阅读说明：本技术 一种具有高效吸附尿素功能的特定形貌纳米淀粉及其制备方法与应用 (Specific-morphology nano starch with efficient urea adsorption function and preparation method and application thereof ) 是由 刘培 潘欣 张黄琴 张晔钧 钱大玮 段金廒 于 2021-08-02 设计创作，主要内容包括：本发明公开了一种具有高效吸附尿素功能的特定形貌纳米淀粉及其制备方法,本发明以具有各种结晶构型的淀粉为原料,在超声的辅助下,利用二甲亚砜(DMSO)破坏淀粉间的相互作用力的方法制得淀粉纳米粒。通过改变DMSO和水的体积比以及淀粉的投入量,可以形成包括花状、丝状、片状等形貌的纳米淀粉粒,所形成的纳米淀粉粒的粒径分布在95-180 nm之间,可以有效吸附尿素,吸附量在27.31-135.60 mg/g之间。通过本发明制备的纳米淀粉粒尺寸较小,形貌均一,产量较高,具有较好的尿素吸附能力,可作为透析液再生剂应用于血液透析系统或腹透透析系统。(The invention discloses a specific-morphology nano-starch with a function of efficiently adsorbing urea and a preparation method thereof. By changing the volume ratio of DMSO to water and the input amount of starch, nano starch grains with flower-shaped, thread-shaped, sheet-shaped and other shapes can be formed, the grain size distribution of the formed nano starch grains is between 95 and 180nm, urea can be effectively adsorbed, and the adsorption amount is between 27.31 and 135.60 mg/g. The nano starch prepared by the method has the advantages of small particle size, uniform appearance, high yield and good urea adsorption capacity, and can be used as a dialysate regenerant to be applied to a hemodialysis system or a peritoneal dialysis system.)

1. The specific-morphology nano starch with the efficient urea adsorption function is characterized in that the nano starch with flower-shaped, thread-shaped and sheet-shaped morphologies and particle sizes distributed between 95 nm and 180nm is obtained from starch with various crystal configurations.

2. The preparation method of the nano starch with the specific morphology and the function of efficiently adsorbing urea as claimed in claim 1, characterized by comprising the following steps:

a. adding corn starch, potato starch or fructus Trichosanthis starch into DMSO-water solution;

b. b, stirring the suspension obtained in the step a, and then performing ultrasonic treatment;

c. b, adding pure water into the suspension obtained in the step b, stirring again, and performing ultrasonic treatment;

d. and c, centrifuging the suspension obtained in the step c, taking the precipitate, performing ultrasonic dispersion again by using deionized water, repeating for 3 times, removing impurities from the product obtained by dialysis, and performing freeze drying to obtain the nano starch.

3. The preparation method of the nano-starch with the specific morphology and the high-efficiency urea adsorption function according to claim 2, characterized by comprising the following steps:

a. adding DMSO-water solution into starch;

b. b, stirring the suspension obtained in the step a for 10min, and carrying out 400W ultrasonic treatment for 1 h;

c. b, adding 30mL of pure water into the suspension obtained in the step b, stirring for 10min again, and performing 400W ultrasonic treatment for 1 h;

d. and c, centrifuging 30000g of the suspension obtained in the step c for 30min, taking the precipitate, performing ultrasonic dispersion again by using deionized water, repeating the ultrasonic dispersion for 3 times, removing impurities from the product obtained by dialysis, and performing freeze drying to obtain the nano starch.

4. The method for preparing nano starch with specific morphology and high urea adsorption function according to claim 2 or 3, characterized in that: the starch in the step a comprises A-type crystalline corn starch, B-type crystalline potato starch and C-type crystalline trichosanthes starch.

5. The method for preparing nano starch with specific morphology and high urea adsorption function according to claim 2 or 3, characterized in that: treatment with ultrasound-assisted DMSO-water solution was used.

6. The method for preparing nano starch with specific morphology and high urea adsorption function according to claim 2 or 3, characterized in that: by controlling different feed ratios and the ratio of DMSO to water, nano starch with various shapes and sizes can be obtained.

7. The method for preparing nano starch with specific morphology and high urea adsorption function according to claim 2 or 3, characterized in that: in the preparation method, the input amount of the starch in the step a is 250-750 g/L, and the concentration in DMSO is 50-100%.

8. The method for preparing nano starch with specific morphology and high urea adsorption function according to claim 2 or 3, characterized in that: in the preparation method, the input amount of the starch in the step a is 250g/L, 500g/L and 750g/L, and the concentration of DMSO is 80%, 90% and 100%.

9. The application of the nano-starch with specific morphology and high urea adsorption efficiency in the hemodialysis system or the peritoneal dialysis system as a dialysate regenerating agent in claim 1.

Technical Field

The invention relates to specific-morphology nano starch, in particular to a preparation method of specific-morphology nano starch with a function of efficiently adsorbing urea, which is obtained from corn starch, potato starch and trichosanthes starch (the crystal configuration is A, B or C type respectively).

Background

The nano-Starch (SNPs) is a natural novel nano-material with low cost and easy biodegradation, and has wide application prospect in the biomedical field taking antibiotics or anticancer drugs as a targeted drug delivery system. The final properties of SNPs are greatly influenced by the synthesis method and conditions, and nano-starch with different shapes and sizes can be prepared by adjusting the reaction conditions.

At present, the preparation of the nano starch is mainly obtained by an ultrasonic-assisted acid method or an enzyme method, or by adding a DMSO solution and heating. The acid treatment time is long, and the enzyme treatment cost is high.

The invention adopts ultrasonic wave assistance to ensure that the organic solvent dimethyl sulfoxide (DMSO) with different water contents can quickly convert starch into nano starch with specific morphology in a mild environment. The preparation method has the advantages of short time consumption, high efficiency and controllable product appearance, can greatly shorten the preparation time of the nano starch, and further meets the industrial requirement of the nano starch. The obtained nano starch with various shapes has the function of efficiently adsorbing urea, and can be used as a dialysate regenerant to be applied to a hemodialysis system or a peritoneal dialysis system.

Disclosure of Invention

The purpose of the invention is as follows: the invention aims to provide a method for preparing nano starch which is suitable for starch with various crystal configurations, short in time consumption, high in efficiency, controllable in product form, recyclable in solvent and high in urea adsorption function.

The technical scheme is as follows: in order to realize the purpose, the invention adopts the technical scheme that:

a nano-starch with specific morphology and high urea adsorption function is prepared from starch with various crystal configurations through preparing nano-starch with flower, thread and sheet morphologies and particle size distribution of 95-180 nm.

A preparation method of nano starch with a specific morphology and a function of efficiently adsorbing urea comprises the following steps:

a. adding corn starch, potato starch or fructus Trichosanthis starch into DMSO-water solution;

b. b, stirring the suspension obtained in the step a, and then performing ultrasonic treatment;

c. b, adding pure water into the suspension obtained in the step b, stirring again, and performing ultrasonic treatment;

d. and c, centrifuging the suspension obtained in the step c, taking the precipitate, performing ultrasonic dispersion again by using deionized water, repeating for 3 times, removing impurities from the product obtained by dialysis, and performing freeze drying to obtain the nano starch.

A preparation method of nano starch with a specific morphology and a function of efficiently adsorbing urea comprises the following steps:

a. adding DMSO-water solution into starch;

b. b, stirring the suspension obtained in the step a for 10min, and carrying out 400W ultrasonic treatment for 1 h;

c. b, adding 30mL of pure water into the suspension obtained in the step b, stirring for 10min again, and performing 400W ultrasonic treatment for 1 h;

d. and c, centrifuging 30000g of the suspension obtained in the step c for 30min, taking the precipitate, performing ultrasonic dispersion again by using deionized water, repeating the ultrasonic dispersion for 3 times, removing impurities from the product obtained by dialysis, and performing freeze drying to obtain the nano starch.

As a preferred scheme, the preparation method of the nano starch with the specific morphology and the function of efficiently adsorbing urea is characterized by comprising the following steps: the starch in the step a comprises A-type crystalline corn starch, B-type crystalline potato starch and C-type crystalline trichosanthes starch.

As a preferable scheme, the preparation method of the nano starch with the specific morphology and the function of efficiently adsorbing urea uses the DMSO-water solution assisted by ultrasound for treatment.

As a preferable scheme, the preparation method of the nano starch with the specific morphology and the function of efficiently adsorbing urea can obtain the nano starch with various morphologies and sizes by controlling different feed ratios and the ratio of DMSO to water.

Preferably, in the preparation method of the nano starch with the specific morphology and the function of efficiently adsorbing urea, the input amount of the starch in the step a is 250-750 g/L, and the concentration in DMSO is 50-100%.

Preferably, in the preparation method of the nano starch with the specific morphology and the function of efficiently adsorbing urea, the input amount of the starch in the step a is 250g/L, 500g/L and 750g/L, and the concentration in DMSO is 80%, 90% and 100%.

An application of nano starch with a specific shape and a function of efficiently adsorbing urea in a hemodialysis system or a peritoneal dialysis system as a dialysate regenerating agent.

Has the advantages that: compared with the prior art, the invention has the following advantages:

(1) the preparation method of the nano starch provided by the invention is high in efficiency, the solvent can be recycled, and the production of the nano starch with different shapes can be effectively improved.

(2) The nano starch provided by the invention has small particle size and uniform appearance, and the appearance of the product can be controlled according to the amount of the controlled reactant.

(3) The nano starch provided by the invention has a function of efficiently adsorbing urea, and can be used as a dialysate regenerant to be applied to a hemodialysis system or a peritoneal dialysis system.

Drawings

FIG. 1 is a schematic diagram of XRD of different starches and a schematic diagram of absorption of 7 kinds of SNPs, wherein A is three kinds of common starch, B is corn starch and processed corn SNPs, C is potato starch and processed potato SNPs, and D is trichosanthes starch and processed trichosanthes SNPs; e is an adsorption kinetic curve of 7 SNPs, and F is an adsorption isotherm of 7 SNPs.

FIG. 2 is scanning electron microscope atlas of corn nanometer starch in different conditions.

FIG. 3 is scanning electron microscope atlas of potato nanometer starch of different conditions.

FIG. 4 is a scanning electron microscope atlas of Trichosanthes kirilowii Maxim nanometer starch under different conditions.

Detailed description of the preferred embodiments

The invention will be better understood from the following examples. However, one skilled in the art will readily appreciate that the specific manufacturing processes and functional evaluations described in the examples are merely illustrative of the present invention and should not, nor should they be construed as limiting the invention as detailed in the claims.

Example 1

The preparation method of the corn flake SNPs comprises the following steps:

taking 0.5g of corn starch, adding 20mL of 100% DMSO, stirring for 10min, performing ultrasonic treatment for 1h, adding 30mL of pure water, stirring for 10min, continuing ultrasonic treatment for 1h, finally centrifuging 30000g for 30min, performing ultrasonic dispersion again by using deionized water, repeating for 3 times, removing impurities from a product obtained by dialysis, and performing freeze drying to obtain corn flake SNPs (AD1), wherein SEM is shown in figure 2, XRD is shown in figure 1B, and the average particle size is shown in table 1.

Example 2

The preparation method of the corn flake SNPs comprises the following steps:

taking 1g of corn starch, adding 20mL of 90% DMSO, stirring for 10min, performing ultrasonic treatment for 1h, adding 30mL of pure water, stirring for 10min, continuing ultrasonic treatment for 1h, finally centrifuging 30000g for 30min, performing ultrasonic dispersion again by using deionized water, repeating for 3 times, removing impurities from a product obtained by dialysis, and performing freeze drying to obtain corn flake SNPs (AD5), wherein SEM is shown in figure 2, XRD is shown in figure 1B, and the average particle size is shown in table 1.

Example 3

A preparation method of potato flake SNPs comprises the following steps:

taking 0.5g of potato starch, adding 20mL of 100% DMSO, stirring for 10min, performing ultrasonic treatment for 1h, adding 30mL of pure water, stirring for 10min, continuing ultrasonic treatment for 1h, finally centrifuging 30000g for 30min, performing ultrasonic dispersion again by using deionized water, repeating for 3 times, removing impurities from the product obtained by dialysis, and performing freeze drying to obtain potato flake SNPs (AD16), wherein SEM is shown in figure 3, XRD is shown in figure 1C, and the average particle size is shown in table 1.

Example 4

A preparation method of potato filamentous SNPs comprises the following steps:

taking 1.5g of potato starch, adding 20mL of 90% DMSO, stirring for 10min, performing ultrasonic treatment for 1h, adding 30mL of pure water, stirring for 10min, continuing ultrasonic treatment for 1h, finally centrifuging 30000g for 30min, performing ultrasonic dispersion again by using deionized water, repeating for 3 times, removing impurities from the product obtained by dialysis, and performing freeze drying to obtain potato flake SNPs (AD21), wherein SEM is shown in figure 3, XRD is shown in figure 1C, and the average particle size is shown in table 1.

Example 5

A preparation method of trichosanthes kirilowii maxim flaky SNPs comprises the following steps:

taking 0.5g of trichosanthes starch, adding 20mL of 100% DMSO, stirring for 10min, performing ultrasonic treatment for 1h, adding 30mL of pure water, stirring for 10min, continuing ultrasonic treatment for 1h, finally centrifuging 30000g for 30min, performing ultrasonic dispersion again by using deionized water, repeating for 3 times, removing impurities from a product obtained by dialysis, and performing freeze drying to obtain trichosanthes slice SNPs (AD34), wherein SEM is shown in figure 4, XRD is shown in figure 1D, and the average particle size is shown in table 1.

Example 6

A preparation method of trichosanthes kirilowii flake SNPs comprises the following steps:

taking 1.5g of trichosanthes starch, adding 20mL of 90% DMSO, stirring for 10min, performing ultrasonic treatment for 1h, adding 30mL of pure water, stirring for 10min, continuing ultrasonic treatment for 1h, finally centrifuging 30000g for 30min, performing ultrasonic dispersion again by using deionized water, repeating for 3 times, removing impurities from a product obtained by dialysis, and performing freeze drying to obtain trichosanthes flaky SNPs (AD36), wherein SEM is shown in figure 4, XRD is shown in figure 1D, and the average particle size is shown in table 1.

Example 7

A preparation method of Trichosanthes kirilowii filiform SNPs comprises the following steps:

taking 1.5g of trichosanthes starch, adding 20mL of 80% DMSO, stirring for 10min, performing ultrasonic treatment for 1h, adding 30mL of pure water, stirring for 10min, continuing ultrasonic treatment for 1h, finally centrifuging 30000g for 30min, performing ultrasonic dispersion again by using deionized water, repeating for 3 times, removing impurities from a product obtained by dialysis, and performing freeze drying to obtain trichosanthes filamentous SNPs (AD38), wherein SEM is shown in figure 4, XRD is shown in figure 1D, and the average particle size is shown in table 1.

Wherein AD2, AD3 and AD4 of Table 1 are prepared by the same process as in example 1; AD6, AD7, AD8 and AD9 were prepared by the same procedures as in example 2; AD17, AD18, AD19 and AD20 were prepared by the same procedures as in example 3; AD21, TABLE 1 sample preparation conditions for different SNPs

Example 8 Urea adsorption experiment

7 SNPs prepared in examples 1 to 7 and having different forms were measured as adsorption models, and their relative adsorption amounts in PBS were measured, and the parameters of adsorption curve fitting are shown in Table 2. Adsorption Capacity of the model for Urea (c)₀0.4mg/mL) showed that five SNPs (AD5, AD16, AD21, AD34, AD36) showed almost the same adsorption kinetics when urea was removed from PBS within 900 minutes, except for the sheet-like SNPs (AD1 and AD34) (fig. 1). The adsorption equilibrium time of the plate-like SNP was 120 minutes, and the adsorption equilibrium time of the other SNPs was 180 minutes.

When the adsorbate was gradually increased to 1.00mg/L, the adsorption amount of urea was different for the seven SNPs. The adsorption capacity of the corn starch nanoparticles AD1 and AD5 to urea is 52.67mg/g and 36.18 mg/g. The urea adsorption capacity of the potato starch nanoparticles AD16 and AD21 is up to 28.05mg/g and 27.31 mg/g. The urea content of the trichosanthes starch nanoparticles AD34, AD36 and AD38 is up to 135.60mg/g, 105.51mg/g and 62.19 mg/g.

TABLE 27 fitting curves for adsorption of Nano-starch

The invention develops a preparation method of novel nano starch, which can prepare the nano starch efficiently and rapidly; meanwhile, the prepared nano starch has an effective adsorption effect on urea, can provide raw materials for the development of a follow-up dialysate regenerating agent, is applied to a hemodialysis system or a peritoneal dialysis system, and has an important practical application value.

The foregoing is only a preferred embodiment of the present invention, and it should be noted that, for those skilled in the art, various modifications and decorations can be made without departing from the principle of the present invention, and these modifications and decorations should also be regarded as the protection scope of the present invention.