Preparation method of corncob-based essence carrier with high loading capacity and fragrance loading stability

Abstract

The invention discloses a preparation method of a corncob-based essence carrier with high loading capacity and fragrance loading stability, which comprises the following steps: adding corncob particles into a compound modification reagent, and heating; after the reaction is finished, washing with deionized water, and drying to obtain modified corncob particles with high loading rate and fragrance loading stability; the compound modification reagent is composed of a modification reagent A and a modification reagent B according to the mass ratio of (1-4): (1-4), the modification reagent A is one of acid, alkali, an oxidizing agent and an organic solvent, and the modification reagent B is one of acid, alkali, an oxidizing agent and an organic solvent. The corncob particles are chemically modified according to the principle of partially removing lignin, cellulose and hemicellulose for the first time, so that the surface and internal pore structures of the corncob particles are improved, and the modified corncob particles with high loading capacity and fragrance loading stability are further obtained and can be used as good green carriers for loading essence.

Description

Technical Field

[0001] The present invention belongs to the technical field of fragrance loading and slow release, and particularly relates to a preparation method of a corncob-based fragrance carrier with high loading capacity and fragrance loading stability. Background Art

[0002] Due to their unique aroma and functional properties, flavors and fragrances are widely used in industries such as food, pharmaceuticals, cosmetics, and tobacco. These compounds help improve the quality and uniqueness of the flavor profiles of various products. However, the inherently high volatility of flavors and fragrances causes the aroma to rapidly dissipate when exposed to air, thereby compromising the storage stability of the final products. Therefore, the development of advanced fragrance delivery systems to ensure extended aroma release has become a key research area.

[0003] In recent years, porous materials have been widely used as adsorbents for fragrance adsorption and controlled release. Representative examples of such materials include silica nanoparticles, zeolites, activated carbon, and aluminosilicates. Due to their fine pore structures, these materials exhibit special aroma storage and release properties. However, existing delivery systems generally have some drawbacks, including higher costs, more complex manufacturing processes, high loading capacity but weak release capacity.

[0004] Corncob is a waste byproduct of agricultural production. As an organic biomass material, the vast majority of it is used for incineration, which not only causes environmental pollution but also wastes organic resources. Against the backdrop of global shortages of petrochemical energy, the high-value utilization of biomass resources has attracted much attention. Corncob is a lignocellulosic material with a regular pore structure. Lignocellulosic fibers are mainly composed of cellulose, hemicellulose, and lignin, forming a complex skeletal structure. However, there is little research on using corncob as an aroma carrier. Summary of the Invention

[0005] The purpose of this section is to outline some aspects of the embodiments of the present invention and briefly introduce some preferred embodiments. Some simplifications or omissions may be made in this section, as well as in the abstract and title of the present application, to avoid obscuring the purpose of this section, the abstract, and the title. However, such simplifications or omissions shall not be used to limit the scope of the present invention.

[0006] In view of the above and / or problems existing in the prior art, the present invention is proposed.

[0007] Therefore, the purpose of the present invention is to overcome the deficiencies in the prior art and provide a preparation method of a corncob-based fragrance carrier with high loading capacity and fragrance loading stability.

[0008] To solve the above technical problems, the present invention provides the following technical solution: A preparation method of a corncob-based fragrance carrier with high loading capacity and fragrance loading stability, comprising,

[0009] Add corncob particles to the compound modification reagent and heat-treat them.

[0010] After completion, wash with deionized water and obtain modified corncob particles with high loading rate and fragrance stability through drying.

[0011] The compound modification reagent is composed of modification reagent A and modification reagent B in a mass ratio of 1-4:1-4. Among them, modification reagent A is one of an acid, a base, an oxidant, and an organic solvent, and modification reagent B is one of an acid, a base, an oxidant, and an organic solvent.

[0012] As a preferred embodiment of the preparation method of the present invention, among them: the base includes sodium hydroxide and potassium hydroxide, the acid includes dilute hydrochloric acid, dilute sulfuric acid, and dilute acetic acid, the oxidant includes hydrogen peroxide, and the organic solvent includes absolute ethanol.

[0013] As a preferred embodiment of the preparation method of the present invention, among them: the compound modification reagent includes one or more of acid-base, acid-oxidant, base-oxidant, acid-absolute ethanol, base-absolute ethanol, and oxidant-absolute ethanol.

[0014] As a preferred embodiment of the preparation method of the present invention, among them: the mass ratio of the acid to the base in the acid-base is 1-4:1-4.

[0015] The mass ratio of the acid to the oxidant in the acid-oxidant is 1-4:1-4.

[0016] The mass ratio of the base to the oxidant in the base-oxidant is 1-4:1-4.

[0017] The mass ratio of the acid to the absolute ethanol in the acid-absolute ethanol is 1-4:1-4.

[0018] The mass ratio of the base to the absolute ethanol in the base-absolute ethanol is 1-4:1-4.

[0019] The mass ratio of the oxidant to the absolute ethanol in the oxidant-absolute ethanol is 1-4:1-4.

[0020] As a preferred embodiment of the preparation method of the present invention, among them: the particle size of the corncob particles is 14-18 mesh.

[0021] As a preferred embodiment of the preparation method of the present invention, among them: for the heat treatment, the treatment temperature is 50-90 °C and the treatment time is 2-6 h.

[0022] As a preferred embodiment of the preparation method of the present invention, among them: for the deionized water washing, the washing end point is that the pH of the washing liquid is 7.

[0023] As a preferred embodiment of the preparation method of the present invention, wherein: for the drying, the drying method is freeze-drying at -50°C, and the drying time is 24 h.

[0024] Another object of the present invention is to overcome the deficiencies in the prior art and provide a corncob-based flavor carrier with high loading capacity and flavor loading stability.

[0025] Another object of the present invention is to overcome the deficiencies in the prior art and provide an application of a corncob-based flavor carrier with high loading capacity and flavor loading stability in the preparation of a flavor sustained-release agent.

[0026] Advantages of the present invention:

[0027] (1) For the first time, the present invention chemically modifies corncob particles based on the principle of partial removal of lignin, cellulose and hemicellulose, so as to improve their surface and internal pore structures, and then obtains modified corncob particles with high loading capacity and flavor loading stability, which can be used as a good green carrier for flavor loading.

[0028] (2) The flavor-loaded modified particles prepared by the present invention have a good flavor loading capacity. Since the modification increases the specific surface area and total pore volume inside the particles, there is more accommodation space for the flavor to be loaded into the inside of the particles. Therefore, the flavor-loaded modified particles obtained by the modification can all reach a flavor loading content of more than 1.4 g / g.

[0029] (3) The flavor-loaded modified particles prepared by the present invention still have a good flavor content after 90 days of storage. Since more hydroxyl groups and other groups inside the particles are exposed after the modification, the hydrogen bond force between the flavor and the internal skeleton of the particles increases, thereby increasing its flavor loading stability. Therefore, the flavor loss amount after the storage period is only about 30% of the initial loading amount.

[0030] (4) The raw material of the corncob particles of the present invention is widely available in nature. It is a by-product waste of agricultural product processing, and most of it is burned, which not only pollutes the environment but also wastes biomass resources. As a natural green lignocellulosic material, it has a high potential for flavor loading. Description of the drawings

[0031] In order to more clearly illustrate the technical solutions of the embodiments of the present invention, the following will briefly introduce the drawings required for the description of the embodiments. Obviously, the following drawings are only some embodiments of the present invention. For those of ordinary skill in the art, without creative efforts, other drawings can also be obtained according to these drawings. Among them:

[0032] Figure 1 It is a comparison chart of the flavor loading amounts of the particle samples prepared in Examples 1 to 3 and the control example of the present invention.

[0033] Figure 2 This is a graph showing the change in the remaining fragrance loading of the granular samples prepared in Examples 1 to 3 and the control example at 0 days and 90 days of storage period.

[0034] Figure 3 This is a comparison graph of the surface morphologies of the granular samples prepared in Examples 1 to 3 and the control example. Among them, a1 and a2 are the cross-sectional view and longitudinal-sectional view of the granular sample of Control Example 1 respectively, b1 and b2 are the cross-sectional view and longitudinal-sectional view of the granular sample of Example 1 respectively, c1 and c2 are the cross-sectional view and longitudinal-sectional view of the granular sample of Example 2 respectively, and d1 and d2 are the cross-sectional view and longitudinal-sectional view of the granular sample of Example 3 respectively. Detailed implementation manners

[0035] To make the above objects, features and advantages of the present invention more obvious and understandable, the following will describe the detailed implementation manners of the present invention in conjunction with the embodiments of the specification.

[0036] In the following description, many specific details are set forth to fully understand the present invention. However, the present invention can also be implemented in other ways different from those described herein. Those skilled in the art can make similar generalizations without departing from the connotation of the present invention. Therefore, the present invention is not limited by the specific embodiments disclosed below.

[0037] Secondly, the so-called "one embodiment" or "embodiment" herein refers to specific features, structures or characteristics that can be included in at least one implementation manner of the present invention. The "in one embodiment" appearing in different places in this specification does not all refer to the same embodiment, nor is it a separate or alternative embodiment that is mutually exclusive with other embodiments.

[0038] Determination of the fragrance loading of the fragrance-loaded modified particles in the present invention:

[0039] Accurately pipette 10 mL of absolute ethanol into a 15 mL centrifuge tube. Take about 200 mg of the fragrance-loaded modified particles and add them to the centrifuge tube filled with the extractant. Oscillate 3 times on a vortex oscillator, 30 seconds each time. Then put it into an ultrasonic cleaner for ultrasonic extraction. The ultrasonic conditions are: ultrasonic power 500 W, ultrasonic frequency 40 kHz, ultrasonic time 1 h. Then centrifuge at 5000 rpm for 5 min. Take 2 mL of the centrifuged supernatant and add it to a liquid phase bottle, and store it in the dark. Use liquid chromatography to quantitatively analyze the fragrance content.

[0040] The standard curve for quantitatively analyzing the fragrance content by liquid chromatography is:

[0041] y = 107179x - 264.94 (R 2 = 0.9998)

[0042] Wherein, y -- peak area;

[0043] x -- concentration of essence, mg / mL.

[0044] The calculation method for the content of essence in the centrifuged supernatant of the sample is as follows:

[0045]

[0046] Wherein, M Fra -- mass of essence, mg;

[0047] y -- peak area.

[0048] The calculation method for the loading rate of the essence-loaded modified particles is as follows:

[0049]

[0050] Wherein: LC -- loading rate of the essence-loaded modified particles, g / g;

[0051] Mb -- content of essence loaded into the essence-loaded modified particles, g

[0052] Ma -- mass of the essence-loaded modified particles, g.

[0053] The calculation method for the essence-loading stability of the essence-loaded modified particles is as follows:

[0054]

[0055] Wherein: CR -- cumulative release rate of the essence-loaded modified particles, %;

[0056] M1 -- initial essence loading in the essence-loaded modified particles (at the 0th day), mg;

[0057] M2 -- remaining essence loading in the essence-loaded modified particles after storage for a certain period of time, mg.

[0058] The corncob particles used in the present invention are purchased from Taiqian Ruida Biotechnology Co., Ltd., with a size of 14 - 18 mesh; the peppermint essence is purchased from Huabao Flavors & Fragrances Co., Ltd.; the essence standard D,L-menthol (100%) is purchased from Merck Experimental Equipment (Shanghai) Co., Ltd.

[0059] Example 1

[0060] This example provides a preparation method for modified corncob particles with high loading capacity and essence-loading stability:

[0061] (1) Prepare a compound modification reagent: Add 0.25 parts of 1M dilute hydrochloric acid to 1 part of absolute ethanol, stir and mix evenly, and then perform preheating treatment at 70°C for 5 min;

[0062] (2) Preparation of modified particles: After the compound modified solution is preheated, corncob particles are added, stirred at 200 rpm, and subjected to modification treatment at 70 °C for 3 h to obtain undried modified corncob particles.

[0063] (3) Place the undried modified corncob particles in a -10 °C refrigerator for pre-freezing, and then use a freeze dryer for freeze-drying at -50 °C for 24 h to obtain the final modified corncob particle product with high loading capacity and fragrance stability.

[0064] Example 2

[0065] This example provides a preparation method of modified corncob particles with high loading capacity and fragrance stability:

[0066] (1) Preparation of compound modified reagent: Add 1 part of 1 M dilute hydrochloric acid to 1 part of 15 wt% hydrogen peroxide solution, stir and mix evenly, and then preheat at 80 °C for 5 min;

[0067] (2) Preparation of modified particles: After the compound modified solution is preheated, corncob particles are added, stirred at 200 rpm, and subjected to modification treatment at 80 °C for 4 h to obtain undried modified corncob particles.

[0068] (3) Place the undried modified corncob particles in a -10 °C refrigerator for pre-freezing, and then use a freeze dryer for freeze-drying at -50 °C for 24 h to obtain the final modified corncob particle product with high loading capacity and fragrance stability.

[0069] Example 3

[0070] This example provides a preparation method of modified corncob particles with high loading capacity and fragrance stability:

[0071] (1) Preparation of compound modified reagent: Add 2 parts of 1 M sodium hydroxide solution to 1 part of absolute ethanol, stir and mix evenly, and then preheat at 60 °C for 5 min;

[0072] (2) Preparation of modified particles: After the compound modified solution is preheated, corncob particles are added, stirred at 200 rpm, and subjected to modification treatment at 60 °C for 2 h to obtain undried modified corncob particles.

[0073] (3) Place the undried modified corncob particles in a -10 °C refrigerator for pre-freezing, and then use a freeze dryer for freeze-drying at -50 °C for 24 h to obtain the final modified corncob particle product with high loading capacity and fragrance stability.

[0074] Control Example 1

[0075] (1) Preparation of modified particles: After preheating deionized water, add corncob particles and stir at 200 rpm. Conduct modification treatment at 70 °C for 2 h to obtain undried modified corncob particles.

[0076] (2) Place the undried modified corncob particles in a -10 °C refrigerator for pre-freezing, and then use a freeze dryer for freeze-drying at -50 °C for 24 h to obtain a product of corncob particles modified without using reagents.

[0077] Control Example 2

[0078] (1) Preparation of a single modification reagent: Preheat 4 parts of 1M sodium hydroxide solution at 60 °C for 5 min;

[0079] (2) Preparation of modified particles: After the single modification reagent is preheated, add corncob particles and stir at 200 rpm. Conduct modification treatment at 60 °C for 2 h to obtain undried modified corncob particles.

[0080] (3) Place the undried modified corncob particles in a -10 °C refrigerator for pre-freezing, and then use a freeze dryer for freeze-drying at -50 °C for 24 h to obtain the final product of single-modified corncob particles.

[0081] Control Example 3

[0082] (1) Preparation of a single modification reagent: Preheat 4 parts of 1M hydrochloric acid solution at 80 °C for 5 min;

[0083] (2) Preparation of modified particles: After the single modification reagent is preheated, add corncob particles and stir at 200 rpm. Conduct modification treatment at 80 °C for 4 h to obtain undried modified corncob particles.

[0084] (3) Place the undried modified corncob particles in a -10 °C refrigerator for pre-freezing, and then use a freeze dryer for freeze-drying at -50 °C for 24 h to obtain the final product of single-modified corncob particles.

[0085] Control Example 4

[0086] (1) Preparation of a single modification reagent: Preheat 4 parts of 15 wt% hydrogen peroxide solution at 80 °C for 5 min;

[0087] (2) Preparation of modified particles: After the single modification reagent is preheated, add corncob particles and stir at 200 rpm. Conduct modification treatment at 80 °C for 4 h to obtain undried modified corncob particles.

[0088] (3) Place the undried modified corncob particles in a refrigerator at -10 °C for pre-freezing, and then use a freeze dryer for freeze-drying at -50 °C for 24 hours to obtain the final single modified corncob particle product.

[0089] The fragrance loading amounts of the modified particle samples prepared in Examples 1 to 3 are shown. It can be seen that the fragrance loading amounts of the particles modified with hydrochloric acid-hydrogen peroxide, hydrochloric acid-absolute ethanol, and sodium hydroxide-absolute ethanol are significantly higher than those of the control example, proving the effectiveness of compound modification compared with single modification. See Figure 1 , and its main mechanism is as follows: Corncob is a lignocellulosic material, and its main components are cellulose, hemicellulose, and lignin, which are intertwined with each other. A single modifying reagent will only remove one of cellulose, hemicellulose, and lignin. Due to the compactness of the structure, the removal will only target the surface substances, resulting in low efficiency; while compound modification will remove multiple components simultaneously, improving the modification efficiency, and thus greatly increasing the pore volume and specific surface area inside the particles. Therefore, it has a significant improvement effect on the fragrance loading amount and storage stability.

[0090] The fragrance release amounts of the modified particle samples prepared in Examples 1 to 3 after storage for 0 days and 90 days are shown in Figure 2 , and it can be seen that the fragrance storage stability of the particles modified with hydrochloric acid-hydrogen peroxide, hydrochloric acid-absolute ethanol, and sodium hydroxide-absolute ethanol is much higher than that of Control Group 1. Figures 1 - 2 The results show that the fragrance loading performance of corncob particles has been greatly improved through modification.

[0091] The surface and cross-sectional morphology characteristics of the modified particle samples prepared in Examples 1 to 3 are shown in Figure 3 , and it can be seen that the modification of the particles in Examples 1 to 3 opens the surface structure of the corncob particles and makes the internal structure more porous, providing sufficient volume for the loading of fragrance, explaining the reasons for the high loading amount and fragrance storage stability after modification.

[0092] It should be noted that the above examples are only used to illustrate the technical solutions of the present invention and are not intended to limit them. Although the present invention has been described in detail with reference to the preferred embodiments, those of ordinary skill in the art should understand that the technical solutions of the present invention can be modified or equivalently replaced without departing from the spirit and scope of the technical solutions of the present invention, and they should all be covered within the scope of the present invention.

Claims

1. A preparation method of a corncob-based essence carrier with high loading capacity and essence loading stability, characterized in that: Including, Adding corncob particles to a compound modification reagent and performing heat treatment; After completion, washing with deionized water and drying to obtain modified corncob particles with a high loading rate and fragrance loading stability; The compound modification reagent is composed of modification reagent A and modification reagent B in a mass ratio of 1-4:1-4, wherein modification reagent A is one of an acid, a base, an oxidant, and an organic solvent, and modification reagent B is one of an acid, a base, an oxidant, and an organic solvent.

2. The preparation method according to claim 1, characterized in that: The base includes sodium hydroxide and potassium hydroxide, the acid includes dilute hydrochloric acid, dilute sulfuric acid, and dilute acetic acid, the oxidant includes hydrogen peroxide, and the organic solvent includes absolute ethanol.

3. The preparation method according to claim 1 or 2, characterized in that: The compound modification reagent includes one or more of acid-base, acid-oxidant, base-oxidant, acid-absolute ethanol, base-absolute ethanol, and oxidant-absolute ethanol.

4. The preparation method according to claim 3, characterized in that: In the acid-base, the mass ratio of the acid to the base is 1-4:1-4; In the acid-oxidant, the mass ratio of the acid to the oxidant is 1-4:1-4; In the base-oxidant, the mass ratio of the base to the oxidant is 1-4:1-4; In the acid-absolute ethanol, the mass ratio of the acid to the absolute ethanol is 1-4:1-4; In the base-absolute ethanol, the mass ratio of the base to the absolute ethanol is 1-4:1-4; In the oxidant-absolute ethanol, the mass ratio of the oxidant to the absolute ethanol is 1-4:1-4.

5. The preparation method according to any one of claims 1, 2 or 4, characterized in that: The particle size of the corncob particles is 14-18 mesh.

6. The preparation method according to claim 5, characterized in that: For the heat treatment, the treatment temperature is 50-90 °C and the treatment time is 2-6 h.

7. The preparation method according to claim 1 or 6, characterized in that: For the washing with deionized water, the washing end point is that the pH of the washing liquid is 7.

8. The preparation method according to claim 7, characterized in that: For the drying, the drying method is freeze-drying at -50 °C and the drying time is 24 h.

9. A corncob-based fragrance carrier with high loading and fragrance loading stability prepared by the preparation method according to any one of claims 1-8.

10. Use of the corncob-based fragrance carrier with high loading and fragrance loading stability according to claim 9 in the preparation of a fragrance loading sustained-release agent.

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