CN115785292B - Preparation method of V-shaped granular porous starch - Google Patents

Preparation method of V-shaped granular porous starch Download PDF

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CN115785292B
CN115785292B CN202211522788.3A CN202211522788A CN115785292B CN 115785292 B CN115785292 B CN 115785292B CN 202211522788 A CN202211522788 A CN 202211522788A CN 115785292 B CN115785292 B CN 115785292B
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starch
temperature
enzyme
shaped
porous starch
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CN115785292A (en
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周星
颜昊聪
金征宇
王韧
赵建伟
谢正军
龙杰
陈龙
邱超
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Jiangnan University
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Abstract

The invention relates to a preparation method of V-shaped porous starch, and belongs to the technical field of starch modification. The porous starch prepared by using high Wen Chunshui heat treatment and enzyme to act on starch simultaneously has a single-helix V-shaped crystal structure, has higher specific surface area and average pore diameter, and has better water and oil absorption capacity: the specific surface area of the V-shaped porous starch is 13.79-38.89 m 2 Per gram, the average pore diameter is 20.56-24.58 nm, the oil absorption rate is up to 190.54-252.11%, and the water absorption rate is up to 250.79-382.97%. The V-shaped crystalline starch has a large number of hydrophilic hydroxyl groups exposed on the surface, has strong binding capacity with enzyme, is favorable for enzymolysis reaction, and simultaneously has a loose VGS particle structure and a larger specific surface area, so that the enzymolysis efficiency is remarkably improved. Compared with the existing method for preparing the V-shaped porous starch, the method has the advantages that the product with excellent adsorption performance can be prepared within 2 hours in enzymolysis time, the enzymolysis time is obviously shortened, and the preparation efficiency is greatly improved.

Description

Preparation method of V-shaped granular porous starch
Technical Field
The invention relates to a preparation method of V-shaped porous starch, and belongs to the technical field of starch modification.
Background
Porous starch, also known as microporous starch, is a modified starch that is used to biologically or physically form pores in raw starch particles from the surface to the interior. Porous starch is used as a green adsorbent and is commonly applied to microencapsulation and adsorption carriers. For example, porous starch can be used as an adsorbent to adsorb natural active substances with poor water solubility in foods and protect substances which are easily oxidized and decomposed under light. However, raw starch has poor water solubility and adsorption properties and low reactivity due to its special semi-crystalline particle structure. The raw starch is used as a raw material to prepare the porous starch, so that the specific surface area of the raw starch can be increased, and the adsorption performance of the raw starch can be improved, but the obtained porous starch has limited adsorption performance and is insoluble in water, so that the application range of the traditional porous starch is limited.
Compared with the traditional porous starch, the V-shaped porous starch is prepared by taking V-shaped granular starch as a raw material and adopting an enzymolysis or acidolysis method. The V-shaped granular starch benefits from a loose granular structure and higher reactivity, and is easy to be acted by enzyme, so that the prepared V-shaped porous starch has excellent adsorption characteristics.
At present, an example of preparing V-shaped porous starch by adopting a two-step method is available, namely, preparing V-shaped granular starch by adopting a high-temperature high-pressure alcohol method, and treating the V-shaped granular starch by using amylase to obtain the V-shaped porous starch. The V-shaped porous starch prepared by the method has higher oil absorption rate, but the preparation process is complicated, and the enzymolysis time is as long as 6-12 hours, so that the efficiency of preparing the V-shaped porous starch is lower, and the application of the method in industrial production is limited.
Therefore, a method for preparing V-shaped porous starch is provided, which can remarkably improve the preparation efficiency of the V-shaped porous starch. However, in the implementation of the method, the formation of the V-shaped structure and the simultaneous performance of the enzymolysis reaction are a key problem to be explored by the invention.
Disclosure of Invention
[ problem ]
The technical problems to be solved by the invention are as follows: the method for preparing the porous starch simply and efficiently is provided, and the obtained product has higher specific surface area and excellent water and oil absorption capacity; meanwhile, the optimized conditions ensure that the V-shaped crystal structure can be fully formed and the enzymolysis reaction can be smoothly carried out in the preparation method.
[ technical solution ]
In order to solve the problems, the invention prepares the V-shaped porous starch by simultaneously treating starch by using a high-temperature high-pressure alcohol method and an enzymolysis method, and the porous starch has a single-helix V-shaped crystal structure and a higher specific surface area, so that the water absorption and oil absorption capacities of the porous starch are obviously improved compared with those of the porous starch prepared by the traditional method.
The first object of the invention is to provide a method for preparing V-shaped granular porous starch, which comprises the steps of firstly uniformly mixing raw starch, ethanol and enzyme to form uniform starch emulsion, and then directly preparing porous starch by adopting a high-temperature high-pressure alcohol method; the temperature in the high-temperature alcohol method is 75-90 ℃; the enzyme is alpha-amylase.
In one embodiment of the invention, the concentration of ethanol in the ethanol system is 40-70% v/v.
In one embodiment of the invention, the mass ratio of starch to ethanol is 1 (2-5).
In one embodiment of the invention, the starch comprises one or more of common corn starch, tapioca starch, rice starch, barley starch, wheat starch, potato starch.
In one embodiment of the invention, the enzyme is added in an amount of 50-200U/g starch.
Preferably, the enzyme is added in an amount of 110-140U/g starch.
In one embodiment of the invention, the enzymatic hydrolysis conditions are: the temperature is 75-90 ℃, and the enzymolysis time is 60-160min.
In one embodiment of the invention, the method comprises the steps of:
(2) Pouring starch, enzyme and ethanol solution into a high-temperature high-pressure reaction kettle to prepare V-shaped granular porous starch;
(3) And (3) filtering out the starch after the reaction liquid in the step (1) is cooled, washing the starch with ethanol solution, drying, cooling and putting the dried starch into a pulverizer for pulverizing to obtain the V-shaped granular porous starch.
In one embodiment of the present invention, the operation parameters of the high temperature and high pressure reactor in step (1) are set as follows: the reaction temperature is 70-90 ℃, the reaction rotating speed is 500r/min, the temperature is kept for 60-160min after the reaction temperature is reached, and the reaction is stopped when the temperature is reduced to 40 ℃.
In one embodiment of the present invention, the ethanol concentration used in step (1) is 40-70%; starch concentration is 10% -40%; the enzyme is added in an amount of 50-200U/g starch.
In one embodiment of the invention, the starch is washed with ethanol in the suction filtration process of step (2), the ethanol concentration being 95%, 2-3 times; the drying temperature is 105 ℃, the drying time is 2 hours, and the powder is ground and then passes through a 100-mesh screen.
The V-shaped porous starch prepared by the method is provided.
The second object of the present invention is to apply the V-shaped porous starch prepared as described above to the fields of foods, pharmaceutical preparations, agriculture and cosmetics.
The invention has the beneficial effects that:
the method for preparing the V-shaped porous starch simultaneously by the formation process and the enzymolysis process of the V-shaped granular cold water soluble starch through the high Wen Chunfa has the advantages of simple process, easy control of conditions, high enzymolysis efficiency and excellent adsorption property. Compared with the prior art, the method has the obvious advantages that:
(1) According to the invention, the high Wen Chunshui heat treatment and the enzyme are used for simultaneously acting on the starch, so that the prepared porous starch has a single-helix V-shaped crystal structure, has higher specific surface area and average pore diameter, and has better water and oil absorption capacity at the same time: the specific surface area of the V-shaped porous starch is 13.79-38.89 m 2 Per gram, the average pore diameter is 20.56-24.58 nm, the oil absorption rate is up to 190.54-252.11%, and the water absorption rate is up to 250.79-382.97%.
(2) The high Wen Chunshui heat treatment effect enables the compact double-helix structure of the raw starch to be opened, and the raw starch presents a single-helix structure. At the same time, the crystal state is changed from A-type crystal to V-type crystal. The enzyme acts on the amorphous area of the starch preferentially and then acts on the crystallization area of the starch, and under the proper enzymolysis condition, the product has higher relative crystallinity which is as high as 16.69-25.93 percent.
(3) The V-shaped crystalline starch has a large number of hydrophilic hydroxyl groups exposed on the surface, has strong binding capacity with enzyme, is favorable for enzymolysis reaction, and simultaneously has a loose VGS particle structure and a larger specific surface area, so that the enzymolysis efficiency is remarkably improved. Compared with the existing method for preparing the V-shaped porous starch, the method has the advantages that the product with excellent adsorption performance can be prepared and obtained within 2 hours of enzymolysis time, the enzymolysis time is obviously shortened, and the preparation efficiency is greatly improved; the single enzyme enzymolysis has the advantages of easier control of conditions, wider temperature application range and lower preparation cost.
Drawings
FIG. 1 is a graph showing the X-ray diffraction patterns and corresponding relative crystallinity of the V-type porous starch, V-type granular starch, raw starch and conventional A-type porous starch prepared in example 1 of the present invention;
FIG. 2 is a scanning electron microscope map of raw starch;
FIG. 3 is a scanning electron microscope image of a V-type granular starch;
FIG. 4 is a scanning electron microscope image of a conventional A-type porous starch;
FIG. 5 is a scanning electron microscope spectrum of the V-shaped porous starch prepared in example 1 of the present invention.
Detailed Description
The following description of the preferred embodiments of the present invention is provided for better illustration of the invention, and should not be construed as limiting the invention.
1. Specific surface area and average pore size test method:
accurately weighing 0.1000-0.2000 g of starch sample, and drying for 4 hours at 105 ℃ in an dilatometer matched with ASAP 2020MP for removing moisture and gas in the sample. The sample was then placed in high purity liquid nitrogen at-195.8 ℃ (nitrogen concentration ≡99.999%). The specific surface area of five measurement points at the relative pressure range P/p0=0.06 to 0.3 (P represents the partial pressure of nitrogen, P0 represents the saturated vapor pressure of nitrogen at the adsorption temperature) was calculated using the Brunauer-Emmett-Teller (BET) equation. The average pore size of the porous material was determined using Barrett-Joyner-Halenda (BJH) analytical model under P/p0=0.99.
2. The oil absorption rate testing method comprises the following steps:
1.00g of porous starch (mass M1) is weighed and placed in a 50ml centrifuge tube (mass M2 of the centrifuge tube), 5ml of soybean oil is added, stirring is carried out for 60min at 25 ℃ and 200r/min, after stirring, the mixture is centrifuged for 15 min at 3500r/min by a centrifuge at 4 ℃, and the weight M3 is recorded. And calculating the oil absorption rate according to a formula.
Oil absorption = (M3-M1-M2)/m1×100%
3. The water absorption test method comprises the following steps:
1.00g of porous starch (mass M1) is weighed and placed in a 50ml centrifuge tube (mass M2 of the centrifuge tube), 25ml of deionized water is added, stirring is carried out for 60min at 25 ℃ and 200r/min, after stirring, the mixture is centrifuged for 15 min at 3500r/min and 4 ℃ by a centrifuge, and the weight M3 is recorded. The water absorption is calculated according to the formula:
water absorption= (M3-M1-M2)/m1×100%.
4. Starch crystallinity test method:
the crystal structure of the sample was analyzed by an X-ray diffractometer, the scanning angle was 4 to 35 degrees (2. Theta.) and the scanning speed was 0.05 degrees/s. The relative crystallinity was calculated by MDI jar software: the ratio of the area of the characteristic peaks of V type crystallization (7.8 °,13.5 ° and 20.8 °) or the area of the characteristic peaks of A type crystallization (15 °,17 °,18 ° and 23 °) to the total dispersion area is calculated as follows:
relative crystallinity (%) =cda/TDA x 100,
where CDA represents the peak area of the characteristic crystallization peak and TDA represents the total area of all diffraction peaks in the scan interval.
The enzyme activity of the thermostable alpha-amylase in the following examples was 40000U/g.
Example 1:
40g of common corn starch and 160g of 50% ethanol are weighed in a high-temperature high-pressure reaction kettleIn the process, thermostable alpha-amylase (the addition amount of the enzyme is 150U/g starch) is added to start the reaction, and the operation parameters of the high-temperature high-pressure reaction kettle are as follows: the reaction temperature is 80 ℃, the reaction rotating speed is 500r/min, and the reaction time is 120min. Cooling after the reaction is finished, taking out the reaction liquid for centrifugation when the temperature is reduced to 40 ℃, then carrying out vacuum suction filtration, washing 2-3 times by using ethanol with the concentration of 95%, drying for 2 hours at the temperature of 105 ℃, crushing, and sieving by a 100-mesh sieve to obtain the V-shaped porous starch. The specific surface area of the V-shaped porous starch is 38.89m 2 The average pore diameter is 20.56nm, the oil absorption rate is up to 253.11 percent, and the water absorption rate is up to 250.79 percent.
Example 2:
40g of common corn starch and 160g of 70% ethanol are weighed into a high-temperature high-pressure reaction kettle, and thermostable alpha-amylase (the addition amount of the enzyme is 200U/g starch) is added for reaction, and the operation parameters of the high-temperature high-pressure reaction kettle are as follows: the reaction temperature is 90 ℃, the reaction rotating speed is 500r/min, and the reaction time is 160min. Cooling after the reaction is finished, taking out the reaction liquid for centrifugation when the temperature is reduced to 40 ℃, then carrying out vacuum suction filtration, washing 2-3 times by using ethanol with the concentration of 95%, drying for 2 hours at the temperature of 105 ℃, crushing, and sieving by a 100-mesh sieve to obtain the V-shaped porous starch. The specific surface area of the V-shaped porous starch is 15.64m 2 The average pore diameter is 20.77nm, the oil absorption rate is up to 192.33 percent, and the water absorption rate is up to 300.33 percent.
Example 3:
20g of common corn starch and 100g of 40% ethanol are weighed into a high-temperature high-pressure reaction kettle, and thermostable alpha-amylase (the addition amount of the enzyme is 50U/g starch) is added for reaction, and the operation parameters of the high-temperature high-pressure reaction kettle are as follows: the reaction temperature is 75 ℃, the reaction rotating speed is 500r/min, and the reaction time is 140min. Cooling after the reaction is finished, taking out the reaction liquid for centrifugation when the temperature is reduced to 40 ℃, then carrying out vacuum suction filtration, washing 2-3 times by using ethanol with the concentration of 95%, drying for 2 hours at the temperature of 105 ℃, crushing, and sieving by a 100-mesh sieve to obtain the V-shaped porous starch. The specific surface area of the V-shaped porous starch is 30.56m 2 The average pore diameter is 24.64nm, the oil absorption rate is up to 222.45 percent, and the water absorption rate is up to 310.60 percent.
Example 4:
60g of common corn starch and 120g of 60% ethanol are weighed into a high-temperature high-pressure reaction kettle, and thermostable alpha-amylase (the addition amount of enzyme120U/g starch), the operation parameters of the high-temperature high-pressure reaction kettle are as follows: the reaction temperature is 90 ℃, the reaction rotating speed is 500r/min, and the reaction time is 60min. Cooling after the reaction is finished, taking out the reaction liquid for centrifugation when the temperature is reduced to 40 ℃, then carrying out vacuum suction filtration, washing 2-3 times by using ethanol with the concentration of 95%, drying for 2 hours at the temperature of 105 ℃, crushing, and sieving by a 100-mesh sieve to obtain the V-shaped porous starch. The specific surface area of the V-shaped porous starch is 18.08m 2 The average pore diameter is 21.61nm, the oil absorption rate is up to 198.58%, and the water absorption rate is up to 305.64%.
Example 5:
30g of common corn starch and 90g of 50% ethanol are weighed into a high-temperature high-pressure reaction kettle, and thermostable alpha-amylase (the addition amount of the enzyme is 150U/g starch) is added for reaction, and the operation parameters of the high-temperature high-pressure reaction kettle are as follows: the reaction temperature is 80 ℃, the reaction rotating speed is 500r/min, and the reaction time is 80min. Cooling after the reaction is finished, taking out the reaction liquid for centrifugation when the temperature is reduced to 40 ℃, then carrying out vacuum suction filtration, washing 2-3 times by using ethanol with the concentration of 95%, drying for 2 hours at the temperature of 105 ℃, crushing, and sieving by a 100-mesh sieve to obtain the V-shaped porous starch. The specific surface area of the V-shaped porous starch is 35.64m 2 The average pore diameter is 25.21nm, the oil absorption rate is up to 238.16 percent, and the water absorption rate is up to 382.97 percent.
Example 6
A V-type porous starch was prepared according to the method of example 1, except that the amount of thermostable alpha-amylase added was changed, 50U/g, 80U/g, 110U/g, 140U/g, 170U/g, 200U/g starch, and the remaining conditions were unchanged, and the results are shown in Table 1.
TABLE 1 influence of alpha-amylase dosage on porous starch Properties
The inventors examined the influence of the enzyme addition amount on the adsorption characteristics of V-shaped porous starch. Under the condition of 50U/g of starch, the starch is insufficiently hydrolyzed in a high-temperature high-pressure reaction kettle due to lower enzyme adding amount, and more hole structures are not formed on the surfaces of starch particles, so that the oil absorption rate is lower, and the adsorption effect of the prepared V-shaped porous starch is best when the enzyme adding amount is 140U/g of starch. As the enzyme loading further increases, the adsorption effect of the V-shaped porous starch begins to decrease, as the starch structure collapses due to excessive enzymatic hydrolysis. Thus, the preferred enzyme loading range is 110-140U/g starch.
Example 7
The V-shaped porous starch was prepared by the method of reference example 1, except that the reaction vessel temperature was changed to 75℃80℃85℃90℃95 ℃. The remaining conditions were unchanged, and the results are shown in Table 2.
TABLE 2 influence of different reaction temperatures on the properties of porous starch
The inventors examined the influence of the reaction temperature on the adsorption characteristics of V-type porous starch. When the reaction temperature is below 80 ℃, the double helix structure of the starch in the 50% ethanol solution is not fully opened, so that a good V-shaped structure is not formed, and the adsorption property of the obtained sample is poor. When the temperature is higher than 90 ℃, the activity of the enzyme is reduced in a high-temperature and high-pressure environment, and starch cannot be effectively hydrolyzed; when the temperature was raised to 95 ℃ again, the sample had gelatinized and had poor adsorptivity.

Claims (2)

1. A method for preparing V-shaped granular porous starch is characterized in that raw starch, ethanol and enzyme are uniformly mixed to form uniform starch emulsion, and then the porous starch is directly prepared by adopting a high-temperature high-pressure alcohol method; the temperature in the high-temperature alcohol method is 80 ℃; the enzyme adopts thermostable alpha-amylase; the addition amount of the enzyme is 150U/g starch; the enzymolysis time is 120 min; ethanol concentration is 50% v/v; the mass ratio of the starch to the ethanol is 1:4; the starch is common corn starch;
the method comprises the following steps:
(1) Pouring starch, enzyme and ethanol solution into a high-temperature high-pressure reaction kettle to prepare V-shaped granular porous starch;
(2) And (3) filtering out the starch after the reaction liquid in the step (1) is cooled, washing the starch with ethanol solution, drying, cooling and putting the dried starch into a pulverizer for pulverizing to obtain the V-shaped granular porous starch.
2. The method according to claim 1, wherein the filtration in step (2) is vacuum filtration, and the starch is washed with ethanol for 2-3 times during the suction filtration process; the drying temperature is 100-105 ℃, the drying time is 2-3 hours, and the powder is ground and then passes through a 100-mesh screen.
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Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1661028A (en) * 2004-12-22 2005-08-31 华南理工大学 Method for preparing porous starch through enzyme method in high temperature
CN102533908A (en) * 2012-01-04 2012-07-04 江南大学 Method for preparing porous starch with high oil absorption rate through preprocessing starch
CA2977835A1 (en) * 2014-02-27 2015-09-03 B-Organic Films Corp. Bioactive agents under water dispersible solid forms for food, nutraceutical, agricultural and pharmaceutical applications
CN112831081A (en) * 2020-12-31 2021-05-25 江南大学 Preparation method of V-shaped granular porous starch

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1661028A (en) * 2004-12-22 2005-08-31 华南理工大学 Method for preparing porous starch through enzyme method in high temperature
CN102533908A (en) * 2012-01-04 2012-07-04 江南大学 Method for preparing porous starch with high oil absorption rate through preprocessing starch
CA2977835A1 (en) * 2014-02-27 2015-09-03 B-Organic Films Corp. Bioactive agents under water dispersible solid forms for food, nutraceutical, agricultural and pharmaceutical applications
CN112831081A (en) * 2020-12-31 2021-05-25 江南大学 Preparation method of V-shaped granular porous starch

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
"Preparation of V-type porous starch by amylase hydrolysis of V-type granular starch in aqueous ethanol solution";Xing Zhou等;《International Journal of Biological Macromolecules》;第183卷;第890–897页 *

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