Method for preparing tobacco flavor through polysaccharide Maillard reaction and application of tobacco flavor

Abstract

The invention belongs to the technical field of tobacco flavor preparation, and discloses a method for preparing tobacco flavor based on polysaccharide Maillard reaction and application of the tobacco flavor. The method comprises the following steps: dissolving amino acid and polysaccharide in a solvent according to a certain molar ratio to obtain a reaction material; putting the reaction materials into a reaction kettle, and carrying out Maillard reaction under a closed condition; and after the reaction is finished, rapidly cooling the reaction kettle to room temperature to obtain a Maillard reaction product. In the reaction process, polysaccharide is cracked into various reducing sugars step by step and is subjected to Maillard reaction with amino acid, so that the problems that monosaccharide participates in the Maillard reaction, the aroma is single, and the reaction is violent and difficult to control are effectively solved. When the tobacco flavor is applied to cigarettes, the irritation of smoke can be remarkably reduced, offensive odor can be covered, meanwhile, the smoke is softened, the aftertaste is improved, the smoke concentration is increased, and the baking fragrance and the sweet aftertaste are increased. The method is low in cost, simple in equipment and convenient to operate, can be put into production without modifying existing production equipment, and has a good industrial application prospect.

Description

A method for preparing tobacco flavorings by Maillard reaction of polysaccharides and its application Technical Field

[0001] This invention belongs to the field of tobacco flavoring technology, and particularly relates to a method for preparing tobacco flavorings by the Maillard reaction of polysaccharides and its application. Background Technology

[0002] In the tobacco industry, low-grade tobacco leaves suffer from sensory defects such as high irritation, bitter aftertaste, and insufficient aroma, which greatly affect their use in mid- to high-grade cigarettes. Cigarette manufacturers compensate for these sensory deficiencies by adding various flavorings when formulating cigarette recipes. Therefore, developing safe tobacco flavorings that can enhance the taste and aroma of cigarettes is essential.

[0003] The Maillard reaction is a common method for preparing tobacco flavorings. Essentially, it involves the transformation of reducing sugars and amino acids under heating conditions through carbonyl-amine condensation, rearrangement, sugar dehydration, sugar molecule breakage, and Strecker degradation, ultimately producing brown or even dark brown macromolecular substances. Among these, melanoidins account for more than 90%, while volatile aroma components are the minor products, accounting for less than 10%. These volatile substances mainly include furans, pyrans, pyrazines, pyridines, thiophenes, and thiazoles. Although they constitute a small proportion, many of these compounds have extremely low aroma thresholds, making them crucial to the style and quality of cigarettes.

[0004] Compared to monosaccharides, polysaccharides exhibit different sugar degradation behaviors in the Maillard reaction, thus significantly impacting the sensory properties of the Maillard reaction products. For example, Amadori compounds formed from glucose and amino acids undergo 1,2-enolization and 2,3-enolization to form 3-deoxyglucuronide and 1-deoxyglucodide intermediates; while disaccharides, influenced by 1,4-glycosidic bonds, specifically degrade into 4-deoxyglucosidone and 1,4-dideoxyglucodide intermediates. These different intermediates inevitably lead to differences in the types of final products and their sensory characteristics. Furthermore, kinetic studies show that oligosaccharides exhibit a relatively long induction period during browning, reacting slowly and requiring conversion into more reactive and smaller intermediates to participate in the reaction, thereby achieving the stepwise release of aroma compounds. Currently, there are few reports on technologies utilizing polysaccharide Maillard reactions to prepare tobacco flavorings to improve the sensory quality of low-grade tobacco leaves, especially regarding trisaccharides, which remain largely unexplored.

[0005] D-raffinose, one of the most abundant water-soluble oligosaccharides in the plant kingdom, is a naturally occurring compound composed of D-galactose, D-glucose, and D-fructose, found in soybeans, beets, cottonseed, cabbage, and other vegetables. It is a non-reducing trisaccharide, also known as metriose, and is a white crystalline powder. In recent years, D-raffinose has become a focus of research due to its excellent source of dietary fiber and prebiotics, and its potential to improve food quality, flavor, and physicochemical properties. For example, it can effectively reduce biofilm formation by attaching to carbohydrate-binding proteins and stimulate the growth of bifidobacteria and lactic acid bacteria in the gut. However, research on the role of D-raffinose in the Maillard reaction is still in its early stages, and its application value remains unclear. Summary of the Invention

[0006] This invention aims to overcome the shortcomings of existing technologies and provide a method for preparing tobacco flavorings by the Maillard reaction of polysaccharides. Using D-raffinose and amino acids as raw materials, the method achieves the synergistic process of polysaccharide stepwise cleavage and Maillard reaction by controlling the reaction conditions, thus solving the problems of insufficient aroma and uncontrollable intensity of the Maillard reaction of monosaccharides. At the same time, it provides the application of this flavoring in cigarettes to improve the sensory quality of low-grade tobacco leaves.

[0007] To achieve the above-mentioned objectives, the technical solution of the present invention is as follows:

[0008] A method for preparing tobacco flavorings via the Maillard reaction of polysaccharides includes the following steps:

[0009] (1) Dissolve amino acids and polysaccharides in a solvent at a molar ratio of (1-5):1, stir until homogeneous, and obtain the reaction material;

[0010] (2) Place the reactants in a high-temperature and high-pressure reactor, and adjust the temperature to 80℃~210℃ and the pressure to 0~1bar under sealed conditions, and carry out the Maillard reaction for 30min~120min.

[0011] (3) After the reaction is completed, the reactor is immediately cooled to room temperature to quench the reaction and obtain Maillard reaction tobacco fragrance product.

[0012] The amino acid is one or a combination of several of the following: serine, glycine, valine, proline, leucine, phenylalanine, lysine, and glutamic acid.

[0013] The polysaccharide is preferably D-raffinose.

[0014] The solvent is one or a combination of propylene glycol, glycerol, and water.

[0015] The application of tobacco flavoring prepared by the Maillard reaction of polysaccharides involves diluting the tobacco flavoring with water to a mass concentration of 1% to 5%, and spraying it evenly onto the tobacco shreds at a ratio of 1‰ to 5‰ of the dry weight of the tobacco shreds. After the tobacco shreds are dried and the moisture content is balanced, they are made into cigarettes.

[0016] The present invention has the following beneficial effects:

[0017] (1) Significantly enhanced aroma diversity of products: This invention uses D-raffinose (polysaccharide) and amino acids as raw materials. Compared with monosaccharides, D-raffinose has a more complex carbon chain structure and a rich variety of degradation products. It can generate more diverse aroma substances through Maillard reaction. At the same time, the polysaccharide pyrolysis rate can be adjusted by precisely controlling the reaction temperature to achieve stepwise pyrolysis, effectively avoiding the problem of violent and difficult-to-control Maillard reaction of monosaccharides.

[0018] (2) Excellent effect on improving the sensory quality of cigarettes: Selecting one or more amino acids to react with D-raffinose, the aroma substances generated by different amino acids form a synergistic effect, which can not only enrich and coordinate the aroma layers and optimize the aroma components, but also significantly improve the taste of cigarettes, increase the roasting aroma and sweetness, reduce the irritation and impurities of the smoke, and increase the smoke concentration. This is of great significance for optimizing the sensory quality of low-grade tobacco leaves.

[0019] (3) Optimized and reasonable reaction conditions: After repeated experiments, the optimal reaction parameters were determined. If the reaction temperature is too low, D-raffinose will be difficult to decompose into active intermediates, the reaction will be slow and the amount of aroma substances generated will be small; if the temperature is too high, the decomposition rate will be too fast and the reaction will be violent and out of control. A high-temperature and high-pressure reactor (pressure 0-1 bar) was used. The closed environment can not only accelerate the reaction rate and promote the reaction, but also reduce the loss of volatile aroma components and significantly improve the quality of the product.

[0020] (4) Broad prospects for industrial application: The raw materials D-raffinose and amino acids are cheap and readily available, the preparation process is simple, and production can be started without modifying existing production equipment; the product has a significant effect on improving the poor sensory characteristics of low-grade cigarettes, and the closed production ensures the stability of product quality and is easy to promote industrialization. Attached Figure Description

[0021] Figure 1: Browning of the Maillard reaction products of valine and D-raffinose at different temperatures in Example 3 (A is the absorbance of the intermediate product at 294 nm, and B is the absorbance of the final browned product at 420 nm).

[0022] Figure 2: Fluorescence images of the Maillard reaction products of valine and D-raffinose at different temperatures in Example 3;

[0023] Figure 3: Thermogravimetric (TG) and differential thermogravimetric (DTG) analysis of D-raffinose. Detailed Implementation

[0024] The present invention will be described in detail below with reference to specific embodiments. The embodiments are only used to explain the present invention and are not intended to limit the scope of protection of the present invention.

[0025] Example 1: Preparation of Tobacco Flavorings via Maillard Reaction of Polysaccharides

[0026] Add 45 mL of glycerol to a 100 mL lined cup, and add 4.5 g of valine and 5.4 g of D-raffinose at a molar ratio of 3.59:1. Stir until completely dissolved to obtain the reaction mixture. Place the reaction mixture in a high-temperature and high-pressure reactor, and react for 80 min under sealed conditions at 150 °C and 0.05 bar. After the reaction is completed, immediately cool with an ice-water bath to quench the reaction and obtain the tobacco flavoring product.

[0027] Example 2: Effect of different addition amounts on the sensory effects of flavoring

[0028] The tobacco flavoring prepared in Example 1 was diluted with water to 3% and sprayed evenly onto low-grade tobacco at proportions of 1‰, 2‰, and 5‰ of the dry weight of the tobacco, respectively, forming experimental group 1, experimental group 2, and experimental group 3; tobacco sprayed with an equal amount of distilled water served as the control group.

[0029] Each group of tobacco shreds was placed in a 125℃ oven and dried to a moisture content of 11%–12%. They were then hand-rolled into cigarettes and their moisture content was balanced to a constant in a 22℃ and 60% relative humidity chamber before sensory evaluation was conducted. The results are shown in Table 1.

[0030] Table 1 Sensory evaluation of polysaccharide Maillard reaction tobacco flavorings with different addition amounts

[0031]

[0032] As shown in Table 1, the sensory enhancement effect is best when the amount of added flavoring is 2‰, which can significantly improve the taste characteristics of low-grade tobacco.

[0033] Example 3: Effect of reaction temperature on fragrance properties

[0034] Following the preparation scheme of Example 1, only the reaction temperature was set to 90℃, 120℃, 150℃, 180℃, and 210℃ respectively, while keeping the other conditions the same. Five groups of tobacco flavorings were prepared, namely experimental group 4, experimental group 5, experimental group 6, experimental group 7, and experimental group 8. Browning detection, fluorescence detection, and cigarette sensory evaluation experiments were conducted respectively.

[0035] 1. Browning detection

[0036] Each group of fragrances was prepared into a 4 mg / mL solution using distilled water. The absorbance was measured at 294 nm (characteristic wavelength of Maillard reaction intermediates) and 420 nm (characteristic wavelength of the final browning product) using a UV-Vis spectrophotometer. The results are shown in Figure 1. The absorbance intensity was used as an indicator to predict the formation of Maillard reaction intermediates and final products.

[0037] As shown in Figure 1, the absorbance at both wavelengths was lowest at 90℃, indicating that the Maillard reaction proceeded slowly. As the temperature increased, the absorbance increased significantly, indicating that high temperature can promote the cleavage of D-raffinose, accelerate the Maillard reaction, and increase the content of intermediate and final products simultaneously.

[0038] 2. Fluorescence detection

[0039] Each group of fragrances was prepared into a 1 mg / mL solution with distilled water. Distilled water was used as a blank control. A fluorescence spectrometer was used with an excitation wavelength of 347 nm and an emission spectrum range of 360–550 nm. The results are shown in Figure 2.

[0040] As shown in Figure 2, the products in the initial stage of the Maillard reaction exhibit no fluorescence. Before the advanced browning reaction, the early reaction products undergo cleavage and interconversion to form fluorescent substances. At an excitation wavelength of 347 nm, the strongest fluorescence emission wavelength is in the range of 415–420 nm, consistent with the characteristics of fluorescent substances in the Maillard reaction. The fluorescence intensity at 420 nm increases with increasing temperature and tends to stabilize at 180 °C, indicating that higher reaction temperatures can promote the D-raffinose Maillard reaction, consistent with the browning detection results.

[0041] 3. Sensory evaluation experiment

[0042] Each group of flavorings was sprayed onto low-grade tobacco at a ratio of 2‰ of the dry weight of the tobacco. Cigarettes were prepared and the moisture content was balanced according to the method of Example 2. Tobacco sprayed with an equal amount of distilled water was used as the control group. The sensory evaluation results are shown in Table 2.

[0043] Table 2 Sensory evaluation of polysaccharide Maillard reaction tobacco flavorings at different temperatures

[0044]

[0045] Based on the test results and sensory evaluation, it can be seen that 180℃ is the optimal reaction temperature. At this temperature, the flavoring can significantly increase the aroma of the cigarette, reduce its irritation, and achieve the best smoke concentration and permeability.

[0046] 4. Aroma component analysis

[0047] The pyrazine derivative content of the D-raffinose-valine Maillard reaction flavoring of this invention and the D-glucose-valine Maillard reaction flavoring (prepared under the same conditions) were compared and analyzed using GC-MS technology at 180℃. The detection conditions are as follows:

[0048] Chromatographic column: DB-5MS (60m×0.25mm id×0.25μm df); carrier gas: He, constant flow rate 1.0mL / min; injection port temperature 250℃, split injection (split ratio 10:1), injection volume 1μL; temperature program: 40℃ to 140℃ at 4℃ / min, hold for 5min; then increase to 210℃ at 2℃ / min, hold for 3min; finally increase to 280℃ at 5℃ / min, hold for 10min.

[0049] Mass spectrometry conditions: solvent delay 8 min; ionization mode EI, electron bombardment energy 70 eV; ion source temperature 230℃, quadrupole temperature 150℃, transfer line temperature 280℃; qualitative scanning mode, mass scan range 35~450 amu.

[0050] The test results are shown in Tables 3 and 4. Pyrazine derivatives are the core aroma compounds of flue-cured tobacco. Only 7 pyrazine derivatives were detected in the glucose-valine system, with a total of 869.2197 μg / g; while 12 pyrazine derivatives were detected in the D-raffinose-valine system, with a total of 19881.7013 μg / g. Both the types and contents were significantly increased, indicating that D-raffinose can generate more dicarbonyl compounds to participate in Strecker degradation, promote the generation of pyrazine aroma substances, and thus improve the sensory quality of cigarettes.

[0051] Table 3. Content of pyrazine derivatives in glucose-valine Maillard reaction flavorings

[0052]

[0053] Table 4. Content of pyrazine derivatives in D-raffinose-valine Maillard reaction flavorings

[0054]

[0055] Note: The relative contents in Tables 3 and 4 refer to the content of the substance in the flavoring products.

[0056] Example 4: Effects of different solvents on the sensory effects of fragrances

[0057] In two 100mL lined cups, 45mL of glycerol (experimental group 9) and 45mL of propylene glycol (experimental group 10) were added respectively. At the molar ratio of valine to D-raffinose of 3.59:1, 4.5g of valine and 5.4g of D-raffinose were added. After stirring and dissolving, the mixture was placed in a high-temperature and high-pressure reactor and reacted at 180℃ for 80min under sealed conditions. After the reaction was completed, the mixture was cooled in an ice-water bath to obtain two groups of fragrances, namely experimental group 9 and experimental group 10.

[0058] Two groups of flavorings were sprayed onto low-grade tobacco at a ratio of 2‰ of the dry weight of the tobacco. Cigarettes were prepared according to the method in Example 2, and the moisture content was balanced. The sensory evaluation results are shown in Table 5, with tobacco sprayed with an equal amount of distilled water as a control. As shown in Table 5, the flavoring prepared with glycerin as a solvent has a better sensory effect, with no off-flavors and a more pronounced roasted aroma.

[0059] Table 5 Sensory evaluation results of flavorings prepared with different solvents

[0060]

[0061] Example 5: Effects of different amino acid combinations on the sensory effects of flavorings

[0062] 1. Spice preparation

[0063] In experimental group 11: 45 mL of glycerol was added to a 100 mL beaker, and 1.8 g of valine, 2.3 g of serine and 5.4 g of D-raffinose were added according to the molar ratio of valine:serine:D-raffinose = 1.5:2:1. After stirring to dissolve, the mixture was reacted at 180 °C in a sealed environment for 80 min and then cooled in an ice water bath to obtain the fragrance.

[0064] Experimental Group 12: Add 45 mL of glycerol to a 100 mL beaker, and add 1.5 g of valine, 3.3 g of leucine and 5.4 g of D-raffinose according to the molar ratio of valine:leucine:D-raffinose = 1.2:2.4:1. The other conditions are the same as those in Experimental Group 11.

[0065] Experimental Group 13: Add 45 mL of glycerol to a 100 mL beaker, and add 1.2 g of valine, 1.4 g of serine, 2.4 g of phenylalanine and 5.4 g of D-raffinose according to the molar ratio of valine:serine:phenylalanine:D-raffinose = 1:1.3:1.5:1.1. The other conditions are the same as those in Experimental Group 11.

[0066] 2. Sensory evaluation

[0067] The three flavorings were sprayed onto the low-grade tobacco at a ratio of 2‰ of the dry weight of the tobacco. Cigarettes were prepared and the moisture content was balanced according to the method of Example 2. The tobacco sprayed with an equal amount of distilled water was used as a control. The sensory evaluation results are shown in Table 6.

[0068] Table 6 Sensory evaluation results of flavorings prepared with different amino acid combinations

[0069]

[0070] As shown in Table 6, the flavoring prepared by reacting the ternary combination of valine, serine, and phenylalanine with D-raffinose has the best sensory effect and can achieve comprehensive optimization of aroma, smoke, and aftertaste.

[0071] Example 6 Thermogravimetric Analysis of D-Raffinose

[0072] To clarify the thermal decomposition characteristics of D-raffinose, thermogravimetric-differential thermogravimetric analysis (TG-DTG) was used for testing: 3 mg of D-raffinose was weighed and placed in a ceramic crucible. The temperature was increased from 25 °C to 800 °C at a rate of 10 °C / min using a thermogravimetric-differential thermogravimetric analyzer. High-purity nitrogen was used as the carrier gas. TG and DTG curves were collected, and the results are shown in Figure 3.

[0073] As shown in Figure 3, the TG curve shows three distinct stages of mass loss: 8.49% mass loss in the range of 100–250℃, the maximum mass loss of 72.76% in the range of 250–630℃, and the subsequent mass loss tends to level off until it becomes constant; the DTG curve shows two characteristic peaks, corresponding to 120℃ and 320℃ respectively.

[0074] The above results indicate that the decomposition of D-raffinose proceeds gradually with increasing temperature, reaching a peak decomposition rate at 334℃. At 180℃, D-raffinose can slowly decompose and participate in the Maillard reaction. Excessively high temperatures lead to excessively rapid decomposition rates, resulting in a decrease in the coordination between the generated aroma substances and the tobacco aroma. This further verifies the rationality of the reaction temperature setting in this invention.

Claims

1. A method for preparing tobacco flavorings via the Maillard reaction of polysaccharides, characterized in that, The process includes the following steps: (1) Dissolving amino acids and polysaccharides in a molar ratio of (1-5):1 in a solvent and stirring until homogeneous to obtain the reaction material; (2) Placing the reaction material in a high-temperature and high-pressure reactor and adjusting the temperature to 80℃-210℃ and the pressure to 0-1 bar under sealed conditions, and reacting for 30-120 minutes under these conditions; (3) After the reaction is completed, immediately cooling the reactor to room temperature to quench the reaction and obtain the Maillard reaction tobacco fragrance product.

2. The method according to claim 1, characterized in that, The amino acid is one or a combination of several of the following: serine, glycine, valine, proline, leucine, phenylalanine, lysine, and glutamic acid.

3. The method according to claim 1, characterized in that, The polysaccharide is D-raffinose.

4. The method according to claim 1, characterized in that, The solvent is one or a combination of propylene glycol, glycerol, and water.

5. The application of a tobacco flavoring prepared by the Maillard reaction of a polysaccharide as described in claim 1.

6. The application of the tobacco flavoring prepared by the Maillard reaction of polysaccharides according to claim 5, characterized in that, The tobacco flavoring is diluted with water to a mass concentration of 1% to 5%, and then evenly sprayed onto the tobacco shreds at a ratio of 1‰ to 5‰ of the dry weight of the tobacco shreds. After the tobacco shreds are dried and the moisture content is balanced, cigarettes are made.

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