Allulose with enhanced stability

Abstract

The present invention relates to an allulose storage package that enhances the storage stability of allulose syrup, and a method for enhancing the storage stability of allulose.

Description

[Technical field]

[0001] The present invention relates to an allulose storage package that enhances the storage stability of allulose syrup, and a method for enhancing the storage stability of allulose. [Background technology]

[0002] Allulose is an epimer of fructose (D-fructose) and is a type of functional sugar known as a rare sugar, and is known to be effective in preventing and improving diabetes because it has a high sweetness of about 60-70% of sugar while having almost zero calories. Allulose is also known to have excellent solubility, and is one of the materials that is attracting attention for use in food.

[0003] Recently, a method for producing allulose by a biological method involves contacting a fructose-containing substrate solution with an allulose epimerization enzyme or a fungus that produces the enzyme to carry out an allulose conversion reaction. The fructose-containing solution, which is the reaction raw material used in the allulose conversion process, can be a fructose isomerization product obtained by isomerization of glucose obtained by decomposition of starch, etc. In addition, the reaction solution containing allulose is made into a high-purity solution using chromatography, and then the product is produced by syrup or crystallization.

[0004] Allulose has low crystallinity and is difficult to crystallize, so it is stored and distributed in the form of allulose syrup. However, the allulose syrup has a problem in that the allulose content gradually decreases over the storage period due to various influencing factors such as pH, temperature, and electrical conductivity.

[0005] When allulose syrup is stored for a long time, the allulose content decreases and allulose is converted or decomposed into other substances. The allulose conversion reaction product may be, for example, other sugars such as fructose, or may be converted into a furfural-based substance such as HMF. Thus, the allulose syrup is decomposed or converted into other substances during the storage period, and the content gradually decreases. Summary of the Invention [Problem to be solved by the invention]

[0006] One embodiment of the present invention is to provide an allulose syrup with improved storage stability.

[0007] Another example of the present invention relates to an allulose storage package comprising an allulose syrup having improved storage stability and a storage container.

[0008] Another example of the present invention relates to a method for increasing the storage stability of allulose by creating free space in the storage container of allulose syrup, filling with nitrogen and / or optimizing the storage container of allulose. [Means for solving the problem]

[0009] The present invention relates to an allulose storage package for improving the storage stability of allulose syrup, and a method for improving the storage stability of allulose. Specifically, the method for improving the storage stability of allulose syrup according to the present invention can be performed by one or more methods selected from the group consisting of a method for adjusting the free space volume in a storage container to 20% or less based on 100% of the total storage container volume, a method for filling an allulose storage container with nitrogen, and a method for reducing direct contact between allulose syrup and the container material, in which the container is made of tin or tin alloy material and the inner surface includes a polymer resin coating layer.

[0010] The present invention provides an allulose syrup that has improved storage stability and maintains the maximum allulose content under storage conditions such as immediately after production, storage, and distribution. In this specification, the storage stability of allulose syrup means that the allulose content contained in the allulose syrup is the same as immediately after production or the decrease in the allulose content is minimized, for example, based on the solid content (wt%) of allulose immediately after production or at 0 weeks of storage being 100 wt%, the allulose content during the storage period is maintained as close to 100 wt%, for example, 99.9 wt% or more, 97 wt% or more, 95 wt% or more, 92.5 wt% or more, or 90 wt% or more. Effect of the Invention

[0011] The present invention provides an allulose storage package that enhances the storage stability of allulose syrup, and a method for enhancing the storage stability of allulose, thereby preventing the decomposition of allulose or its conversion to other substances, thereby minimizing the reduction in allulose content, even when allulose syrup is stored and distributed for a long period of time. DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

[0012] The present invention will now be described in more detail. One example of the present invention may be an allulose storage package comprising a storage container and allulose syrup, in which the allulose syrup is filled so that the volume of the empty space excluding allulose is 20% (v / v) or less, based on the volume of the storage container being 100% (v / v).

[0013] Based on the capacity of the storage container (100% (v / v)), the capacity (volume) of the empty space may be 20% or less, 17.5% or less, 15% or less, 12.5% ​​or less, 10% or less, 7.5% or less, or 6% or less in consideration of the storage stability of allulose, for example, 1 to 20%, 1 to 20%, 1 to 17.5%, 1 to 15%, 1 to 12.5%, 1 to 10%, 1 to 7.5%, 1 to 6%, 1.5 to 20%, 1.5 to 17.5%, 1.5 to 15%, 1.5 to 12.5%, 1.5 to 10%, 1.5 to 7.5%, 1.5 to 6%, 2 to 20%, 2 to 17.5%, 2 to 15%, 2 to 12.5%, 2 to 10%, 2 to 7.5%, 2 to 6%, 2.5 to 20%, 2.5~17.5%, 2.5~15%, 2.5~12.5%, 2.5~10%, 2.5~7.5%, 2.5~6%, 3~20%, 3~17.5%, 3~15%, 3~12.5%, 3~10%, 3~7.5%, 3~6%, 3.5~20%, 3.5~17.5%, 3.5~15%, 3.5~12.5%, It may be 3.5-10%, 3.5-7.5%, 3.5-6%, 4-20%, 4-17.5%, 4-15%, 4-12.5%, 4-10%, 4-7.5%, 4-6%, 4.5-20%, 4.5-17.5%, 4.5-15%, 4.5-12.5%, 4.5-10%, 4.5-7.5%, or 4.5-6%. The smaller the volume of the empty space, the better, considering the storage stability of allulose, but it is preferable to set it within an appropriate range, considering the possibility of volume expansion during storage.

[0014] The allulose preservation or storage container applicable to the present invention includes a container body having a storage space formed therein and an inlet formed at the top thereof to be connected to the storage space, and a cover member detachably coupled to the inlet of the container body to seal the storage space. The shape or form of the container is not particularly limited.

[0015] When the allulose storage package according to the present invention is filled with allulose syrup with the volume of the empty space excluding allulose being 20% ​​or less based on the capacity (volume) of the allulose storage container or storage container being 100%, the allulose syrup can be stored at 25°C for 3 weeks and then at 35°C for 7 weeks for a total storage period of 10 weeks, and the relative allulose content can be 99.9 wt% or more, 97 wt% or more, 95 wt% or more, 92.5 wt% or more, or 90 wt% or more based on the allulose content (wt%) at the start of storage, 0 weeks of storage, which is 100 wt%.

[0016] The container for storing allulose syrup according to an embodiment of the present invention may be made of a metal, metal alloy, or polymer material, and when the container is made of a metal or metal alloy material, the inner surface of the container is preferably coated with a polymer to minimize direct contact with the allulose syrup. The coating on the inner surface of the container preferably coats the entire inside of the container, and the coating may include a single coating, a double coating, or a multiple coating of three or more times, and more preferably a multiple coating of two or more times to minimize direct contact between the allulose syrup and the metal or metal alloy material. The metal or metal alloy material is not particularly limited as long as it is a material that can be used for food containers, and may be, for example, tin or a tin alloy. The coating agent on the inner surface of the container is not particularly limited as long as it is a material that can be used for food containers, and may be, for example, an epoxy phenol-based resin that can be used for food containers, and may be, for example, a commercially available product, Canguard 5K-872 (trade name).

[0017] In the present invention, allulose can be provided in the form of allulose syrup. For example, the allulose syrup may contain 0.1-100% by weight of allulose based on the solid content, for example, low-purity allulose syrup containing 1-50% by weight, 3-35% by weight, 3-25% by weight, or 3-20% by weight, or high-purity allulose syrup containing 70% by weight or more, 80% by weight or more, 85% by weight or more, 90% by weight or more, 95% by weight or more, 96% by weight or more, 97% by weight or more, or 99% by weight or more.

[0018] The viscosity and electrical conductivity of the allulose syrup can be set in various ways, and as necessary, the allulose syrup obtained in the manufacturing process can be poured directly into a storage container, or the allulose syrup obtained after adding an adjuster for adjusting the viscosity and / or electrical conductivity or performing an additional process can be poured into a storage container and stored. For example, the viscosity of the allulose syrup may be 2 cps to 200 cps at a temperature of 45° C., and the electrical conductivity may be 1000 μS / cm or less, for example, 0.01 to 1000 μS / cm, preferably 200 μS / cm or less, 150 μS / cm or less, 100 μS / cm or less, 80 μS / cm or less, 50 μS / cm or less, 30 μS / cm or less, for example, 0.1 to 200 μS / cm, 0.1 to 150 μS / cm, 0.1 to 100 μS / cm, 0.1 to 0.1 to 80 μS / cm, 0.1 to 50 μS / cm, or 0.1 to 30 μS / cm.

[0019] According to the present invention, the pH of the allulose syrup at the start of storage may be 3.8 or more and 5.5 or less, for example, 3.8 to 5.5 or less, 3.9 to 5.5 or less, 4.0 to 5.5 or less, 4.1 to 5.5 or less, 4.2 to 5.5 or less, 4.3 to 5.5 or less, 4.4 to 5.5 or less, 4.5 to 5.5 or less, 4.6 to 5.5 or less, 4.7 to 5.5 or less, or 4.8 to 5.5 or less.

[0020] In a specific example, the allulose syrup can be obtained by a manufacturing method including a biologically obtained allulose-containing solution, activated carbon treatment, high-purity separation by SMB chromatography, and an ion purification step, and optionally a step of concentrating the allulose syrup treated by the purification step can be further performed, or an ion purification step can be further performed before high-purity separation after the activated carbon treatment step of the allulose-containing solution. The ion purification step performed after the activated carbon treatment step can be the same as or different from the ion purification step performed after the high-purity separation step, and the ion exchange resin is not particularly limited.

[0021] The biologically derived allulose-containing solution can be produced by culturing a microorganism producing allulose epimerization enzyme or a recombinant microorganism into which a gene encoding allulose epimerization enzyme has been introduced, and reacting the microorganism producing allulose epimerization enzyme or the allulose epimerization enzyme obtained therefrom with a fructose-containing raw material. The allulose epimerization enzyme can be carried out in a liquid reaction or a solid-phase reaction using an immobilized enzyme. An example of an allulose conversion reaction is described in Korean Patent No. 10-1318422, etc.

[0022] The allulose-containing solution is subjected to SMB chromatography separation to separate an allulose fraction having a higher allulose content than the conversion reaction product and a fructose raffinate, and the allulose fraction can be subjected to an ion purification process to produce an allulose syrup product, or further subjected to a concentration process to produce a concentrated product. The psicose fraction can be separated / purified so that the psicose content is 85% by weight or more, for example, 85% to 95% by weight (w / w) or more.

[0023] A preferred embodiment of the present invention is an allulose storage package including a container and allulose syrup, in which the volume of the empty space excluding allulose is 20% or less based on the container volume of 100%, and the empty space of the container is filled with allulose syrup, and the container may be made of tin or tin alloy material, and the inner surface may include a coating layer of epoxy phenol resin. More preferably, the allulose storage package may further include the allulose syrup having a pH of 3.8 to 5.5 at the start of storage, and the allulose fraction obtained by subjecting the allulose conversion reaction product using a substrate to a decolorization process using activated carbon and a high-purity separation process using a chromatography filled with a calcium (Ca2+) type ion exchange resin is subjected to ion purification. Therefore, the allulose syrup contained in the allulose storage package may have storage stability such that the allulose content is 90.0% or more or 92.5% or more when stored at 45°C for 4 weeks, based on the allulose content (wt%) at 100% at the time of storage for 0 weeks. EXAMPLES

[0024] The present invention will be described in more detail with reference to the following examples, but the scope of the present invention is not intended to be limited to the following examples.

[0025] Example 1: Stabilization test by container empty space volume Allulose syrup (liquid sample) with a solid content of 70bx, an allulose purity of 97wt / wt%, and a pH of 4.1 was poured into a 1L polyethylene sample container at 90% of the total volume of the sample container (head space 10%), and experimental group 1-2 (head space 90%) was poured at 10% of the total volume of the sample container. The head space volume of the container was adjusted to the weight of allulose to be poured, taking into account the density of the allulose syrup and the volume of the storage container. The prepared sample container filled with allulose was stored in an incubator at 25°C for 3 weeks, and then stored at 25°C until the 3rd week to observe the change quickly. Samples were taken in the 3rd week, and then stored at 35°C from the 3rd week for an accelerated experiment. From the 4th week, the allulose syrup stored at 35°C was analyzed from the time the sample was taken. During the storage period, a small amount of allulose sample was taken at weekly intervals and diluted to 3bx with water to prepare an analysis sample. The allulose content of the analysis sample was measured by HPLC analysis. The specific HPLC analysis conditions were 87C (Biorad HPX-87C, 7.8mmΦ×300mm) column at 80℃, 100% water as mobile phase at 0.6ml / min flow rate, and detection was performed using an RI Detector. Table 1 below shows the results of measuring the allulose content (wt%) and change (wt%) of experimental group 1-1 (head space 10%) and experimental group 1-2 (head space 90%) depending on the storage temperature and storage period of allulose.

[0026] [Table 1]

[0027] As shown in Table 1, the samples were stored at 25°C for 3 weeks and then at 35°C for 7 weeks, for a total of 10 weeks of storage. Based on the allulose content (wt%) at the start of storage, 0 weeks of storage, which is 100 wt%, the allulose content of experimental group 1-1 (head space 10%) was 92.37 wt%, and the allulose content of experimental group 1-2 (head space 90%) was 89.59 wt%. It was confirmed that the allulose content of experimental group 1-1, which has 10% empty space, was 90% or more and had excellent storage stability. The larger the head space of the storage container containing allulose syrup, the more rapidly the solid allulose content decreased.The reason for this decrease in allulose content was confirmed to be that the larger the head space, the higher the air content inside the container, making allulose more unstable, resulting in a more significant decrease in allulose content.

[0028] Example 2: Stabilization test by filling with nitrogen Three sample containers were prepared by pouring 250 g of allulose syrup (liquid sample) having a solid content of 70bx, an allulose purity of 97 wt / wt%, and a pH of 4.1 into a polyethylene sample container with a capacity of approximately 250 mL so that the sample container was filled to 95% of the total capacity. Therefore, the free space in the allulose syrup storage container was 5% of the container capacity. In the control experiment, the sample container filled with the allulose sample was sealed under atmospheric conditions and stored in an incubator at 45°C. Experimental group 2-1 is an experimental group in which the air in the head space of the sample container filled with the allulose sample was replaced with nitrogen, and after allulose syrup was poured into the sample container, nitrogen (purity 99% or more) was poured into the head space through a supply line into the container at 2 L / min for 5 minutes, the sample container was sealed, and stored in an incubator at 45° C. Experimental group 2-2 is an experimental group in which the air in the head space of the sample container filled with the allulose sample was poured into the allulose syrup through a supply line into the allulose syrup, nitrogen (purity 99% or more) was poured into the head space at 2 L / min for 5 minutes, the sample container was sealed, and stored in an incubator at 45° C. For the control group, experimental group 2-1, and experimental group 2-2, a small amount of allulose sample was taken at intervals of one week during the storage period, and diluted to 3bx with water to prepare an analysis sample. The analysis sample was measured for allulose content by HPLC analysis. The specific HPLC analysis conditions were 87C (Biorad HPX-87C, 7.8 mmΦ×300 mm) column, 100% water as the mobile phase at a flow rate of 0.6 ml / min at a temperature of 80° C., and detection was performed using an RI Detector. Table 2 below shows the results of measuring the allulose content (wt%) and change (wt%) of the control group (air in the head space), experimental group 2-1 (nitrogen injected into the head space), and experimental group 2-1 (nitrogen injected into the allulose syrup) depending on the storage period of allulose.

[0029] [Table 2]

[0030] As shown in the experimental results in Table 2, it was confirmed that the decrease in allulose content was smaller in experimental groups 2-1 and 2-2, which were filled with nitrogen, compared to the control group, which was not filled with nitrogen during the three-week storage period. The reason for this decrease in allulose content was that substances such as carbon dioxide and oxygen in the air reacted with allulose, resulting in a decrease in content. Experimental group 2-1, in which nitrogen was injected into the head space of the sample container filled with allulose syrup, and experimental group 2-2, in which nitrogen was injected into the allulose syrup, showed a lower reduction in allulose content compared to the control group, and there was no significant difference due to the nitrogen filling method, but it was confirmed that experimental group 2-2, in which nitrogen was injected into allulose syrup, was preferable because it had the effect of reducing the air in the allulose syrup.

[0031] Example 3: Stability test using the inner material of the container As storage containers for allulose syrup with a capacity of 20 L, we prepared a tin can with the entire inside of the cylindrical container double-coated with Canguard 5K-872 (epoxy phenolic) (Experiment 3-1), a TIN can with the entire inside of the container single-coated with Canguard 5K-872 (epoxy phenolic) (Experiment 3-2), a TIN can with the inside of the cylindrical container single-coated with Canguard 5K-872 (epoxy phenolic) (Experiment 3-3), and a polyethylene container (Experiment 3-4). Canguard 5K-872 (epoxy phenolic) is a paint that can be used as a food coating in Korea. Each of the four prepared storage containers was filled with 20 kg of allulose syrup having a solid content of 70bx, an allulose purity of 97 wt / wt%, and a pH of 4.1, and the head space volume was filled to 5% based on the storage volume of each storage container being 100%, and then the containers were sealed and stored in an incubator at 45°C in the atmosphere for 10 weeks without filling with nitrogen. During the storage period, a small amount of allulose sample was taken at weekly intervals and diluted to 3bx with water to prepare an analysis sample. The analysis sample was subjected to measurement of allulose content by HPLC analysis. The specific HPLC analysis conditions were as follows: 87C (Biorad HPX-87C, 7.8mmΦ×300mm) column, temperature 80℃, 100% water as mobile phase at a flow rate of 0.6ml / min, and detection was performed using an RI detector.

[0032] [Table 3]

[0033] The decrease in content was smaller in the fully coated containers such as experimental groups 3-1 and 3-2 compared to the side coating in experimental group 3-3 and the polyethylene material container in experimental group 3-4. When the entire surface of the sample container is coated, the area of ​​contact between the TIN material and allulose is reduced, so it was confirmed that there is less impact on the decrease in content due to allulose decomposition. In addition, it was confirmed that, among the fully coated containers, the decrease was smaller in the double coated container (experimental group 3-1) compared to the single coated container (experimental group 3-2), and it was confirmed that the smaller the area of ​​contact with the TIN material, the greater the stability of the content.

Claims

1. An allulose storage package comprising a container and allulose syrup, The container is filled with allulose syrup so that the volume of the empty space excluding allulose is 20% or less based on the volume of the container being 100%; The container is filled with nitrogen; The container is made of tin or a tin alloy material and includes an epoxy phenol resin coating layer formed on the entire inner surface of the container, said allulose storage package.

2. The allulose syrup is stored at 25°C for 3 weeks and then at 35°C for 7 weeks for a total of 10 weeks, and has an allulose content of 90% by weight or more, based on the allulose content (wt%) at 0 weeks of storage being 100% by weight. The allulose storage package described in claim 1.

3. The allulose storage package according to claim 1 or 2, wherein the nitrogen filling is achieved by injecting nitrogen gas into the empty space of the container or into the allulose syrup.

4. The allulose storage package according to any one of claims 1 to 3, wherein the allulose syrup has an allulose content of 5 wt% or more based on a total solid content of the syrup of 100 wt%.

5. The allulose storage package according to any one of claims 1 to 4, wherein the pH of the allulose syrup immediately after production is 3.8 or higher.

6. A step of filling an allulose storage package containing a container and allulose syrup with allulose syrup so that the volume of the empty space excluding allulose is 20% or less based on 100% of the volume of the container; and Filling the container with nitrogen; The container is made of tin or a tin alloy material and includes a coating layer of an epoxy phenolic resin formed on the entire inner surface of the container.

7. The method according to claim 6, wherein the allulose syrup is stored at 25°C for 3 weeks and then at 35°C for 7 weeks for a total of 10 weeks, and the allulose content is 90% by weight or more, based on the allulose content (wt%) at 0 weeks of storage being 100% by weight.

8. The method described in claim 6, wherein the allulose syrup is obtained by subjecting an allulose conversion reaction product using a fructose substrate to a decolorization process using activated carbon, a high-purity separation process using a chromatography filled with a calcium (Ca2+) type ion exchange resin, and an ion process for the allulose fraction obtained in the high-purity separation process.

9. The method described in claim 6, wherein the nitrogen filling is achieved by injecting nitrogen gas into the empty space of the container or into the allulose syrup.

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