve the generation amount of the meat flavor compounds in the thiamine degradation process, the adopted phosphate or lactate raw materials are low in price, the reaction process and the operation are simple, the method is suitable for batch preparation, the thiamine degradation products can be directly used in the preparation of reaction essences, the meat flavor is enhanced, and the cost is reduced. In addition, the thiamine degradation products are extracted, separated and dried through edible oil or caprylic capric glyceride to obtain the meat flavor seasoning oil, bitter substances in the taste are removed, and the meat flavor seasoning oil can be used in meat flavor reaction or flavor blending products, can also play a role in enhancing meat flavor and reducing cost, and has wide application prospects.

Drawings

FIG. 1 is a gas chromatogram of a thiamine degradation product in comparative example 1;

FIG. 2 is a gas chromatogram of the thiamine degradation product in comparative example 2;

FIG. 3 is a gas chromatogram of the thiamine degradation product in comparative example 3;

FIG. 4 is a gas chromatogram of the thiamine degradation product in comparative example 4;

FIG. 5 is a gas chromatogram of the thiamine degradation product of example 1;

FIG. 6 is a gas chromatogram of the thiamine degradation product of example 2;

FIG. 7 is a gas chromatogram of the thiamine degradation product of example 3;

FIG. 8 is a gas chromatogram of the thiamine degradation product of example 4;

FIG. 9 is a gas chromatogram of the thiamine degradation product of example 5;

FIG. 10 is a gas chromatogram of the thiamine degradation product of example 6;

FIG. 11 is a gas chromatogram of the thiamine degradation product of example 7;

FIG. 12 is a gas chromatogram of the thiamine degradation product of example 8;

FIG. 13 is a gas chromatogram of the thiamine degradation product of example 9;

FIG. 14 is a gas chromatogram of the thiamine degradation product of example 10;

FIG. 15 is a gas chromatogram of the thiamine degradation product of example 11;

FIG. 16 is a gas chromatogram of the thiamine degradation product of example 12;

FIG. 17 is a gas chromatogram of a thiamine degradation product of example 13;

FIG. 18 is a gas chromatogram of a thiamine degradation product of example 14;

FIG. 19 is a gas chromatogram of a thiamine degradation product of example 15;

FIG. 20 is a gas chromatogram of a thiamine degradation product of example 16;

FIG. 21 is a gas chromatogram of a thiamine degradation product of example 17;

FIG. 22 is a gas chromatogram of a thiamine degradation product of example 18;

FIG. 23 is a gas chromatogram of a thiamine degradation product of example 19;

FIG. 24 is a gas chromatogram of a thiamine degradation product of example 20;

FIG. 25 is a gas chromatogram of the thiamine degradation product of example 21.

Detailed Description

The invention will be further described with reference to specific examples for better understanding of the present invention, but the scope of the present invention is not limited thereto.

The thiamine degradation products prepared in the comparative example and the example are analyzed by combining headspace-solid phase microextraction with gas chromatography-mass spectrometry (HS-SPME-GC-MS), and the adsorption needle of the solid phase microextraction adsorbs the fragrance, then is analyzed at a sample inlet of a gas chromatograph, and enters a mass spectrometer after being separated by a gas chromatographic column. The method comprises the following specific operations: accurately weighing 0.500g of sample in a 20ml sample bottle, carrying out pretreatment at the equilibrium temperature of 60 ℃, keeping the temperature for 20min, and adsorbing for 20 min. After the headspace-solid phase microextraction adsorption is completed, the adsorption needle is inserted into a sample inlet of the gas chromatography-mass spectrometer by an automatic sample injector and is analyzed for 5 min. DB-WAX capillary column (60m × 0.25mm, 0.25 μm); temperature programming: the initial temperature is 40 ℃, the temperature is kept for 3min, the temperature is increased to 230 ℃ at the speed of 3 ℃/min, and the temperature is kept for 10 min. The carrier gas is He, the constant flow rate mode is 1mL/min, the injection inlet temperature is 250 ℃, the pressure is 16.087psi, the split ratio is 5:1, and the spacer purge flow is 5 mL/min. Electron Impact (EI) ion source, electron energy 70eV, transmission line temperature 250 ℃, ion source temperature 230 ℃, quadrupole rod temperature 150 ℃, and mass scanning range m/z range 30-550. The peak area of the substance in the analysis result represents the relative content of each substance in the reaction product, and compared with the substance itself, the larger the peak area is, the higher the concentration is.

Comparative example 1:

and sequentially adding thiamine hydrochloride and deionized water into a reaction kettle with a magnetic rotor, wherein the mass ratio of the thiamine hydrochloride to the deionized water is 1: 1. The reaction mixture reacts for 1 hour at 80 ℃ and is cooled to obtain the thiamine degradation product. And extracting the degradation product by adopting sunflower seed oil, wherein the mass ratio of the sunflower seed oil to the thiamine degradation product is 1:1, and further separating and drying to obtain the meat flavor seasoning oil.

Performing HS-SPME-GC-MS analysis on the thiamine degradation product: as shown in FIG. 1, the total peak area of 2-methyl-3-mercaptofuran and bis (2-methyl-3-furyl) disulfide in the analysis result was 1.25X 10⁶。

Comparative example 2:

refer to the method reported in Journal of Food science.1972,37,689: sequentially adding thiamine hydrochloride and phosphate buffer solution (prepared from potassium dihydrogen phosphate and dipotassium hydrogen phosphate) into a reaction kettle with a magnetic rotor, adjusting the pH value to 5.0, reacting for 30 minutes at 121 ℃, and cooling to obtain a thiamine degradation product.

Performing HS-SPME-GC-MS analysis on the thiamine degradation product: as shown in FIG. 2, the total peak area of 2-methyl-3-mercaptofuran and bis (2-methyl-3-furyl) disulfide in the analysis result was 4.08X 10⁶。

Comparative example 3:

refer to the method reported in Journal of Food science.1972,37,689: sequentially adding thiamine hydrochloride and phosphate buffer solution (prepared from potassium dihydrogen phosphate and dipotassium hydrogen phosphate) into a reaction kettle with a magnetic rotor, adjusting the pH value to 6.0, reacting for 30 minutes at 121 ℃, and cooling to obtain a thiamine degradation product.

Performing HS-SPME-GC-MS analysis on the thiamine degradation product: as shown in FIG. 3, 2-formazan was contained in the analysis resultsThe total peak area of the yl-3-mercaptofuran and bis (2-methyl-3-furanyl) disulfide was 1.10X 10⁶。

Comparative example 4:

refer to the method reported in Journal of Food science.1972,37,689: adding thiamine hydrochloride and phosphate buffer solution (prepared from potassium dihydrogen phosphate and dipotassium hydrogen phosphate) into a reaction kettle with a magnetic rotor in sequence, adjusting the pH value to 7.0, reacting for 30 minutes at 120 ℃, and cooling to obtain a thiamine degradation product.

Performing HS-SPME-GC-MS analysis on the thiamine degradation product: as shown in FIG. 4, the formation of two carnosol compounds, 2-methyl-3-mercaptofuran and bis (2-methyl-3-furanyl) disulfide, was not detected in the results of the analysis.