CN110835424A - Preparation method of A + V type structure starch - Google Patents

Preparation method of A + V type structure starch Download PDF

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CN110835424A
CN110835424A CN201911088884.XA CN201911088884A CN110835424A CN 110835424 A CN110835424 A CN 110835424A CN 201911088884 A CN201911088884 A CN 201911088884A CN 110835424 A CN110835424 A CN 110835424A
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starch
ferric chloride
alcohol solution
reaction kettle
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CN110835424B (en
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林日辉
黄彩梅
樊艳叶
蒋心濛
韦玉燕
吴继婷
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Guangxi University for Nationalities
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    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/16—Halogen-containing compounds
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08B—POLYSACCHARIDES; DERIVATIVES THEREOF
    • C08B30/00—Preparation of starch, degraded or non-chemically modified starch, amylose, or amylopectin
    • C08B30/02—Preparatory treatment, e.g. crushing of raw materials or steeping process
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
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Abstract

The invention discloses a preparation method of starch with an A + V type structure, belonging to the technical field of preparation and application of natural high polymer materials, wherein the starch with the A + V type structure is obtained by co-reacting ferric chloride/alcohol solution and starch, and the obtained starch with the A + V type structure has the relative crystallinity lower than 10.67 percent and is easy to dissolve in cold water. The preparation method disclosed by the invention is simple, mild in reaction conditions, green and environment-friendly, low in cost, free of toxic substances, environment-friendly and wide in application prospect. The invention analyzes and researches the shape, crystallinity, crystal form, internal structure, group, molecular structure and the like of the obtained A + V-shaped starch, and provides a new direction for starch research.

Description

Preparation method of A + V type structure starch
Technical Field
The invention belongs to the technical field of preparation and application of natural high polymer materials, and particularly relates to a preparation method of starch with an A + V type structure.
Background
According to the X-ray diffraction pattern, the starch can be divided into A type, B type, C type and V type; the A type has diffraction peaks at 15 degrees, 17 degrees, 18 degrees, 23 degrees and the like; the B type has diffraction peaks at 5.6 degrees, 17 degrees, 22 degrees and 24 degrees; the C type is divided into a natural C type and a type A/B conversion type, and diffraction peaks comprise peak types of the A type and the B type; the V form is a compound of amylose-fatty acid, amylose-emulsifier, amylose-alcohol, amylose-iodine and the like, has diffraction peaks at 7.8 degrees, 12.5 degrees and 19.5 degrees, is formed by a single helix structure, and can commonly exist with other crystal forms.
However, the natural starch has poor film forming property, is insoluble in cold water, has poor shearing resistance, is easy to age, cannot form stable colloidal solution and the like, and limits the application of the natural starch in the aspects of medicine and medicine, textile industry, paper making processing, food processing and the like. Therefore, the modification of starch is an intense research in recent years to make up for the deficiencies of native starch. The starch may be modified by physical, chemical or enzymatic treatment. Although the use of chemical modification has certain disadvantages, it is desirable to obtain good functionality from chemically modified starch.
The chemical modification method of starch has been partially researched at present, and comprises the steps of synthesizing crosslinked AA/AM grafted esterified cyanoethyl cassava starch by cassava starch and then taking magnetic particles as Fe3O4Preparing magnetic cross-linked AA/AM grafted esterified cyanoethyl cassava starch microspheres and taking template ions as Cu2+The magnetic imprinted polymer Cu-IIPs is obtained by imprinting modification, so that the adsorption performance and biocompatibility of the starch are improved. Also by modifying the starch using an ozone process and changing the process conditions, hydrogels with enhanced pasting properties, gel texture and printability can be obtained, thereby expanding the potential of starch applications in 3D printing. And the initiator is sodium bisulfite and ammonium persulfate, and the PVA modified glutinous rice flour PVA is used for graft modification of the starch adhesive, so that the production cost can be reduced, the viscosity can be improved, the water resistance can be improved, and the stability can be improved. Or dry-treating waxy corn and waxy rice with phytic acid under mild alkaline conditionThe rice starch is subjected to phosphorylation treatment to obtain phosphorylated waxy starch, so that the pasty transparency, expansibility and viscosity of starch granules are increased, the melting point temperature and enthalpy of the starch granules are reduced, and the defects of natural starch are overcome. The Chinese patent publication No. CN105061818B discloses a modified composite film prepared by adding three components into starch and chitosan, wherein eight components such as ferric chloride, ferric nitrate, glycerol and glycol are disclosed.
Although the research on starch is in many directions at present, the research on the high-temperature treatment of the cassava starch by the ferric chloride/alcohol solution is not reported at present. There is a need to develop a method for preparing a new type of structured starch.
Disclosure of Invention
In order to solve the problems, the invention provides a preparation method of starch with an A + V type structure, which is characterized in that starch particles are subjected to high-temperature treatment by ferric chloride/alcohol solution, the appearance of the starch particles is obviously changed, the crystal form of the starch particles is gradually changed from the A type to the A + V type, and the starch particles are easy to dissolve in cold water and have wide application prospect.
In order to achieve the purpose, the scheme provided by the invention is as follows:
a preparation method of A + V type structure starch comprises the following steps:
(1) dissolving ferric chloride in ethanol to prepare ferric chloride/alcohol solution;
(2) weighing starch, putting the starch into a reaction kettle, dripping ferric chloride/alcohol solution into the reaction kettle while stirring uniformly, and then putting the reaction kettle into a drying box for reaction;
(3) and (3) taking out the reaction kettle after the reaction is finished, naturally cooling at room temperature, removing supernatant in the reaction kettle, taking out the residual solid matter, refrigerating for storage, and freeze-drying to constant weight.
Further, in the step (1), the volume concentration of the ethanol is 90% or more.
Further, in the step (1), the concentration of the ferric chloride/alcohol solution is 0.005-0.025 mol/L.
Further, in the step (2), the starch is cassava starch or corn starch or wheat starch; the dosage ratio of the starch to the ferric chloride/alcohol solution is 1 g: 13-18 ml.
Further, in the step (2), the temperature in the drying box is maintained at 110-120 ℃; the reaction time is 3-4 h.
Further, in the step (3), the refrigeration preservation is ice-sealing in a refrigerator at 4 ℃ for 10-14 h.
Further, in the step (3), the freeze-drying treatment is carried out in a vacuum freeze-drying machine at-40 ℃ under a vacuum degree of 0-0.3 mpa.
The A + V type structure starch prepared by the preparation method has the relative crystallinity as low as 10.67%.
The raw materials used in the invention, namely cassava starch, ferric chloride, ethanol, corn starch, wheat starch and the like, are purchased from chemical raw material companies at home and abroad and are directly used without being continuously purified.
The cassava starch used in the invention has the advantages of mostly oval section shape, good swelling degree and solubility, low gelatinization temperature, high viscosity and starch paste transparency, good film forming property, strong permeability, better processing performance and the like. The structure of the corn starch and the wheat starch is similar to that of cassava starch.
The preparation principle of the invention is as follows: the ferric chloride treated starch makes the surface of starch granules rough, the surface is covered with a plurality of small granules, part of the starch surface is shriveled and gelatinized, and the destructive power is enhanced along with the increase of the concentration of ferric chloride/alcohol solution; the crystal form of the starch is destroyed, and the destroyed crystal form structure develops to the starch with the V-shaped structure along with the increase of the concentration of ferric chloride/alcohol solution, so that the starch with the A + V-shaped structure is processed; and ferric chloride can permeate into the starch granules to destroy the structure of a crystalline layer in the starch, the stronger the concentration of ferric chloride/alcohol solution is, the more obvious the destruction degree is, and the product with low relative crystallinity is obtained. In addition, the ferric chloride/alcohol solution is used for treating the starch, so that the crystallinity of the starch is reduced, the short-range molecular order degree of starch granules is damaged, the acting force of hydrogen bonds is reduced, and the quantity of crystal water in the starch can be reduced.
The invention has the following beneficial effects:
1. the preparation method of the invention adopts ferric chloride/alcohol solution to treat starch, which not only changes the appearance of the starch, but also changes the surface of the starch granules into rough and shriveling, but also destroys the crystalline layer and amorphous area of the starch granules, destroys the short-range molecular order degree, reduces the acting force of hydrogen bonds and reduces the amount of crystal water in the starch.
2. The product obtained by the preparation method is A + V-type structure starch, the crystallinity of the starch is as low as 10.67%, the obtained product is easy to dissolve in cold water, the preparation method is simple, the reaction condition is mild, the environment is protected, the cost is low, no toxic substance is generated, the preparation method is environment-friendly, and the preparation method has wide application prospect.
3. The preparation method of the invention can make ferric chloride permeate into the interior of the starch granules, combine with amylose to form amylose-ferric chloride compound, open the channel of the starch granules and make ethanol molecules enter the starch granules to form ethanol-starch compound.
Drawings
FIG. 1 is an electron microscope scan of the raw starch, blank group, product of example 2, and product of example 1 of the present invention.
FIG. 2 is an X-ray diffraction pattern of the raw starch, the blank, the product of example 2, and the product of example 1 of the present invention.
Figure 3 is a CLSM image of the starting starch, the blank, the product of example 2, the product of example 1 according to the invention.
FIG. 4 shows the raw starch, the blank, the product of example 2, and the product of example 1 according to the present invention13C-NMR spectrum.
FIG. 5 is an FTIR spectrum of the raw starch, blank, product from example 2, product from example 1 of the present invention.
FIG. 6 shows LCM-Raman spectra of raw starch, blank, product of example 2, and product of example 1.
FIG. 7 is a UV-Vis spectrum of a raw starch, a blank, a product of example 2, a product of example 1 according to the invention; wherein, fig. 7A is a map before each sample is stained with iodine, and fig. 7B is a map after each sample is stained with iodine.
In the above fig. 1-7, a is a raw starch image or map, b is a blank group image or map, c is a product image or map of embodiment 2, and d is a product image or map of embodiment 1.
Detailed Description
The invention is further described with reference to the following examples:
example 1
The preparation method of the A + V type structure starch comprises the following steps:
(1) dissolving ferric chloride in 90% ethanol by volume to prepare ferric chloride/alcohol solution, wherein the concentration of the obtained ferric chloride/alcohol solution is 0.025 mol/L;
(2) weighing cassava starch, putting the cassava starch into a reaction kettle, dripping ferric chloride/alcohol solution into the reaction kettle while uniformly stirring, then putting the reaction kettle into a drying box, keeping the temperature at 120 ℃, and drying for 4 hours; the dosage ratio of the cassava starch to the ferric chloride/alcohol solution is 1 g: 15 ml;
(3) and (3) taking out the reaction kettle after drying is finished, naturally cooling at room temperature, removing supernatant in the reaction kettle, taking out the residual solid, carrying out ice sealing in a refrigerator at 4 ℃ for 12 hours, and then carrying out freeze-drying treatment in a vacuum freeze-drying machine at-40 ℃ and under the condition that the vacuum degree is 0.3mpa to constant weight.
Example 2
The preparation method of the A + V type structure starch comprises the following steps:
(1) dissolving ferric chloride in 92% ethanol by volume to prepare ferric chloride/alcohol solution, wherein the concentration of the obtained ferric chloride/alcohol solution is 0.005 mol/L;
(2) weighing cassava starch, putting the cassava starch into a reaction kettle, dripping ferric chloride/alcohol solution into the reaction kettle while uniformly stirring, then putting the reaction kettle into a drying box, keeping the temperature at 110 ℃, and drying for 3 hours; the dosage ratio of the cassava starch to the ferric chloride/alcohol solution is 1 g: 13 ml;
(3) and (3) taking out the reaction kettle after drying is finished, naturally cooling at room temperature, removing supernatant in the reaction kettle, taking out the residual solid, carrying out ice sealing in a refrigerator at 4 ℃ for 11h, and carrying out freeze-drying treatment in a vacuum freeze-drying machine at-40 ℃ and under the condition that the vacuum degree is 0mpa until the weight is constant.
Example 3
The preparation method of the A + V type structure starch comprises the following steps:
(1) dissolving ferric chloride in 93% ethanol by volume to prepare ferric chloride/alcohol solution, wherein the concentration of the obtained ferric chloride/alcohol solution is 0.015 mol/L;
(2) weighing cassava starch, putting the cassava starch into a reaction kettle, dripping ferric chloride/alcohol solution into the reaction kettle while stirring uniformly, then putting the reaction kettle into a drying box, keeping the temperature at 115 ℃, and drying for 3.5 hours; the dosage ratio of the cassava starch to the ferric chloride/alcohol solution is 1 g: 18 ml;
(3) and (3) taking out the reaction kettle after drying is finished, naturally cooling at room temperature, removing supernatant in the reaction kettle, taking out the residual solid, carrying out ice sealing in a refrigerator at 4 ℃ for 14h, and carrying out freeze-drying treatment in a vacuum freeze-drying machine at-40 ℃ and under the condition that the vacuum degree is 0.1mpa to constant weight.
Example 4
The preparation method of the A + V type structure starch comprises the following steps:
(1) dissolving ferric chloride in 95% ethanol to prepare ferric chloride/alcohol solution, wherein the concentration of the ferric chloride/alcohol solution is 0.020 mol/L;
(2) weighing corn starch, putting the corn starch into a reaction kettle, dripping ferric chloride/alcohol solution into the reaction kettle while uniformly stirring, then putting the reaction kettle into a drying box, keeping the temperature at 118 ℃, and drying for 4 hours; the dosage ratio of the corn starch to the ferric chloride/alcohol solution is 1 g: 16ml of the solution;
(3) and (3) taking out the reaction kettle after drying is finished, naturally cooling at room temperature, removing supernatant in the reaction kettle, taking out the residual solid, carrying out ice sealing in a refrigerator at 4 ℃ for 13 hours, and carrying out freeze-drying treatment in a vacuum freeze-drying machine at-40 ℃ and under the condition that the vacuum degree is 0.1mpa to constant weight.
Example 5
The preparation method of the A + V type structure starch comprises the following steps:
(1) dissolving ferric chloride in 96% ethanol by volume concentration to prepare ferric chloride/alcohol solution, wherein the concentration of the obtained ferric chloride/alcohol solution is 0.010 mol/L;
(2) weighing wheat starch, putting the wheat starch into a reaction kettle, dripping ferric chloride/alcohol solution into the reaction kettle while uniformly stirring, then putting the reaction kettle into a drying box, keeping the temperature at 116 ℃, and drying for 3.5 hours; the dosage ratio of the wheat starch to the ferric chloride/alcohol solution is 1 g: 14ml of the solution;
(3) and (3) taking out the reaction kettle after drying is finished, naturally cooling at room temperature, removing supernatant in the reaction kettle, taking out the residual solid, carrying out ice sealing in a refrigerator at 4 ℃ for 10 hours, and carrying out freeze-drying treatment in a vacuum freeze-drying machine at-40 ℃ and under the condition that the vacuum degree is 0.15mpa to constant weight.
Blank group
The preparation method of the structural starch comprises the following steps:
(1) weighing cassava starch, putting the cassava starch into a reaction kettle, dripping 90% ethanol solution into the reaction kettle while stirring uniformly, putting the reaction kettle into a drying box, keeping the temperature at 120 ℃, and drying for 4 hours; the dosage ratio of the cassava starch to the ethanol solution is 1 g: 15 ml;
(2) and (3) taking out the reaction kettle after drying is finished, naturally cooling at room temperature, removing supernatant in the reaction kettle, taking out the residual solid, carrying out ice sealing in a refrigerator at 4 ℃ for 8 hours, and then carrying out freeze-drying treatment in a vacuum freeze-drying machine at-40 ℃ and 0.3mpa until the weight is constant.
Firstly, the following analyses are respectively carried out on the products prepared in the embodiment 1, the embodiment 2 and the blank group of the invention and raw starch:
1. the apparent morphology of the product was studied with a scanning electron microscope. Sucking micro sample, coating the double-sided adhesive tape on the sample carrier uniformly, wiping off redundant sample, spraying gold for 20min, and observing and taking picture in a scanning electron microscope with accelerating voltage of 3.0kV and magnification of 2000 times.
2. The crystallinity and crystal form of the processed starch can be analyzed by using an X-ray diffractometer, Cu-K α rays and Ni filtering are used for continuous scanning, and the measuring conditions are that the scanning speed is 8 degrees/min, the scanning range is 4-60 degrees, the tube pressure is 40kV, the tube flow is 15mA, and the step size is 0.02 degrees.
3. The CLSM can be used for researching the internal microstructure of the product, and the detection is carried out according to the fluorescence phenomenon of the reaction of the starch reducing group tail end and the stain. Accurately weighing 10.00mg of sample, mixing with 15.00 mu L of 10mM APTS acetic acid solution prepared at present and 15.00 mu L of 1M sodium cyanoborohydride prepared at present uniformly, reacting in a constant-temperature water bath at 30 ℃ for 15h, then carefully cleaning with 1mL of distilled water for 5 times, then placing starch particles in 100 mu L of 50% glycerol and water mixed solution, and placing a drop of starch milk in a laser emission wavelength of 488nm for observation.
4. The nuclear magnetic resonance carbon spectrum of the product can judge the atomic structure of the C atoms through the chemical shift of the C atoms, thereby presuming the C atom framework of the substance. Accurately weighing 0.20g of sample, placing the sample in 5ml of DMSO-d6 reagent, fully mixing in a constant-temperature water bath at 80 ℃ until the sample is dissolved, placing 0.50ml of starch milk in a 5mm nuclear magnetic resonance tube, and testing at 25 ℃ with the testing power of 600 MHz.
5. The product was scanned in a fourier infrared spectrometer using potassium bromide tableting. Fully mixing and grinding a sample and KBr according to the ratio of 1: 100, carrying out vacuum tabletting for 1min under 10MPa, taking a potassium bromide sheet as a reference, and then scanning within the range of 4000-400 cm-1Resolution of 4cm-1And scanning in a Fourier infrared spectrometer with the scanning times of 32.
6. A Raman spectrometer is used for the product, the rotation or vibration of molecules can be reflected according to the intensity and the position of a scattering peak, some chemical bonds and functional groups in a substance are analyzed, and the molecular structure information of a chemical substance is obtained from the chemical bonds and the functional groups. The Raman instrument test conditions are as follows: the laser is a 532nm helium-neon laser, the laser power is 4.5W, the scanning is carried out for 20 times, the exposure time is 10s, and the length of the laser is 4000-200 cm-1The number of sweep waves of the range. 476cm was calculated using software from WIRE 4.3-1The Full width of half height of the characteristic peak (FWHH).
7. Before and after iodine staining of the product, respectively scanning by an ultraviolet-visible spectrophotometer. Specifically, 0.10g sample is taken in a test tube, 10mL distilled water is added into the sample, the mixture is shaken up in a boiling water bath for 3min to prepare starch suspension, and 2.5mL starch milk is transferred into the test tube after the temperature is room temperatureIn the above step, 10ml of distilled water and 5. mu.L of 2% I were continuously added2Mixing the KI (1:2) solutions, uniformly mixing the solutions, standing for 20min, scanning by an ultraviolet-visible spectrophotometer within the range of 200-800 nm, and adding I2Scanning the starch milk before and after KI solution.
Second, result analysis
1. FIG. 1 is an electron microscope scanning image of the product of the present invention. As can be seen from FIG. 1, the raw starch granules are different in size, mostly polygonal, elliptical and round, and have smooth surfaces, and only a few starch granules are concave; the blank group of starch treated by only 90% ethanol has smooth and unbroken particle appearance, and the particle state and appearance of the starch are not greatly different from those of raw starch, so that the micro-morphology of the starch is not greatly influenced by only 90% absolute ethanol treatment; example 2 the surface becomes rough, the surface is covered with a plurality of small particles, part of the starch surface is shriveled and gelatinized, but the starch can still maintain the granularity of the starch, and the ethanol tends to protect the stability of the structure of the starch particles, inhibits the expansion of the starch particles to a certain extent and improves the heat stability of the starch; the surface roughness of the particles in the embodiment 1 of the invention is particularly obvious, and the appearance of most starch particles is completely changed by observing that the surface of the particles is provided with one convex bubble, wrinkles and deformation with different degrees occur, which shows that ferric chloride/alcohol solution can interact with the starch to destroy a starch particle crystallization layer and an unformed area, and the shape and the appearance of the raw starch are greatly changed along with the addition of the ferric chloride concentration.
2. FIG. 2 is an X-ray diffraction pattern of the product of the present invention. As can be seen from fig. 2, the raw starch has distinct diffraction peaks at 2 θ of 15.1 °, 17 °, 18 °, and 23 °, and is a typical a-type starch structure. The diffraction peak position of the starch treated by only 90% ethanol in the blank group is not different when the starch is placed in natural starch, and the relative crystallinity is reduced, so that ethanol molecules mainly act on an amorphous area of the starch to keep the crystal form of the starch. Example 2 starch treated with ferric chloride/alcohol solution, which showed new diffraction peaks at 7.9 °, 13.6 °, and 20.8 ° 2 θ, typical of type V starch diffraction peaks; the diffraction peak intensity of inventive example 1 at 2 θ of 15.1 °, 17 °, 23 ° gradually decreased, and the original peak at 18 ° disappeared. The result shows that the crystal form of the raw starch is completely destroyed, and the destroyed crystal form structure develops to the starch with the V-shaped structure, so that the crystal form structure of the product of the embodiment 1 is the starch with the A + V-shaped structure, and the formation of a compound formed by the starch and the absolute ethyl alcohol, which is beneficial to the formation of the V-shaped crystal structure, is promoted along with the addition of the ferric chloride/the alcohol solution, and the complex is formed by the starch and the ferric chloride.
The relative crystallinity is calculated according to the detection result, and is specifically shown in table 1.
TABLE 1
Figure BDA0002266265220000071
In table 1, the relative crystallinity of the raw starch is 21.91%, the relative crystallinity of all starches treated with ferric chloride/alcohol solution is lower than that of the raw starch, and the relative crystallinity of the inventive example 1 is as low as 10.67% at least, because the ferric chloride/alcohol solution promotes the depolymerization of amylopectin and the unwinding of amylose, thereby destroying the crystalline sequence of the starch, and the roughness and the wrinkle degree of the surface and the appearance of irregular deformation are combined with the electron microscope image analysis, which is more beneficial for the ferric chloride/alcohol solution to destroy the crystalline structure and form new crystals, so that the relative crystallinity is reduced.
3. Fig. 3 is a CLSM image of the product of the present invention. As can be seen from FIG. 3, the raw material starch granules have circular or star-shaped pore structures inside to form a central cavity, and light micro cracks are arranged around the central cavity to form a pore structure of the starch. Blank 90% ethanol treated starch was similar to the CLSM image of the raw starch, indicating that the alcohol had no effect on the internal structure of the starch. In the embodiment 2, the fluorescence brightness of the particles is weakened integrally, cracks extend from the central cavity to the surface layers of the particles, the pore channels become changeable and thick and are in an annual ring shape, and the starch particles can keep the original particle state integrally. The annual ring shape of the particles in the embodiment 1 of the invention is more obvious, the fluorescence brightness of the starch is integrally enhanced compared with that in the embodiment 2, most of the particles are fuzzy in shell and are in a fragment shape, and only a few particles keep the original starch particle state.
The ferric chloride which illustrates the method of the embodiment can permeate into the starch granules to destroy the internal crystalline layer structure of the starch, and during the period when the starch granules are destroyed, the pore channels of the starch granules are filled with amylose to form a new ordered crystalline structure, which presents obvious annual ring-shaped and fragmented starch granules with increased number and enhanced fluorescence brightness. As can be seen from FIG. 1, the action of the ferric chloride/alcohol solution on the starch granules mainly acts on the interior of the starch granules, the rough surface and the raised bubbles of the starch are caused by the destruction of the crystals in the starch granules, and the deformation of the starch granules is caused by the excessive destruction and breakage of the starch granules due to the excessive concentration of 0.025mol/L ferric chloride/alcohol solution.
4. FIG. 4 shows a product of the invention13C-NMR spectrum. As can be seen from FIG. 4, in the glucose building block of the raw material starch, 100.6ppm was C-1, 79.2ppm was C-4, 73.4, 72.5, 72.1ppm were C-3, C-2 and C-5, respectively, 61.0ppm was the absorption peak of C-6, and the absorption peak of DMSO was 40.1 ppm. Of blanks with raw starch13The C-NMR spectrum is similar, which shows that alcohol has no influence on the chemical shift of the carbon of the starch. Example 2 of13In the C-NMR spectrum, new absorption peaks appeared at 19.0ppm, 56.5ppm and 79.8ppm, and 19.0ppm is ethanol-CH3Medium carbon absorption peak, 56.5ppm ethanol-CH2Absorption peak of carbon in OH. Example 1 of the invention13In the C-NMR spectrum, new absorption peaks appeared at 19.0ppm, 56.5ppm, 70.4ppm, 77.2ppm and 79.8ppm, 70.4ppm and 77.2ppm were further new absorption peaks appeared, and the intensities of the absorption peaks at 19.0ppm and 56.5ppm were enhanced, as compared with the spectrum of example 2.
The ferric chloride/alcohol solution treatment of starch in the method of the embodiment can cause multiple reactions of starch, and absorption peaks appear at 70.4ppm, 77.2ppm and 79.8ppm, which are caused by three reasons in combination with the XRD pattern and CLSM image analysis: 1. ferric chloride permeates into the interior of the starch granules, opens the channels of the starch granules, and enables ethanol molecules to enter the starch granules to form ethanol-starch complexes, thereby displaying a carbon absorption peak of ethanol, wherein the peak increases along with the increase of the concentration of ferric chloride/alcohol solution; 2. ferric chloride is infiltrated into the starch and combined with amylose to form an amylose-ferric chloride compound; 3. it is starch that can form unknown complexes with ferric chloride.
5. FIG. 5 is an FTIR spectrum of a product of the present invention. As can be seen from FIG. 5, the FTIR spectra of the raw starch are similar to those of other groups, the stretching vibration absorption peak of-OH in the blank group generates blue shift, and other characteristic peaks have no obvious change, which indicates that the alcohol treatment can reduce the acting force of hydrogen bonds and the number of the hydrogen bonds. In the spectra of the embodiment 2 and the embodiment 1, the stretching vibration absorption peak of-OH and the bending vibration absorption peak of-OH both have blue shift, and other characteristic peaks have no obvious change; in example 1, the more the wave number of the stretching vibration peak of-OH shifts to a low wave number, the absorption peak of the crystal water-OH bending vibration does not change.
The result shows that the treatment of the example 1 of the invention can not only reduce the acting force of hydrogen bonds, but also reduce the amount of crystal water in starch and weaken the acting force of the hydrogen bonds. Bonding of13C-NMR spectroscopy analysis shows that the new carbon signal appears in the starch treated by ferric chloride/alcohol solution, but the FTIR spectrum does not show, because the absorption band of the substance is very weak and cannot be detected by the instrument or the absorption band of the substance is beyond the detection range of the instrument.
6. FIG. 6 is a LCM-Raman spectrum of a product of the invention. As can be seen in FIG. 6, the LCM-Raman spectra of the 4 starch groups are similar, the starch being treated but at 476cm-1The peak value rises and increases with the addition of ferric chloride/alcohol solution concentration. The results show that treatment of starch with ferric chloride/alcohol solution reduces the crystallinity of starch, destroys the short range molecular order of starch granules, and increases its destructive power with increasing ferric chloride/alcohol solution concentration, evidencing the results of XRD analysis.
7. FIG. 7 is a UV-Vis spectrum of the product of the invention, FIG. 7A is a spectrum of a sample before iodine staining, and FIG. 7B is a spectrum of the sample after iodine staining. As can be seen from FIG. 7A, example 1 of the present invention has an absorption peak at 281nm, which indicates that there is a certain force between starch and ferric chloride, while example 2 has no absorption peak at 281nm, which is not detected because the force between starch and a small amount of ferric chloride is small. As can be seen from FIG. 7B, the raw starch has an absorption peak at 580nm, which is a typical absorption peak of a branched/straight starch mixture and an iodine complex; the starch of the blank group has a red shift phenomenon of an absorption peak, and ethanol can promote the combination of iodine and starch to widen the absorption peak; the absorption peaks of the embodiment 1 and the embodiment 2 have a blue shift phenomenon, on one hand, ferric chloride destroys molecular chains of starch, so that the molecular chains cannot form a complete double-spiral structure after being shortened, and cannot be combined with iodine, and on the other hand, ferric chloride can be combined with amylose, so that the combination chance of the amylose and the iodine is reduced.
The starches having the structure of type A + V obtained in examples 3 to 5 were characterized as in example 1, and the results of characterization of the starches having the structure of type A + V obtained in examples 3 to 5 were highly coincident with those of example 1, indicating that the products obtained were excellent in reproducibility.
Although the embodiments of the present invention have been described with reference to the accompanying drawings, it is not intended to limit the scope of the invention, and it should be understood by those skilled in the art that various modifications and variations can be made without inventive faculty, based on the technical solutions of the present invention.

Claims (8)

1. A preparation method of A + V type structure starch is characterized by comprising the following steps:
(1) dissolving ferric chloride in ethanol to prepare ferric chloride/alcohol solution;
(2) weighing starch, putting the starch into a reaction kettle, dripping ferric chloride/alcohol solution into the reaction kettle while stirring uniformly, and then putting the reaction kettle into a drying box for reaction;
(3) and (3) taking out the reaction kettle after the reaction is finished, naturally cooling at room temperature, removing supernatant in the reaction kettle, taking out the residual solid matter, refrigerating for storage, and freeze-drying to constant weight.
2. The method for preparing A + V type structured starch according to claim 1, wherein the volume concentration of ethanol in step (1) is 90% or more.
3. The method for preparing A + V type structural starch according to claim 1, wherein the concentration of the ferric chloride/alcohol solution in step (1) is 0.005-0.025 mol/L.
4. The method for preparing the A + V type structural starch according to the claim 1, wherein in the step (2), the starch is tapioca starch or corn starch or wheat starch; the dosage ratio of the starch to the ferric chloride/alcohol solution is 1 g: 13-18 ml.
5. The method for preparing A + V type structural starch as set forth in claim 1, wherein in the step (2), the temperature in the drying oven is maintained at 110-120 ℃; the reaction time is 3-4 h.
6. The method for preparing A + V type structural starch according to claim 1, wherein in the step (3), the cold storage preservation is ice-sealing in a refrigerator at 4 ℃ for 10-14 h.
7. The method for preparing A + V type structured starch according to claim 1, wherein the lyophilization process is performed in a vacuum lyophilizer at-40 ℃ under a vacuum degree of 0-0.3mpa in step (3).
8. The A + V structured starch prepared by the preparation method according to any one of claims 1 to 7, wherein the relative crystallinity of the A + V structured starch is as low as 10.67%.
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CN1515507A (en) * 2003-01-08 2004-07-28 中国科学院沈阳应用生态研究所 Ecological safety composite type iron system high-effective flocculating agent
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