Method for antioxidation synergistic modified atmosphere preservation of jujube sesame pill

Abstract

The present application relates to the field of food processing and preservation technology, and discloses a method for microcapsule antioxidant synergistic modified atmosphere preservation of red jujube sesame pills, which comprises the following steps: mixing anhydrous propylene glycol, liquid soybean lecithin, sodium phytate micro powder and ascorbyl palmitate to obtain composition one; adding rosemary extract microcapsule powder to prepare composition two; dry mixing black sesame micro powder, red date powder, D-erythorbic acid powder and sodium bicarbonate micro powder to obtain premixed dry material; kneading high fructose syrup and composition two, aging, and rolling into pills; vacuum packaging, sequentially injecting pure carbon dioxide and argon-nitrogen mixed gas, and heat sealing the opening. By constructing a composite antioxidant emulsion system, slow release of antioxidant components is realized, internal moisture and free oil are promoted to balance, and multiple aeration processes are combined to establish inert physical shielding and micro-positive pressure environment, thereby reducing the oxidation deterioration rate of red jujube sesame pills and prolonging the product storage period.

Description

Technical Field

[0001] This invention relates to the field of food processing and preservation technology, specifically to a method for synergistic modified atmosphere preservation of jujube and sesame seed pills using microcapsule antioxidants. Background Technology

[0002] Red date and sesame balls, a type of snack, are mainly made from black sesame seeds and red dates. Black sesame seeds contain a relatively high amount of unsaturated fatty acids, while red dates contain a large amount of sugar and a certain amount of water. During conventional processing and storage, the oils inside the red date and sesame balls are prone to oxidation and rancidity due to external environmental factors such as light, oxygen, and temperature changes, resulting in an unpleasant odor.

[0003] At the same time, the moisture inside the product easily evaporates into the external environment, causing the surface of the jujube and sesame balls to become dry and hard, affecting the sensory quality and taste of the product.

[0004] To extend the shelf life of jujube and sesame balls, existing technologies typically involve directly adding synthetic antioxidants or preservatives to the raw materials, or using basic vacuum packaging for physical isolation.

[0005] However, directly added antioxidants tend to be unevenly distributed during the mixing and kneading process and are consumed in the early stages of processing, failing to maintain a stable antioxidant effect over a long storage period. While simple vacuum packaging removes air from the packaging bag, it cannot eliminate residual oxygen in the microscopic physical gaps inside the jujube and sesame balls.

[0006] Under the compression of external atmospheric pressure, the surface of jujube and sesame balls is prone to oil separation. After the oil seeps out, it will still oxidize upon contact with residual oxygen. Conventional modified atmosphere packaging often uses a single gas or a simple mixture of gases as fillers, lacking specific designs for inhibiting aerobic microorganisms and physically shielding against oxygen, thus limiting its protective effect.

[0007] In order to overcome the shortcomings of existing processing and preservation methods, it is necessary to develop a new preservation method that combines the slow release of antioxidants, the stable balance of moisture and oil inside the pills, and multiple physical barriers to gases, thereby effectively extending the shelf life of jujube and sesame pills and maintaining the initial quality of the product. Summary of the Invention

[0008] To address the shortcomings of existing technologies, this invention provides a method for synergistic preservation of jujube and sesame seed pills with microencapsulated antioxidants. This method solves the problems of easy oxidation and rancidity of fats, moisture loss leading to a dry and hard texture, uneven distribution of antioxidant components, and limited effectiveness of conventional preservation methods during the storage of existing jujube and sesame seed pill products.

[0009] To achieve the above objectives, the present invention provides the following technical solution:

[0010] A method for synergistic preservation of jujube and sesame seed pills with microencapsulated antioxidants includes the following steps:

[0011] Anhydrous propylene glycol and liquid soybean lecithin were added to a mixing tank, mechanically stirred and heated to mix. Sodium phytate micropowder and palmitic acid ascorbate were added sequentially, stirred at a constant temperature and then cooled to obtain composition one. Rosemary extract microcapsule powder was added to composition one and processed using a high-shear dispersion emulsifier to obtain composition two.

[0012] Black sesame powder, red date powder, D-isoascorbic acid powder and sodium bicarbonate powder are put into a mixer and dry mixed to obtain a premixed dry material; the premixed dry material is placed in a kneader, high fructose syrup is pumped in and the second composition is added and kneaded to form a wet material; the wet material is sealed and left to stand to mature, and then kneaded into spherical balls to obtain shaped red date and sesame balls.

[0013] The formed jujube and sesame balls are placed in a packaging composite bag and transferred into a modified atmosphere packaging machine. After the cavity is closed, the vacuum pump is started to reduce the absolute pressure and maintain it. Pure carbon dioxide is injected separately to the first preset absolute pressure, and then a mixed gas composed of argon and nitrogen is continuously injected to the second preset absolute pressure for heat sealing, thus obtaining the finished product of modified atmosphere preserved jujube and sesame balls.

[0014] By adopting the above technical solutions, the combination of microencapsulated natural antioxidants with multi-pressure modified atmosphere packaging intervenes from several technical dimensions such as oil anti-oxidation, moisture retention and gas replacement, which can slow down the occurrence of oxidation chain reaction to a certain extent, thereby extending the product shelf life and maintaining its initial sensory quality.

[0015] In terms of specific mechanisms, during the construction of the complex antioxidant emulsion system, anhydrous propylene glycol, acting as a solvent and humectant, is mixed with liquid soybean lecithin to form an amphiphilic matrix. Sodium phytate added to this matrix helps chelate any transition metal ions that may be present in the raw materials, thereby limiting the initiation pathway of metal ion-catalyzed lipid oxidation. Simultaneously, ascorbic acid palmitate, as a fat-soluble component, tends to bind to free fatty acids released from black sesame seeds.

[0016] With the introduction of rosemary extract microcapsule powder, under the action of high mechanical shear force, the phospholipid molecules of soybean lecithin will be oriented on the surface of the microcapsules, forming secondary encapsulated suspension emulsion droplets. This treatment method allows the natural antioxidant components of rosemary to be released relatively slowly during subsequent processing and storage, slowing down the premature consumption of antioxidants caused by the mechanical force of kneading.

[0017] After entering the dry mixing and kneading process, a spatial distribution of hydrophilic and lipophilic antioxidants was established within the system. Water-soluble D-isoascorbic acid powder was introduced during dry mixing to combat free radicals in the aqueous environment. The high-fructose syrup pumped in during kneading not only provided plastic binding force for the powder and reduced the water activity of the matrix, but also facilitated the addition of suspended emulsion droplets to flow along the syrup, shuttle through and distribute into the physical gaps between the sesame and jujube powder particles.

[0018] At this point, considering that sodium bicarbonate micropowder will undergo slight decomposition in a slightly acidic matrix, the resulting free carbon dioxide will form micropores inside the pellet, which objectively promotes the penetration of emulsion droplets into the core area of ​​the pellet.

[0019] The subsequent sealed and static maturation process guides the moisture, syrup, and free oil inside the pellets towards thermodynamic equilibrium, reducing the risk of oil separation or shriveling of the pellets in the early stages of storage.

[0020] In the final packaging stage, modified atmosphere packaging (MAP) provides a stepped gas shielding layer. The initial vacuum evacuation process aims to remove as much residual air as possible from the inside of the packaging bag and the micropores of the pellets. The subsequent injection of pure carbon dioxide dissolves quickly at the moisture and oil interface on the surface of the pellets, creating a slightly acidic environment to inhibit the metabolic enzyme activity of aerobic microorganisms.

[0021] Based on this, a mixed gas of argon and nitrogen is introduced. The large molecular mass and chemical inertness of argon allow it to easily settle and adhere to the surface of the capsules, forming a physical shield and reducing the chance of residual oxygen contacting the sesame oil. Nitrogen acts as a supporting filling medium, maintaining a positive pressure balance inside and outside the packaging bag and resisting the penetration of external oxygen molecules. Overall, the endogenous microcapsule antioxidant network and the exogenous protective gas environment work together to reduce the oxidative degradation rate of the jujube and sesame capsules.

[0022] Preferably, the steps for obtaining Composition 1 specifically include: adding 8.0 to 12.0 parts of anhydrous propylene glycol and 1.5 to 2.5 parts of liquid soybean lecithin to a mixing tank with a water bath jacket; starting mechanical stirring and controlling the stirring speed to be 300 rpm to 500 rpm; heating and maintaining the temperature to 40°C to 45°C, mixing evenly, and then slowly adding 0.8 to 1.2 parts of sodium phytate powder and 1.0 to 2.0 parts of palmitic acid ascorbate; maintaining the temperature at 40°C to 45°C and stirring continuously for 15 to 20 minutes, and then lowering the temperature to 20°C to 25°C to obtain Composition 1.

[0023] By adopting the above technical solution, a constant temperature of 40°C to 45°C is set to enable liquid soybean lecithin to obtain suitable fluidity, while reducing the disturbance to the molecular structure of anhydrous propylene glycol and promoting the dissolution and dispersion of sodium phytate micropowder and palmitic acid ascorbate. The subsequent cooling operation helps to stabilize the emulsion phase of the system, thereby maintaining the physical properties of composition one.

[0024] Preferably, the steps for obtaining composition two specifically include: slowly adding 4.0 to 6.0 parts of rosemary extract microcapsule powder in batches to composition one; processing it using a high-shear dispersion emulsifier at an ambient temperature of 20°C to 25°C; controlling the rotation speed of the high-shear dispersion emulsifier to be 1500 rpm to 2000 rpm; and continuously processing for 3 to 5 minutes to obtain composition two.

[0025] By employing the above technical solution, the slow, batch-feeding process combined with a high shear rate of 1500 rpm to 2000 rpm helps to break up the physical agglomeration of microcapsule powder that may occur in the liquid. Controlling the processing time to a shorter duration allows for the suspension and distribution of microcapsules while minimizing the loss of active ingredients from rosemary extract due to excessive shear friction and heat generation.

[0026] Preferably, before the black sesame powder, jujube powder, D-isoascorbic acid powder and sodium bicarbonate powder are dry-mixed in the mixer, the black sesame powder and jujube powder are subjected to ultra-fine grinding treatment to control the particle size of the black sesame powder and jujube powder to be 80 mesh to 100 mesh, and the mass moisture content of the jujube powder is 3% to 5%.

[0027] By adopting the above technical solution, the particle size control of 80 to 100 mesh ensures that the two-phase dry powder raw materials have similar specific surface areas and bulk densities, thereby reducing the stratification phenomenon caused by the difference in specific gravity during the dry mixing stage. Controlling the moisture content of the jujube powder to 3% to 5% aims to slow down the tendency of pectin and fructose in the jujube powder to absorb water and clump, allowing the syrup and composition two to more fully wet the powder particles in the subsequent kneading process.

[0028] Preferably, the steps for obtaining the premixed dry material specifically include: adding 62.5 to 67.5 parts of black sesame powder and 37.5 to 42.0 parts of jujube powder into a mixer; adding 0.25% to 0.45% of D-isoascorbic acid powder and 0.05% to 0.12% of sodium bicarbonate powder calculated as a percentage of the total mass of black sesame powder and jujube powder; and dry mixing at 20°C to 25°C for 10 to 15 minutes until the mixture is homogeneous to obtain the premixed dry material.

[0029] By adopting the above technical solution, the trace amounts of sodium bicarbonate powder and D-isoascorbic acid powder are initially physically mixed in a dry powder state, which helps to avoid the bitter taste problem that may be caused by excessively high local concentrations, and thus provides a relatively uniform material basis for the subsequent wet kneading process.

[0030] Preferably, the step of kneading to form a wet material specifically includes: weighing 100.0 parts of premixed dry material and placing it in a kneader; slowly pumping in 25.0 to 35.0 parts of high fructose syrup, while simultaneously adding 0.20 to 0.50 parts of composition two; controlling the speed of the kneader to 30 rpm to 50 rpm, and continuously kneading for 8 to 12 minutes at 20°C to 25°C to form a wet material.

[0031] By employing the above technical solution, a low kneading speed of 30 to 50 rpm is used in conjunction with the slow dripping of liquid components. The high-fructose syrup provides conditions for plastic deformation of the powder during kneading, while the antioxidant mixture gradually penetrates into the dry matrix due to the syrup's fluidity. Controlling the kneading time to 8 to 12 minutes allows trace amounts of oil from the black sesame particles to slowly seep out and moderately emulsify with the syrup, avoiding significant oil separation on the surface of the pellets due to over-kneading.

[0032] Preferably, the steps of sealing and allowing the wet material to stand for maturation and kneading it into spherical pellets specifically include: transferring the wet material to a stainless steel tray, sealing it, and allowing it to stand for 30 to 45 minutes at 20°C to 25°C for maturation; after maturation, feeding the wet material into a pelletizing machine and kneading it into spherical pellets with a single pellet weight of 8.0g to 10.0g to obtain the formed jujube and sesame pellets.

[0033] By adopting the above technical solution, the sealed curing process reduces the evaporation of free moisture into the air, providing time for the spontaneous migration of moisture and the release of internal stress within the high fructose syrup, jujube powder, and sesame powder. The cured wet material exhibits better structural flexibility, which is beneficial for subsequent pelleting machinery to press out spherical pellets with more regular dimensions and less prone to surface cracking.

[0034] Preferably, the steps of placing the formed jujube and sesame balls in a packaging composite bag and transferring them into a modified atmosphere packaging machine, closing the cavity, starting a vacuum pump to reduce the absolute pressure and maintaining it, and separately injecting pure carbon dioxide to the first preset absolute pressure specifically include: placing the formed jujube and sesame balls in a packaging composite bag, the packaging composite bag being a high-barrier packaging composite bag, transferring them into a modified atmosphere packaging machine with a pulse control system, closing the cavity, and starting a vacuum pump; reducing the absolute pressure inside the cavity to 15 kPa to 20 kPa within 1.0 to 2.0 seconds, and maintaining it for 3.0 to 5.0 seconds;

[0035] Then, pure carbon dioxide is injected into the cavity until the absolute pressure inside the cavity rises back to the first preset absolute pressure, which is 40 kPa to 45 kPa, at which point the injection of pure carbon dioxide is stopped.

[0036] By employing the above technical solution, the operation of reducing the pressure to 15 kPa to 20 kPa within 1.0 to 2.0 seconds and maintaining it aims to remove as much air as possible from the surface and shallow pores of the pellet. Subsequently, pure carbon dioxide is introduced to 40 kPa to 45 kPa. The negative pressure environment promotes the rapid diffusion of pure carbon dioxide, which preferentially occupies the pores where the air has been expelled, thereby improving its dissolution efficiency at the gas-solid interface.

[0037] Preferably, after stopping the injection of pure carbon dioxide, the injection is switched to a continuous injection of a mixed gas consisting of argon (8% to 12% by volume) and nitrogen (88% to 92% by volume); the injection continues until the absolute pressure inside the cavity reaches the second preset absolute pressure, which is 103 kPa to 105 kPa, and the cavity is heat-sealed under the second preset absolute pressure to obtain the finished product of modified atmosphere preserved jujube and sesame balls.

[0038] By adopting the above technical solution, argon gas with a volume ratio of 8% to 12% is introduced as an inert shielding gas, and nitrogen gas with a volume ratio of 88% to 92% is used as a buffer medium. Heat sealing is performed under a slight positive pressure of 103 kPa to 105 kPa. This helps to keep free carbon dioxide and argon gas in the area close to the surface of the pellets, and also keeps the packaging composite bag in a moderately full state. The slight positive pressure inside the bag slows down the tendency of external oxygen to permeate into the packaging.

[0039] Preferably, after heat sealing, the finished jujube and sesame balls with modified atmosphere packaging are placed in a constant temperature and light-proof warehouse with a temperature of 20°C to 25°C and a relative humidity of 60% to 65% and left to stand for 24 to 48 hours.

[0040] By adopting the above technical solution, and storing the product under specific temperature and humidity conditions for 24 to 48 hours, a buffer period is provided for the diffusion and dissolution of the mixed gas inside the packaging with the moisture and free oil on the surface of the capsules, making the preservation system composed of microcapsules, matrix components and protective gas tend to be stable.

[0041] This invention provides a method for synergistic preservation of jujube and sesame seed pills using microencapsulated antioxidants. It offers the following beneficial effects:

[0042] 1. This invention constructs a composite antioxidant emulsion system by mixing anhydrous propylene glycol with liquid soybean lecithin to form a matrix, and combining it with sodium phytate micropowder, palmitic acid ascorbate, and rosemary extract microcapsule powder. Sodium phytate can chelate metal ions in the raw materials, and palmitic acid ascorbate binds free fatty acids. Combined with the secondary encapsulation structure of soybean lecithin formed by high-shear dispersion emulsifier processing, the natural antioxidant components can be slowly released during subsequent processing and storage, effectively slowing down the oxidative rancidity process of the oil inside the jujube and sesame seed pills.

[0043] 2. This invention introduces D-isoascorbic acid powder and sodium bicarbonate micron powder during the mixing stage, and pumps in high fructose syrup and adds an antioxidant emulsion during the kneading stage, followed by sealed static curing. The trace carbon dioxide produced by the decomposition of sodium bicarbonate micron powder can form micropores inside the pellet, promoting the penetration of the antioxidant emulsion into the pellet along the flow of high fructose syrup, establishing a spatial distribution of hydrophilic and lipophilic antioxidants. This treatment method guides the moisture and free oil inside the pellet towards thermodynamic equilibrium, reducing the risk of oil separation or shriveling in the early stages of storage.

[0044] 3. This invention utilizes a modified atmosphere packaging machine to perform a stepped inflation process, sequentially vacuuming, injecting pure carbon dioxide, and then injecting a mixture of argon and nitrogen, thus establishing multiple gas shielding layers inside the packaging. The initial vacuuming operation removes residual air from the pores of the pellets. Subsequently, the injected pure carbon dioxide dissolves on the surface of the pellets, inhibiting aerobic microbial metabolism. Finally, the injected argon settles to form a physical shield, while nitrogen maintains a slightly positive pressure inside the packaging bag to resist external oxygen penetration. This exogenous protective gas environment reduces the oxidation and deterioration rate of the jujube and sesame pellets. Attached Figure Description

[0045] Figure 1 This is a two-dimensional gas chromatographic spectrum of gas components extracted from the central region of the pellet in Test Example 1 of the present invention.

[0046] Figure 2 This is a high-performance liquid chromatogram of the sample tested on day 15 of the accelerated oxidation test in Test Example 2 of the present invention;

[0047] Figure 3 This is a high-performance liquid chromatogram of the sample taken 24 hours after extraction of free substances in the aqueous phase in Test Example 3 of the present invention;

[0048] Figure 4 This is a graph showing the change in oil peroxide value over time during the accelerated aging test in Test Example 4 of this invention.

[0049] Figure 5 This is a gas chromatography-ion migration spectrum feature extraction diagram of flavor substances after 15 days of accelerated oxidation test in Test Example 5 of the present invention. Detailed Implementation

[0050] The technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the accompanying drawings. Obviously, the described embodiments are only some embodiments of the present invention, and not all embodiments. Based on the embodiments of the present invention, all other embodiments obtained by those skilled in the art without creative effort are within the scope of protection of the present invention.

[0051] Example 1:

[0052] This embodiment provides a method for synergistic preservation of jujube and sesame seed pills with microencapsulated antioxidants, including the following steps:

[0053] 10.0 parts of anhydrous propylene glycol and 2.0 parts of liquid soybean lecithin were added to a mixing tank with a water bath jacket. Mechanical stirring was started and the stirring speed was set to 400 rpm. The temperature was raised and kept constant at 42°C. After mixing evenly, 1.0 part of sodium phytate powder and 1.5 parts of palmitic acid ascorbate were slowly added in sequence. The mixture was stirred continuously at 42°C for 18 minutes. The temperature was then lowered to 22°C to obtain 14.5 parts of composition one.

[0054] 5.0 parts of rosemary extract microcapsule powder were slowly added to 14.5 parts of composition one in batches. The mixture was processed continuously for 4 minutes at an ambient temperature of 22°C using a high shear dispersion emulsifier with the speed set at 1800 rpm to obtain composition two.

[0055] Before being fed into the mixer, the black sesame powder and jujube powder were subjected to ultra-fine grinding to control the particle size of both to 90 mesh, and the moisture content of the jujube powder to be 4.0%. 62.5 parts of black sesame powder, 37.5 parts of jujube powder, 0.35% of D-isoascorbic acid powder (calculated as a percentage of the total mass of black sesame powder and jujube powder), and 0.08% of sodium bicarbonate powder (calculated as a percentage of the total mass of black sesame powder and jujube powder) were added into the mixer and dry-mixed at 22°C for 12 minutes to obtain a premixed dry material.

[0056] Weigh 100.0 parts of the above premixed dry material and place it in a kneader. Slowly pump in 30.0 parts of high fructose syrup and simultaneously add 0.35 parts of Composition II. Control the kneader speed to 40 rpm and knead continuously for 10 minutes at 22°C to form a wet material. Transfer the wet material to a stainless steel tray, cover and seal it, and let it stand at 22°C for 38 minutes to mature. After maturation, put the wet material into a pelleting machine and knead it into spherical pellets with a single weight of 9.0g to obtain the formed jujube and sesame pellets.

[0057] The formed jujube and sesame balls are placed in a high-barrier packaging composite bag and moved into a modified atmosphere packaging machine with a pulse control system. After the modified atmosphere packaging machine cavity is closed, the vacuum pump is started. Within 1.5 seconds, the absolute pressure inside the modified atmosphere packaging machine cavity is reduced to 18 kPa and maintained at 18 kPa pressure for 4.0 seconds.

[0058] Then, pure carbon dioxide is injected into the modified atmosphere packaging machine cavity until the absolute pressure inside the cavity rises to 42 kPa. The injection of pure carbon dioxide is then stopped, and a mixed gas consisting of 10% argon and 90% nitrogen is switched on. The mixed gas is continuously injected until the absolute pressure inside the modified atmosphere packaging machine cavity reaches a slightly positive pressure of 104 kPa. Heat sealing is then performed under this slightly positive pressure of 104 kPa to obtain the finished product of modified atmosphere preserved jujube and sesame balls.

[0059] After heat sealing and packaging, the finished red date and sesame balls with modified atmosphere packaging are transferred to a constant temperature and light-proof warehouse with a temperature of 22℃ and a relative humidity of 62% and left to stand for 36 hours.

[0060] Example 2:

[0061] This embodiment provides a method for synergistic preservation of jujube and sesame seed pills with microencapsulated antioxidants, including the following steps:

[0062] 12.0 parts of anhydrous propylene glycol and 2.5 parts of liquid soybean lecithin were added to a mixing tank with a water bath jacket. Mechanical stirring was started and the stirring speed was set to 500 rpm. The temperature was raised and kept constant at 45°C. After mixing evenly, 1.2 parts of sodium phytate powder and 2.0 parts of palmitic acid ascorbate were slowly added in sequence. The mixture was stirred continuously at 45°C for 20 minutes. The temperature was then lowered to 25°C to obtain 17.7 parts of composition one.

[0063] 6.0 parts of rosemary extract microcapsule powder were slowly added to 17.7 parts of composition one in batches. The mixture was processed continuously for 5 minutes at an ambient temperature of 25°C using a high shear dispersion emulsifier with the speed set at 2000 rpm to obtain composition two.

[0064] Before being fed into the mixer, the black sesame powder and jujube powder were subjected to ultra-fine grinding to control the particle size of both to 100 mesh, and the moisture content of the jujube powder to be 5.0%. 66.0 parts of black sesame powder, 42.0 parts of jujube powder, 0.45% of D-isoascorbic acid powder (calculated as a percentage of the total mass of black sesame powder and jujube powder), and 0.12% of sodium bicarbonate powder (calculated as a percentage of the total mass of black sesame powder and jujube powder) were added into the mixer and dry-mixed at 25°C for 15 minutes to obtain a premixed dry material.

[0065] Weigh 100.0 parts of the above premixed dry material and place it in a kneader. Slowly pump in 35.0 parts of high fructose syrup and simultaneously add 0.50 parts of Composition II. Control the kneader speed to 50 rpm and knead continuously for 12 minutes at 25°C to form a wet material. Transfer the wet material to a stainless steel tray, cover and seal it, and let it stand at 25°C for 45 minutes to mature. After maturation, put the wet material into a pelleting machine and knead it into spherical pellets with a single weight of 10.0g to obtain the formed red date and sesame pellets.

[0066] The formed jujube and sesame balls are placed in a high-barrier packaging composite bag and moved into a modified atmosphere packaging machine with a pulse control system. After the modified atmosphere packaging machine cavity is closed, the vacuum pump is started. Within 2.0 seconds, the absolute pressure inside the modified atmosphere packaging machine cavity is reduced to 20 kPa and maintained at 20 kPa pressure for 5.0 seconds.

[0067] Then, pure carbon dioxide is injected into the modified atmosphere packaging machine cavity until the absolute pressure inside the cavity rises to 45 kPa. The injection of pure carbon dioxide is then stopped, and a mixed gas consisting of 12% argon and 88% nitrogen is switched on. The mixed gas is continuously injected until the absolute pressure inside the modified atmosphere packaging machine cavity reaches a slightly positive pressure of 105 kPa. Heat sealing is then performed under this slightly positive pressure to obtain the finished modified atmosphere preserved jujube and sesame balls.

[0068] After heat sealing and packaging, the finished red date and sesame balls with modified atmosphere packaging are transferred to a constant temperature and light-proof warehouse with a temperature of 25℃ and a relative humidity of 65% and left to stand for 48 hours.

[0069] Example 3:

[0070] This embodiment provides a method for synergistic preservation of jujube and sesame seed pills with microencapsulated antioxidants, including the following steps:

[0071] Add 8.0 parts of anhydrous propylene glycol and 1.5 parts of liquid soybean lecithin to a mixing tank with a water bath jacket, start mechanical stirring, set the mechanical stirring speed to 300 rpm, heat and keep the temperature at 40°C, mix evenly, then slowly add 0.8 parts of sodium phytate powder and 1.0 parts of palmitic acid ascorbate, keep the temperature at 40°C and stir continuously for 15 minutes, then cool to 20°C to obtain 11.3 parts of composition one;

[0072] 4.0 parts of rosemary extract microcapsule powder were slowly added to 11.3 parts of composition one in batches. The mixture was processed continuously for 3 minutes at an ambient temperature of 20°C using a high shear dispersion emulsifier with the speed set at 1500 rpm to obtain composition two.

[0073] Before being fed into the mixer, the black sesame powder and jujube powder were subjected to ultra-fine grinding to control the particle size of both to 80 mesh, and the moisture content of the jujube powder to be 3.0%. 67.5 parts of black sesame powder, 37.5 parts of jujube powder, 0.25% of D-isoascorbic acid powder (calculated as a percentage of the total mass of black sesame powder and jujube powder), and 0.05% of sodium bicarbonate powder (calculated as a percentage of the total mass of black sesame powder and jujube powder) were added into the mixer and dry-mixed at 20°C for 10 minutes to obtain a premixed dry material.

[0074] Weigh 100.0 parts of the above premixed dry material and place it in a kneader. Slowly pump in 25.0 parts of high fructose syrup and simultaneously add 0.20 parts of Composition II. Control the kneader speed to 30 rpm and knead continuously for 8 minutes at 20°C to form a wet material. Transfer the wet material to a stainless steel tray, cover and seal it, and let it stand at 20°C for 30 minutes to mature. After maturation, put the wet material into a pelleting machine and knead it into spherical pellets with a single weight of 8.0g to obtain the formed jujube and sesame pellets.

[0075] The formed jujube and sesame balls are placed in a high-barrier packaging composite bag and moved into a modified atmosphere packaging machine with a pulse control system. After the modified atmosphere packaging machine cavity is closed, the vacuum pump is started. Within 1.0 second, the absolute pressure inside the modified atmosphere packaging machine cavity is reduced to 15 kPa and maintained at 15 kPa pressure for 3.0 seconds.

[0076] Then, pure carbon dioxide is injected into the modified atmosphere packaging machine cavity until the absolute pressure inside the cavity rises to 40 kPa. The injection of pure carbon dioxide is then stopped, and a mixed gas consisting of 8% argon and 92% nitrogen is switched on. The mixed gas is continuously injected until the absolute pressure inside the modified atmosphere packaging machine cavity reaches a slightly positive pressure of 103 kPa. Heat sealing is then performed under this slightly positive pressure of 103 kPa to obtain the finished product of modified atmosphere preserved jujube and sesame balls.

[0077] After heat sealing and packaging, the finished red date and sesame balls with modified atmosphere packaging are transferred to a constant temperature and light-proof warehouse with a temperature of 20℃ and a relative humidity of 60% and left to stand for 24 hours.

[0078] Comparative Example 1:

[0079] Compared with Example 1, the differences are as follows: the preparation processes of Composition 1 and Composition 2 are not performed; D-isoascorbic acid powder and sodium bicarbonate micro powder are not added in the dry mixing step; in the kneading step, the rosemary extract microcapsule powder of the same effective mass calculated according to Example 1 is directly added to the premixed dry material and high fructose syrup for kneading; in the packaging step, after the modified atmosphere packaging machine cavity is closed, it is directly evacuated and filled with 100% pure nitrogen until the absolute pressure reaches 104 kPa for heat sealing, without the absolute pressure reduction and pressure holding, pure carbon dioxide injection and argon mixed gas injection operations, and the rest are the same.

[0080] Comparative Example 2:

[0081] Compared with Example 1, the difference is that the pre-dispersion and encapsulation preparation process of Composition 1 and Composition 2 is not performed; in the kneading step, anhydrous propylene glycol, liquid soybean lecithin, sodium phytate micro powder, palmitic acid ascorbate ester and rosemary extract microcapsule powder of equal mass calculated according to the proportions of Example 1 are directly pumped into the kneader together with high fructose syrup to participate in kneading, and the rest are the same.

[0082] Comparative Example 3:

[0083] Compared with Example 1, the difference is that D-isoascorbic acid powder and sodium bicarbonate micro powder were not added in the dry mixing step (i.e., the in-situ micro-release system was not constructed), and all other steps were the same.

[0084] Comparative Example 4:

[0085] Compared with Example 1, the difference is that palmitic acid ascorbate (i.e., lipid receptors that do not form transphase redox cycles) is not added in the preparation process of Composition 1, while all other aspects are the same.

[0086] Comparative Example 5:

[0087] Compared with Example 1, the difference is that in the packaging step, the negative pressure pulse flash degassing operation (i.e., the operation of reducing the absolute pressure to 18 kPa and maintaining it within 1.5 seconds) and the pure carbon dioxide injection operation are not performed; after the modified atmosphere packaging machine is closed, a conventional vacuum is directly drawn and pure nitrogen is filled in at once until the absolute pressure reaches 104 kPa for heat sealing (i.e., there is no instantaneous gas release opening and protective gas replacement), and the rest are the same.

[0088] Test Example 1:

[0089] The modified atmosphere preserved jujube and sesame balls prepared under the conditions of Example 1 were selected as the first group of test samples, the modified atmosphere preserved jujube and sesame balls prepared under the conditions of Comparative Example 3 were selected as the second group of test samples, and the modified atmosphere preserved jujube and sesame balls prepared under the conditions of Comparative Example 5 were selected as the third group of test samples.

[0090] The first, second, and third sets of test samples were placed in a constant temperature and humidity chamber at 22°C and 65% relative humidity for 24 hours to allow the gas distribution inside the jujube and sesame balls to reach a relative equilibrium with the gas distribution in the packaging environment.

[0091] Using an airtight syringe equipped with a side-hole micro-sampling needle, before the insertion action, a 2mm thick silicone pad is attached to the surface of the packaging composite bag at the corresponding position. The micro-sampling needle is inserted into the center of the jujube and sesame ball from the outside of the packaging composite bag, and the insertion distance is set to the radius of the jujube and sesame ball. 0.5mL of internal gas is extracted outward as a test sample.

[0092] The sample was injected into a gas chromatograph equipped with a thermal conductivity detector for component separation. A 5A molecular sieve capillary column was used. During the test, the injection port heating temperature was set to 150℃, and the constant temperature of the thermal conductivity detector was set to 200℃. Helium gas with a purity of 99.99% was used as the chromatographic carrier gas, and the flow rate of the carrier gas was set to 2.0 mL / min.

[0093] The programmed temperature rise parameters of the column oven are set as follows: start running at 40℃ and maintain at 40℃ for 2 minutes, heat to 120℃ at a rate of 5℃ per minute, maintain at 120℃ for 3 minutes, and then end the single sample injection operation.

[0094] Gas chromatographic signals with retention times between 1.0 min and 4.0 min were collected and recorded. The peak area data of the oxygen response peak (1.2 min retention time), argon response peak (1.5 min retention time), nitrogen response peak (2.1 min retention time), and carbon dioxide response peak (3.5 min retention time) in the gas chromatograms were numerically integrated using the external standard curve method to calculate the mole fraction percentages of oxygen, argon, nitrogen, and carbon dioxide.

[0095] Table 1. Test data on mole fraction of gas components extracted from the central region of the pellet.

[0096] Group oxygen(%) carbon dioxide(%) Argon (%) Nitrogen (%) Example 1 0.13 8.42 10.87 80.58 Comparative Example 3 2.37 1.42 2.15 94.06 Comparative Example 5 1.96 0.15 0.00 97.89

[0097] See attached document Figure 1 , attached Figure 1 The horizontal axis represents retention time in minutes, and the vertical axis represents response signal intensity in mV. The solid line corresponds to the chromatographic data curve of the product prepared under the conditions of Example 1, the first dashed line corresponds to the chromatographic data curve of the product prepared under the conditions of Comparative Example 3, and the second dashed line corresponds to the chromatographic data curve of the product prepared under the conditions of Comparative Example 5.

[0098] The test results are as follows:

[0099] Based on the data in Table 1 and Figure 1 From the results, it can be seen that the oxygen molar fraction of the finished product prepared under the conditions in Example 1 is 0.13%, and the argon molar fraction is 10.87%. Figure 1 The solid line shows an argon signal peak at a retention time of 1.5 minutes.

[0100] The finished product prepared under the conditions of Comparative Example 3 did not contain sodium bicarbonate micropowder or D-isoascorbic acid powder. The oxygen mole fraction measured at the center of the finished product prepared under the conditions of Comparative Example 3 was 2.37%. Figure 1 The peak area of ​​the carbon dioxide signal peak at the retention time of 3.5 minutes, indicated by the first dashed line, is lower than... Figure 1 The peak area of ​​the carbon dioxide signal peak at the retention time of 3.5 minutes in the solid line.

[0101] The product prepared under the conditions of Comparative Example 5, excluding the step of reducing the gas pressure to 18 kPa and maintaining it, and the pure carbon dioxide injection operation, had an internal oxygen molar fraction of 1.96%, an internal carbon dioxide molar fraction of 0.15%, and an internal argon molar fraction of 0. Figure 1 The second dashed line in the middle shows no obvious response signal at the retention times of 1.5 minutes and 3.5 minutes.

[0102] D-isoascorbic acid powder and sodium bicarbonate micron powder undergo a neutralization reaction within the jujube and sesame seed pills to generate carbon dioxide. Under the influence of concentration gradient and internal partial pressure, the carbon dioxide tends to flow outwards. After the absolute pressure is reduced to 18 kPa during the packaging process, the carbon dioxide within the pores expands and escapes. This outward flow of carbon dioxide expels residual air from the pores. Accompanying the escape of carbon dioxide, a region of reduced pressure appears deep within the pores of the jujube and sesame seed pills.

[0103] Subsequently, a mixture of argon and nitrogen gas was introduced and permeated into the inner layer of the jujube and sesame seed pills. Argon has a higher density and molecular weight than nitrogen, and it exhibits dispersion and solubility in lipids. During the convective permeation process of gas pressure flow, argon, along with nitrogen, entered the deeper space of the jujube and sesame seed pills.

[0104] The product prepared under the conditions of Example 1, which underwent a gas-generating reaction and absolute pressure reduction process, retained a higher proportion of argon gas at its center, while the oxygen mole fraction at the center of the product prepared under the conditions of Example 1 was at a lower level. The permeation and diffusion of gas concentration alone was insufficient to drive externally introduced gas deep into the center of the jujube and sesame seed ball.

[0105] The absence of D-isoascorbic acid powder and sodium bicarbonate micron powder results in a significant amount of air trapped in the deep space of the jujube and sesame seed balls. The lack of a rapid absolute pressure reduction process leads to a higher residual oxygen content inside the jujube and sesame seed balls and a lower amount of mixed gas penetration.

[0106] Test Example 2:

[0107] The modified atmosphere preserved jujube and sesame balls prepared under the conditions of Example 1 were selected as the first group of test subjects, the modified atmosphere preserved jujube and sesame balls prepared under the conditions of Comparative Example 3 were selected as the second group of test subjects, and the modified atmosphere preserved jujube and sesame balls prepared under the conditions of Comparative Example 4 were selected as the third group of test subjects.

[0108] The first group of test objects, the second group of test objects, and the third group of test objects were placed in a constant temperature drying oven set at 60℃ for accelerated oxidation test.

[0109] On days 0, 5, 10, 15 and 20 of the accelerated oxidation experiment, the first group of test subjects, the second group of test subjects and the third group of test subjects were taken respectively for liquid-liquid extraction pretreatment.

[0110] Weigh 5.0 g of the pulverized first, second, and third groups of test samples, and add 20 mL of a mixed solvent of methanol and 0.1% formic acid water to each. Extract in an ultrasonic extractor at room temperature for 30 minutes. After extraction, centrifuge at 8000 rpm for 10 minutes, collect the supernatant, and filter through a 0.22 μm microporous membrane to obtain the high-performance liquid chromatography (HPLC) sample.

[0111] The sample was injected into the HPLC system for component separation. A C18 reversed-phase column was used, with dimensions of 250 mm × 4.6 mm and a diameter of 5 μm. Mobile phase A was set to 0.1% formic acid aqueous solution, and mobile phase B was set to acetonitrile. The elution program was set to gradient elution, with the following steps: increasing the volume percentage of mobile phase B from 20% to 50% within 0 to 10 minutes; and increasing the volume percentage of mobile phase B from 50% to 90% within 10 to 30 minutes. The mobile phase flow rate was set to 1.0 mL / min. The detector wavelength was set to 280 nm. The column oven temperature was set to a constant 30 °C.

[0112] High-performance liquid chromatography (HPLC) detection data were collected and recorded. The HPLC workstation software was used to identify the rosmarinic acid response peak with a retention time of 14.1 minutes and the palmitic acid ascorbate response peak with a retention time of 22.3 minutes. The relative retention rates of rosmarinic acid and palmitic acid ascorbate were calculated as percentages by comparing the peak area at each sampling time point with the peak area on day 0. HPLC detection data from day 15 were extracted to construct a two-dimensional chromatogram.

[0113] Table 2. Data on the relative retention rates of palmitic ascorbate and rosmarinic acid.

[0114] Test duration (days) Example 1: Relative retention rate of rosmarinic acid (%) Example 1: Relative retention rate of palmitic acid ascorbate (%) Comparative Example 3: Relative retention rate of rosmarinic acid (%) Comparative Example 3: Relative retention rate of palmitic acid ascorbate (%) Comparative Example 4: Relative retention rate of rosmarinic acid (%) 0 100.0 100.0 100.0 100.0 100.0 5 96.1 92.4 88.5 65.2 82.4 10 90.5 81.7 64.1 31.8 51.2 15 84.2 68.3 38.6 12.3 24.1 20 76.8 53.9 19.4 3.5 9.7

[0115] See attached document Figure 2 , attached Figure 2 The horizontal axis represents retention time in minutes, and the vertical axis represents absorbance in mAU. The solid line with a star corresponds to the chromatographic data curve of the first group of analytes on day 15, the dashed line with a triangle corresponds to the chromatographic data curve of the second group of analytes on day 15, and the solid line with a square corresponds to the chromatographic data curve of the third group of analytes on day 15.

[0116] The test results are as follows:

[0117] Based on the data in Table 2 and Figure 2 According to the results, the modified atmosphere packaging red date and sesame seed balls prepared under the conditions of Example 1 had a relative retention rate of rosmarinic acid of 84.2% and a relative retention rate of palmitic acid ascorbate of 68.3% on day 15. Figure 2 The solid line with a star shape shows a rosmarinic acid response peak at a retention time of 14.1 minutes. Figure 2 The solid line with a star shape shows a palmitic ascorbate response peak at a retention time of 22.3 minutes.

[0118] The modified atmosphere packaging (MAP) jujube and sesame seed balls prepared under the conditions of Comparative Example 3 did not contain D-isoascorbic acid powder. On day 15, the relative retention rate of palmitic acid ascorbic acid in the MAP jujube and sesame seed balls prepared under the conditions of Comparative Example 3 decreased to 12.3%, and the relative retention rate of rosmarinic acid decreased to 38.6%. Figure 2 The dashed line with a triangle in the middle has a response peak area lower than the threshold at the corresponding retention time. Figure 2 The solid line with a star shape represents the peak area of ​​the response at the corresponding retention time.

[0119] The modified atmosphere packaging (MAP) jujube and sesame seed balls prepared under the conditions of Comparative Example 4 did not contain added palmitic acid ascorbate. The relative retention rate of rosmarinic acid in the MAP jujube and sesame seed balls prepared under the conditions of Comparative Example 4 decreased to 24.1% on day 15. Figure 2The solid line with the square in the middle has no response peak at a retention time of 22.3 minutes.

[0120] The modified atmosphere packaging (MAP) jujube and sesame seed balls prepared under the conditions described in Example 1 comprise D-isoascorbic acid powder and palmitic acid ascorbate. The D-isoascorbic acid powder is located in the aqueous environment region composed of high fructose syrup. The palmitic acid ascorbate is located in the non-aqueous environment region composed of anhydrous propylene glycol and liquid soybean lecithin. Rosemary extract microcapsule powder is encapsulated within the non-aqueous environment region.

[0121] Under accelerated oxidation conditions, the outer layer of palmitic ascorbate first contacts the oxidizing agent and undergoes an oxidation reaction. The D-isoascorbic acid powder in the aquatic environment reduces the oxidized palmitic ascorbate to its initial state. This reduction process maintains the concentration of palmitic ascorbate in the non-aquatic environment. This maintenance of palmitic ascorbate concentration slows down the oxidative degradation of rosmarinic acid in the inner layer of the rosemary extract microcapsule powder.

[0122] The modified atmosphere packaging (MAP) jujube and sesame seed balls prepared under the conditions of Comparative Example 3 lacked D-isoascorbic acid powder in the aquatic environment. The lack of reducing agents caused the palmitic acid ascorbate in the non-aquatic environment to be oxidized and consumed. After the palmitic acid ascorbate was consumed, the oxidizing agents destroyed the rosmarinic acid molecules.

[0123] The modified atmosphere packaging (MAP) jujube and sesame seed balls prepared under the conditions of Comparative Example 4 lacked palmitic acid ascorbate in the non-aqueous environment. D-isoascorbic acid powder in the aqueous environment could not participate in the reaction protecting rosmarinic acid. The lack of an antioxidant pathway led to the degradation of rosmarinic acid in an oxidizing environment.

[0124] Test Example 3:

[0125] The modified atmosphere preserved jujube and sesame balls prepared under the conditions of Example 1 were selected as the first group of test samples, and the modified atmosphere preserved jujube and sesame balls prepared under the conditions of Comparative Example 2 were selected as the second group of test samples.

[0126] At 0, 24, 48 and 72 hours after the preparation of the modified atmosphere preserved jujube and sesame balls, the first and second groups of test samples were taken for aqueous phase free substance extraction.

[0127] Weigh 10.0g of the first and second sets of samples after crushing, add 50mL of phosphate buffer solution set at 4℃ to each, place them in a shaker, control the shaker speed at 150rpm, and shake for 15 minutes at 4℃ to dissolve rosmarinic acid into the phosphate buffer solution.

[0128] The shaken mixture was placed in a refrigerated centrifuge and centrifuged at 10,000 rpm for 15 minutes at 4°C. The aqueous clear liquid in the middle layer was collected and filtered through a microporous membrane with a pore size of 0.22 μm to obtain the aqueous free matter detection sample.

[0129] The aqueous sample for free matter detection was injected into the high-performance liquid chromatograph (HPLC) for component separation. A C18 reversed-phase column was used. Mobile phase A was set to 0.1% formic acid aqueous solution, and mobile phase B was set to methanol. The elution program was set to isocratic elution, with a mobile phase A to mobile phase B volume ratio of 60:40. The mobile phase flow rate was set to 0.8 mL / min. The detector wavelength was set to 330 nm. The column oven temperature was set to 25 °C.

[0130] High-performance liquid chromatography (HPLC) detection data were collected and recorded. The HPLC workstation software was used to identify the rosmarinic acid response peak with a retention time of 8.5 minutes. The mass concentration of rosmarinic acid in the aqueous phase of the sample was calculated using a standard curve prepared with rosmarinic acid standards. Two-dimensional chromatograms were plotted using HPLC detection data from the first and second groups of test samples extracted at 24 hours.

[0131] Table 3. Test data of free rosmarinic acid mass concentration in aqueous phase.

[0132] Sampling time (hours) Example 1: Free rosmarinic acid concentration (μg / mL) Comparative Example 2: Free rosmarinic acid concentration (μg / mL) 0 2.1 5.3 24 4.6 45.8 48 8.2 52.1 72 11.5 56.4

[0133] See attached document Figure 3 , attached Figure 3 The horizontal axis represents retention time in minutes, and the vertical axis represents the response signal in mV. The solid line with a star corresponds to the chromatographic data curve of the first group of test samples at 24 hours, and the dashed line with a triangle corresponds to the chromatographic data curve of the second group of test samples at 24 hours.

[0134] The test results are as follows:

[0135] Based on the data in Table 3 and Figure 3 According to the data, the concentration of free rosmarinic acid in the aqueous phase of the modified atmosphere preserved jujube and sesame balls prepared under the conditions of Comparative Example 2 was 45.8 μg / mL after 24 hours. Figure 3 The dashed line with the triangle in the middle shows the rosmarinic acid response peak at a retention time of 8.5 minutes.

[0136] The concentration of free rosmarinic acid in the aqueous phase of the modified atmosphere preserved jujube and sesame balls prepared under the conditions of Comparative Example 2 was 56.4 μg / mL at 72 hours.

[0137] The concentration of free rosmarinic acid in the aqueous phase of the modified atmosphere preserved jujube and sesame seed balls prepared under the conditions of Example 1 was 4.6 μg / mL at 24 hours and 11.5 μg / mL at 72 hours. Figure 3 The solid line with a star shape in the middle has a lower response signal strength at a retention time of 8.5 minutes than... Figure 3 The dashed line with the triangle in the middle represents the response signal strength at a retention time of 8.5 minutes.

[0138] High fructose syrup contains osmotic pressure. In the modified atmosphere packaging of jujube and sesame seed balls prepared under the conditions of Comparative Example 2, rosemary extract microcapsule powder was directly mixed with high fructose syrup. The wall material of the rosemary extract microcapsule powder ruptured upon contact with the high fructose syrup.

[0139] The wall material cracking caused the rosmarinic acid contained within to leak into the aquatic environment of the jujube and sesame seed capsules. The increased concentration of rosmarinic acid in the aquatic environment indicates that the microcapsules have lost their ability to release active substances in a controlled manner.

[0140] In the preparation of the modified atmosphere packaging red date and sesame seed balls obtained under the conditions of Example 1, rosemary extract microcapsule powder was added to Composition 1 for processing during the preparation of Composition 2. Anhydrous propylene glycol and liquid soybean lecithin in Composition 1 formed a coating layer on the outside of the rosemary extract microcapsule powder. This coating layer isolated the contact path between the rosemary extract microcapsule powder and the high fructose syrup.

[0141] The coating layer prevents osmotic pressure-induced wall material rupture. The intact wall material maintains the controlled release process of rosmarinic acid, keeping the concentration of rosmarinic acid in the aquatic environment of the jujube and sesame seed pills at a low level.

[0142] Test Example 4:

[0143] The modified atmosphere preserved jujube and sesame balls prepared under the conditions of Example 1 were selected as the first group of test subjects, the modified atmosphere preserved jujube and sesame balls prepared under the conditions of Comparative Example 1 were selected as the second group of test subjects, the modified atmosphere preserved jujube and sesame balls prepared under the conditions of Comparative Example 3 were selected as the third group of test subjects, and the modified atmosphere preserved jujube and sesame balls prepared under the conditions of Comparative Example 5 were selected as the fourth group of test subjects.

[0144] The first group of test objects, the second group of test objects, the third group of test objects, and the fourth group of test objects were placed in an aging test chamber with a temperature of 60℃ and a relative humidity of 75% for accelerated aging tests.

[0145] On days 0, 3, 6, 9, 12 and 15 of the accelerated aging test, the first group of test subjects, the second group of test subjects, the third group of test subjects and the fourth group of test subjects were taken out and crushed.

[0146] Weigh 20.0g of the first, second, third and fourth groups of test objects after crushing, add 100mL of petroleum ether to each, extract at room temperature for 2 hours, filter and collect the filtrate, and use a rotary evaporator to evaporate the petroleum ether solvent at 40℃ to obtain the oil test sample.

[0147] Weigh 2.0g of the oil test sample and place it in an Erlenmeyer flask. Add 30mL of a mixed solvent of chloroform and glacial acetic acid, and 1mL of saturated potassium iodide solution. Place the sample in the dark for 3 minutes, add 100mL of pure water and starch indicator, and titrate with sodium thiosulfate standard titration solution. Record the volume consumed and calculate the peroxide value.

[0148] Weigh 3.0g of the oil test sample and place it in an Erlenmeyer flask. Add 50mL of a mixed solvent of diethyl ether and isopropanol, add phenolphthalein indicator, and titrate with potassium hydroxide standard titration solution. Record the volume consumed and calculate the acid value.

[0149] Table 4. Data on peroxide value of oils at different time points in accelerated aging test

[0150] Test duration (days) Example 1 (g / 100g) Comparative Example 1 (g / 100g) Comparative Example 3 (g / 100g) Comparative Example 5 (g / 100g) 0 0.11 0.12 0.10 0.13 3 0.14 0.38 0.22 0.19 6 0.18 0.72 0.39 0.31 9 0.23 1.25 0.81 0.62 12 0.29 2.41 1.54 1.18 15 0.35 3.86 2.12 1.89

[0151] Table 5. Data on acid value of oils at different time points in accelerated aging test.

[0152] Test duration (days) Example 1 (mg / g) Comparative Example 1 (mg / g) Comparative Example 3 (mg / g) Comparative Example 5 (mg / g) 0 0.7 0.7 0.6 0.8 3 0.9 1.2 1.0 1.0 6 1.1 1.8 1.4 1.3 9 1.2 2.5 2.0 1.7 12 1.4 3.4 2.7 2.4 15 1.5 4.6 3.6 3.1

[0153] See attached document Figure 4 , attached Figure 4 The horizontal axis represents aging time in days, and the vertical axis represents peroxide value in g / 100g. Specifically, the solid line with a star corresponds to the peroxide value data curves of the first group of test subjects at various time points; the dashed line with a triangle corresponds to the peroxide value data curves of the second group of test subjects at various time points; the solid line with a square corresponds to the peroxide value data curves of the third group of test subjects at various time points; and the dashed line with a circle corresponds to the peroxide value data curves of the fourth group of test subjects at various time points.

[0154] The test results are as follows:

[0155] Based on the data in Tables 4 and 5, and Figure 4 According to the results, the modified atmosphere packaging red date and sesame seed balls prepared under the conditions described in Example 1 had a peroxide value of 0.35 g / 100 g and an acid value of 1.5 mg / g on day 15. Figure 4 The solid line with the star shape in the middle remains stable over time.

[0156] The modified atmosphere packaging red date and sesame seed balls prepared under the conditions of Comparative Example 1 had a peroxide value of 3.86 g / 100 g on day 15. Figure 4 The slope of the dashed line with the triangle in the middle increases.

[0157] The modified atmosphere packaging red date and sesame seed balls prepared under the conditions of Comparative Example 3 had a peroxide value of 2.12 g / 100 g on day 15. Figure 4 The solid line with the square in the middle rises after the 9th day.

[0158] The modified atmosphere packaging red date and sesame seed balls prepared under the conditions of Comparative Example 5 had a peroxide value of 1.89 g / 100 g on day 15. Figure 4 The dotted line with a circle in the middle rises after the 9th day.

[0159] The modified atmosphere packaging red date and sesame seed balls prepared under the conditions of Comparative Example 1 did not contain either Composition 1 or Composition 2. The lipid components in the red date and sesame seed balls undergo oxidation upon contact with oxygen molecules in a high-temperature and high-humidity environment, producing peroxides and free fatty acids, leading to an increase in peroxide value and acid value.

[0160] The modified atmosphere packaging (MAP) jujube and sesame seed balls prepared under the conditions of Comparative Example 3 did not contain D-isoascorbic acid powder or sodium bicarbonate micron powder. Air remained inside the jujube and sesame seed balls. This air contains oxygen. During the accelerated aging test, oxygen combined with lipid molecules, leading to an increase in the peroxide value of the oils. The MAP jujube and sesame seed balls prepared under the conditions of Comparative Example 5 did not undergo an absolute pressure reduction operation. The oxygen inside the jujube and sesame seed balls did not escape, and the introduced mixed gas did not reach the center of the jujube and sesame seed balls. The residual oxygen inside the jujube and sesame seed balls led to the accumulation of peroxides.

[0161] In the modified atmosphere packaging (MAP) jujube and sesame seed balls prepared under the conditions described in Example 1, the carbon dioxide generated from the reaction of D-isoascorbic acid powder and sodium bicarbonate micropowder displaces the oxygen remaining inside the jujube and sesame seed balls. An absolute pressure reduction operation allows the mixed gas to enter the interior of the jujube and sesame seed balls, blocking the pathway for oxygen to enter the lipid interior.

[0162] Anhydrous propylene glycol and liquid soybean lecithin coating prevent the rosemary extract microcapsule powder from rupturing, while D-isoascorbic acid powder maintains the concentration of palmitic acid ascorbate and slows down the oxidative degradation process of rosmarinic acid. The peroxide value and acid value of the lipid components remain at low levels.

[0163] Test Example 5:

[0164] The modified atmosphere preserved jujube and sesame balls prepared under the conditions in Example 1 were selected as the first group of test samples, the modified atmosphere preserved jujube and sesame balls prepared under the conditions in Comparative Example 1 were selected as the second group of test samples, and the modified atmosphere preserved jujube and sesame balls prepared under the conditions in Comparative Example 3 were selected as the third group of test samples.

[0165] The first, second, and third sets of test samples were placed in a constant temperature incubator at 60°C for 15 days to conduct an accelerated oxidation test.

[0166] After the accelerated oxidation test, the first, second, and third sets of test samples were taken out and pulverized. 3.0g of the pulverized first, second, and third sets of test samples were weighed and placed into 20mL headspace vials, which were then sealed with PTFE septa and aluminum caps.

[0167] Place the headspace vial into the heating incubation zone of the gas chromatography-ion mobility spectrometry instrument and incubate at 60°C for 20 minutes, with the heating chamber rotating at 500 rpm during the incubation process.

[0168] After incubation, 500 μL of headspace gas was drawn using a syringe heated to 85 °C and injected into the gas chromatograph-ion mobility spectrometer for separation.

[0169] Gas chromatography analysis was performed using a weakly polar capillary column at a temperature of 60°C. Nitrogen gas with a purity of 99.999% was used as the carrier gas. The programmed pressure parameters were as follows: the carrier gas flow rate was maintained at 2.0 mL / min from 0 to 2 minutes; the carrier gas flow rate was increased to 15.0 mL / min from 2 to 10 minutes; and the carrier gas flow rate was increased to 100.0 mL / min from 10 to 20 minutes.

[0170] The drift tube for ion mobility spectrometry analysis was 98 mm long, the temperature inside the drift tube was 45 °C, the drift gas was 99.999% pure nitrogen, and the drift gas flow rate was 150.0 mL / min. The radiation source was a tritium source.

[0171] Gas chromatography-ion mobility spectrometry (GC-IMS) data were collected, and the hexanal response peak with a retention time of 5.2 minutes and the nonanal response peak with a retention time of 8.7 minutes were identified using the instrument's accompanying workstation software. The three-dimensional volume data of the hexanal and nonanal response peaks were extracted and integrated. One-dimensional gas chromatography data at specific drift times were extracted to plot the signal response spectrum.

[0172] Table 6. Peak volume test data of characteristic oxidative deterioration flavor compounds after 15 days of accelerated oxidation test.

[0173] Test object Hexanal peak volume Nonaldehyde peak volume Example 1 1856 942 Comparative Example 1 14582 6835 Comparative Example 3 8741 4128

[0174] See attached document Figure 5 , attached Figure 5 The horizontal axis represents retention time in minutes, and the vertical axis represents signal intensity in mV. Specifically, the solid line with a star corresponds to the gas chromatography data curve of the first group of test samples on day 15, the dashed line with a triangle corresponds to the gas chromatography data curve of the second group of test samples on day 15, and the solid line with a square corresponds to the gas chromatography data curve of the third group of test samples on day 15.

[0175] The test results are as follows:

[0176] Based on the data in Table 6 and Figure 5 According to the results, the modified atmosphere packaging red date and sesame seed balls prepared under the conditions described in Example 1 showed a peak volume of 1856 for hexanal and 942 for nonanal after 15 days of accelerated oxidation testing. Figure 5 The solid line with a star shape shows lower signal strength at retention times of 5.2 minutes and 8.7 minutes compared to the dashed line with a triangle shape at the same retention times.

[0177] The modified atmosphere packaging (MAP) of the jujube and sesame seed balls prepared under the conditions of Comparative Example 1 showed a peak volume of 14582 for hexanal and 6835 for nonanal. Figure 5 The dashed line with the triangle in the middle shows the response peaks of hexanal and nonanal at retention times of 5.2 minutes and 8.7 minutes.

[0178] The modified atmosphere packaging (MAP) of the jujube and sesame seed balls prepared under the conditions of Comparative Example 3 showed a peak volume of 8741 for hexanal and 4128 for nonanal. Figure 5 The signal strength of the solid line with squares at retention times of 5.2 minutes and 8.7 minutes is higher than that of the solid line with stars at retention times of 5.2 minutes and 8.7 minutes.

[0179] Hexanal and nonanal are volatile flavor compounds produced by the oxidation of unsaturated fatty acids in jujube and sesame seed balls when exposed to oxygen at high temperatures. The accumulation of these flavor compounds reflects the degree of lipid oxidation.

[0180] The modified atmosphere packaging (MAP) jujube and sesame seed balls prepared under the conditions of Comparative Example 1 did not contain any added antioxidants or protective atmosphere. Oxygen in the air combines with unsaturated fatty acids to undergo a chain oxidation reaction. This chain oxidation reaction produces hexanal and nonanal molecules.

[0181] The modified atmosphere packaging (MAP) jujube and sesame seed balls prepared under the conditions of Comparative Example 3 did not contain added D-isoascorbic acid powder or sodium bicarbonate micron powder. No carbon dioxide was generated inside the jujube and sesame seed balls, resulting in residual air within the pores. Oxygen in the air participates in the oxidative degradation process of unsaturated fatty acids.

[0182] The carbon dioxide generated by the internal reaction of the modified atmosphere preserved jujube and sesame balls prepared under the conditions in Example 1 is used to expel the oxygen inside the pores. The pressure reduction operation introduces a mixed gas to fill the pores, blocking the contact between oxygen and lipid molecules.

[0183] Anhydrous propylene glycol and liquid soybean lecithin coating slow down the consumption of antioxidant components. The fatty acid oxidation and cleavage pathway is interrupted, reducing the production of hexanal and nonanal molecules, thus mitigating the changes in flavor of the jujube and sesame balls.

Claims

1. A method for synergistic preservation of jujube and sesame seed pills with microencapsulated antioxidants, characterized in that, Including the following steps: Anhydrous propylene glycol and liquid soybean lecithin were added to a mixing tank, mechanically stirred and heated to mix. Sodium phytate powder and palmitic acid ascorbate were added in sequence, stirred at a constant temperature and then cooled to obtain composition one. Rosemary extract microcapsule powder was added to composition one and processed using a high-shear dispersing emulsifier to obtain composition two. Black sesame powder, jujube powder, D-isoascorbic acid powder and sodium bicarbonate powder are put into a mixer and dry-mixed to obtain a premixed dry material. The premixed dry material is placed in a kneader, high fructose syrup is pumped in and the composition is added dropwise, and kneaded to form a wet material; The wet material is sealed and left to stand for maturation, then kneaded into spherical balls to obtain shaped jujube and sesame balls; the shaped jujube and sesame balls are placed in a packaging composite bag and transferred into a modified atmosphere packaging machine. After the cavity is closed, the vacuum pump is started to reduce the absolute pressure and maintain it, while pure carbon dioxide is injected separately to the first preset absolute pressure. Then, a mixed gas consisting of argon and nitrogen is continuously injected into the second preset absolute pressure for heat sealing, resulting in the finished product of modified atmosphere preserved jujube and sesame balls.

2. The method for synergistic preservation of jujube and sesame seed pills with microencapsulated antioxidants according to claim 1, characterized in that, The steps of adding anhydrous propylene glycol and liquid soybean lecithin to a mixing tank, mechanically stirring and heating to mix, then sequentially adding sodium phytate powder and palmitic acid ascorbate, stirring at a constant temperature, and then cooling to obtain composition one specifically include: 8.0 to 12.0 parts of the anhydrous propylene glycol and 1.5 to 2.5 parts of the liquid soybean lecithin were added to the stirred tank equipped with a water bath jacket; Start the mechanical stirring and control the speed of the mechanical stirring to be 300 rpm to 500 rpm; Heat the mixture to a constant temperature of 40°C to 45°C, mix thoroughly, and then slowly add 0.8 to 1.2 parts of the sodium phytate powder and 1.0 to 2.0 parts of the palmitic acid ascorbate ester. The mixture is stirred continuously at a constant temperature of 40°C to 45°C for 15 to 20 minutes, and then cooled to 20°C to 25°C to obtain the first composition.

3. The method for synergistic preservation of jujube and sesame seed pills with microencapsulated antioxidants according to claim 1, characterized in that, The step of adding rosemary extract microcapsule powder to composition one and processing it using a high-shear dispersing emulsifier to obtain composition two specifically includes: 4.0 to 6.0 parts of the rosemary extract microcapsule powder are slowly added to the first composition in batches; The process is carried out using the high-shear dispersion emulsifier at an ambient temperature of 20°C to 25°C; the rotation speed of the high-shear dispersion emulsifier is controlled to be 1500 rpm to 2000 rpm. The mixture is processed continuously for 3 to 5 minutes to obtain the second composition.

4. The method for synergistic preservation of jujube and sesame seed pills with microencapsulated antioxidants according to claim 1, characterized in that: Before the step of dry mixing black sesame powder, jujube powder, D-isoascorbic acid powder and sodium bicarbonate powder in a mixer to obtain premixed dry material, the black sesame powder and jujube powder are subjected to ultra-fine pulverization treatment to control the particle size of the black sesame powder and jujube powder to be 80 mesh to 100 mesh, and the mass moisture content of the jujube powder is 3% to 5%.

5. The method for synergistic preservation of jujube and sesame seed pills with microencapsulated antioxidants according to claim 1, characterized in that, The step of dry-mixing black sesame powder, jujube powder, D-isoascorbic acid powder, and sodium bicarbonate powder in a mixer to obtain a premixed dry material specifically includes: Add 62.5 to 67.5 parts of the black sesame powder and 37.5 to 42.0 parts of the jujube powder into the mixer; Add 0.25% to 0.45% of the D-isoascorbic acid powder and 0.05% to 0.12% of the sodium bicarbonate powder, calculated as a percentage of the total mass of the black sesame powder and the jujube powder; The premixed dry material is obtained by dry mixing at 20°C to 25°C for 10 to 15 minutes until it is uniformly mixed.

6. The method for synergistic preservation of jujube and sesame seed pills with microencapsulated antioxidants according to claim 1, characterized in that, The step of placing the premixed dry material in a kneader, pumping in high fructose syrup and adding the second composition to knead and form a wet material specifically includes: Weigh 100.0 parts of the premixed dry material and place it in the kneader; Slowly pump in 25.0 to 35.0 parts of the high fructose syrup while simultaneously adding 0.20 to 0.50 parts of the second composition; The kneader is controlled to rotate at 30 rpm to 50 rpm, and kneaded continuously for 8 to 12 minutes at 20°C to 25°C to form the wet material.

7. The method for synergistic preservation of jujube and sesame seed pills with microencapsulated antioxidants according to claim 6, characterized in that, The steps of sealing and allowing the wet material to stand and mature, then kneading it into spherical balls to obtain the formed jujube and sesame balls specifically include: Transfer the wet material to a stainless steel tray, cover and seal it, and let it stand at 20°C to 25°C for 30 to 45 minutes to mature it. After maturation, the wet material is fed into a pelleting machine and kneaded into spherical pellets with a single weight of 8.0g to 10.0g to obtain the formed jujube and sesame pellets.

8. The method for synergistic preservation of jujube and sesame seed pills with microencapsulated antioxidants according to claim 1, characterized in that, The steps of placing the formed jujube and sesame balls into a packaging composite bag and transferring them into a modified atmosphere packaging machine, closing the cavity, starting a vacuum pump to reduce and maintain the absolute pressure, and separately injecting pure carbon dioxide to the first preset absolute pressure specifically include: The formed jujube and sesame balls are placed in the packaging composite bag, which is a high-barrier packaging composite bag, and then moved into the modified atmosphere packaging machine with a pulse control system. After the cavity is closed, the vacuum pump is started. Within a time span of 1.0 to 2.0 seconds, the absolute pressure inside the cavity is reduced to 15 kPa to 20 kPa and held for 3.0 to 5.0 seconds; Then, the pure carbon dioxide is injected into the cavity individually until the absolute pressure inside the cavity rises back to the first preset absolute pressure, which is 40 kPa to 45 kPa, at which point the injection of the pure carbon dioxide is stopped.

9. The method for synergistic preservation of jujube and sesame seed pills with microencapsulated antioxidants according to claim 8, characterized in that, The step of switching back to a mixed gas of argon and nitrogen and continuously injecting it under a second preset absolute pressure for heat sealing to obtain the finished modified atmosphere preserved jujube and sesame balls specifically includes: After the injection of pure carbon dioxide is stopped, the injection is switched to a mixed gas consisting of argon gas (8% to 12% by volume) and nitrogen gas (88% to 92% by volume) for continuous injection. The injection continues until the absolute pressure inside the cavity reaches the second preset absolute pressure, which is 103 kPa to 105 kPa. The cavity is then heat-sealed under the second preset absolute pressure to obtain the finished modified atmosphere preserved jujube and sesame balls.

10. The method for synergistic preservation of jujube and sesame seed pills with microencapsulated antioxidants according to claim 9, characterized in that, After the step of switching back to a mixed gas composed of argon and nitrogen and continuously injecting it to a second preset absolute pressure for heat sealing to obtain the finished product of modified atmosphere preserved jujube and sesame balls, the following steps are also included: The modified atmosphere preserved jujube and sesame balls are placed in a constant temperature and light-proof warehouse with a temperature of 20°C to 25°C and a relative humidity of 60% to 65% and left to stand for 24 to 48 hours.

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