Ligusticum wallichii irradiation fresh-keeping process

Abstract

The invention discloses a ligusticum wallichii irradiation fresh-keeping technology, and relates to the technical field of ligusticum wallichii fresh-keeping. The method includes the following steps that after ligusticum wallichii is pretreated, first electron beam irradiation treatment is conducted, and pretreated ligusticum wallichii is obtained; cuO and CaMoO4 are deposited on the surface of g-C3N4 in situ, and a CuO / CaMoO4 / g-C3N4 composite antibacterial agent is prepared; the preparation method comprises the following steps: by taking porous chitosan as a wall material and a composite antibacterial agent as a core material, preparing an antibacterial microcapsule by adopting a microfluid control process; the antibacterial microcapsules are loaded on packaging paper, and the preservative paper containing the microcapsules is obtained; and carrying out modified atmosphere packaging on the pretreated ligusticum wallichii by using preservative paper containing microcapsules, carrying out secondary electron beam irradiation treatment, and then storing. On the basis of two times of electron beam irradiation treatment and in combination with the packaging paper loaded with the microcapsules, sterilization is more thorough, the antibacterial, corrosion-resistant and insect-resistant effects on ligusticum wallichii are improved, and the storage period of ligusticum wallichii is prolonged.

Description

Technical Field

[0001] The present application relates to the technical field of Chuanxiong preservation, and in particular to a process for irradiation preservation of Chuanxiong. Background Art

[0002] Chuanxiong is a cultivated plant of the genus Ligusticum in the Apiaceae family. It has well-developed rhizomes, which mainly contain alkaloids, phenolic acids, and phthalide active ingredients. It can be used as a medicinal material, and has the effects of promoting blood circulation and qi, dispelling wind and relieving pain. It has certain therapeutic effects on symptoms such as headaches, irregular menstruation, and promoting blood circulation and qi. However, during the storage process of Chuanxiong, the volatile oil and protein in it are easily oxidized, causing the oil of the medicinal material to disappear. The fatty oil in it is easily oxidized and decomposed to eventually produce aldehydes, alcohols, ketones, organic acids and other substances, causing rancidity. In addition, Chuanxiong is also very prone to mildew and insect infestation. At present, the preservation and storage of Chuanxiong is usually carried out by drying, packaging in woven bags, and stacking in a dry and ventilated place indoors. The fumigant aluminum phosphide is used regularly for prevention and insecticide treatment. However, the fumigant is easy to remain on the surface of Chuanxiong after fumigation, and it is easy to damage the quality of Chuanxiong. There are also irradiation treatments in the prior art to achieve Chuanxiong preservation, but they are generally achieved by adjusting the irradiation dose and temperature, and the preservation effect is limited, which is not conducive to the long-term storage of Chuanxiong. Based on this, the present application proposes a process for irradiation preservation of Chuanxiong. Summary of the invention

[0003] The main purpose of the present application is to provide a process for irradiation preservation of Chuanxiong, aiming to solve the technical problem that the prior art is not conducive to the long-term storage of Chuanxiong.

[0004] To achieve the above purpose, the present application proposes a process for irradiation preservation of Chuanxiong, comprising the following steps:

[0005] After the chuanxiong is pretreated, the chuanxiong is subjected to a first electron beam irradiation treatment to obtain a pretreated chuanxiong;

[0006] In gC 3 N 4 In situ deposition of CuO and CaMoO on the surface 4 , preparation of CuO / CaMoO 4 / gC 3 N 4 Composite antibacterial agent; using porous chitosan as the wall material and the composite antibacterial agent as the core material, and adopting a microfluidic control process to prepare antibacterial microcapsules;

[0007] The antibacterial microcapsules are loaded on packaging paper to obtain fresh-keeping paper containing microcapsules;

[0008] The pre-treated Chuanxiong is packaged with modified atmosphere by the fresh-keeping paper containing microcapsules, and then subjected to a second electron beam irradiation treatment before being stored.

[0009] Optionally, the step of pretreating Ligusticum chuanxiong comprises:

[0010] After washing and removing impurities, the rhizome of Chuanxiong is soaked in a preservative solution for 30-60 minutes, then taken out and dried at 40-50°C for 1-4 hours; wherein the preservative solution comprises cinnamaldehyde, eugenol and oligofructose.

[0011] Optionally, in the step of performing the first electron beam irradiation treatment, the energy of the electron beam is 5MeV-6MeV, and the irradiation dose absorbed by Chuanxiong is controlled to be 0.6kGy-1kGy.

[0012] Optionally, the step of preparing the antibacterial microcapsules by using porous chitosan as the wall material and the composite antibacterial agent as the core material and adopting a microfluidic control process comprises:

[0013] preparing porous chitosan wall materials;

[0014] Adding sodium carboxymethyl cellulose to the porous chitosan wall material and mixing to obtain a mixture; then mixing the composite antibacterial agent with water and ball milling for 20 hours to 28 hours, and then adding the composite antibacterial agent to the mixture to obtain a dispersed phase;

[0015] After mixing dimethyl silicone oil with carbon tetrachloride, a continuous phase is obtained;

[0016] The dispersed phase and the continuous phase are placed in a microfluidic control device to form droplets, which are then solidified into gel microspheres in a 68-72° C. coagulation bath. After suction filtration, washing and drying, antibacterial microcapsules are obtained.

[0017] Optionally, the step of preparing the porous chitosan wall material comprises:

[0018] The γ-polyglutamic acid solution and Tween-20 are stirred and mixed at room temperature, and a porogen is added to obtain a mixed solution;

[0019] Acetic acid is added to the chitosan solution and then dripped into the mixed solution. After the reaction, the mixture is centrifuged and hydrochloric acid solution is added to allow the gas to escape. Then, concentrated ammonia water is added and adjusted to a pH of 7. The mixture is washed with deionized water and ethanol in turn and dried at room temperature to a constant weight to obtain the porous chitosan wall material.

[0020] Optionally, the 3 N 4 In situ deposition of CuO and CaMoO on the surface 4 , preparation of CuO / CaMoO 4 / gC 3 N 4 The steps of compounding the antimicrobial agent include:

[0021] After grinding and mixing thiourea and urea, the temperature was raised to 540-560°C at a rate of 2°C / min under a nitrogen atmosphere, kept constant for 3h-5h, and then naturally cooled to room temperature. After grinding, gC 3 N 4 ;

[0022] The gC 3 N 4 and CaMoO 4 ,CuSO 4 Add them together into the reaction kettle, then add sodium borohydride solution, stir, and perform hydrothermal reaction at 180℃-200℃ for 20h-26h. After the reaction, cool to room temperature, collect the product after centrifugation, wash with anhydrous ethanol, and vacuum dry at 75℃-85℃ for 5h-7h to obtain CuO / CaMoO 4 / gC 3 N 4 Composite antimicrobial agent.

[0023] Optionally, the step of loading the antibacterial microcapsules on packaging paper to obtain fresh-keeping paper containing microcapsules comprises:

[0024] Soak the wrapping paper in the m-phenylenediamine solution for 3-8 minutes;

[0025] The antibacterial microcapsules are ultrasonically dispersed in an ethanol solution, the ultrasonic frequency is 50 MHz-180 MHz, the ultrasonic time is 10 min-25 min, and then 1,3,5-triphenylethylene trimesoyl chloride is added, stirred and mixed, and then the soaked wrapping paper is added, and stirred at a speed of 100 r / min-140 r / min for 5 min-10 min, and then the wrapping paper is taken out and dried at 60° C.-70° C. for 1 h-4 h to obtain a cling paper containing microcapsules.

[0026] Optionally, the step of performing modified atmosphere packaging on the pretreated Chuanxiong by using the cling paper containing microcapsules comprises:

[0027] The preservative paper containing the microcapsules is used as a packaging bag to package the pretreated Chuanxiong, and a mixed gas consisting of oxygen and carbon dioxide is filled into the bag; wherein the volume ratio of the mixed gas is O 2 ∶CO 2 It is 8%-10%.

[0028] Optionally, in the step of performing the second electron beam irradiation treatment, the energy of the electron beam is 7MeV-10MeV, and the irradiation dose absorbed by Chuanxiong is controlled to be 3.5kGy-4.5kGy.

[0029] Optionally, the step of storing comprises:

[0030] The chuanxiong treated by the second electron beam irradiation is stored in an environment with a temperature of 5-25° C. and a relative humidity of 35%-60%.

[0031] The present application firstly performs the first electron beam irradiation treatment after the pretreatment of Chuanxiong, and uses the high-energy electron beam rays generated by the electron accelerator to irradiate Chuanxiong, and the high-energy pulse directly acts on the microorganisms on its surface to cause a series of physical and chemical reactions, inhibit the respiratory activity and enzyme activity of the microorganisms, and achieve a preliminary antibacterial effect; and graphite phase carbon nitride (g-C3N4) can be used as a photocatalytic antibacterial agent, and its bandgap width is only 2.7eV-2.8eV, which can absorb light with a wavelength of less than 475nm in solar energy, and at the same time has good biocompatibility, low toxicity, high stability, etc. The superoxide radicals generated under light excitation have strong redox properties and can oxidize the unsaturated phospholipid molecular layer in the bacterial cell membrane, causing cell leakage and ultimately killing bacteria, thereby having strong antibacterial properties. However, the antibacterial properties of g-C3N4 are poor under dark conditions. In order to improve the antibacterial rate of the composite antibacterial agent under light reaction and dark reaction, the present application prepares a CuO / CaMoO4 / g-C3N4 composite antibacterial agent by in-situ deposition of CuO and CaMoO4 on the surface of g-C3N4. The composite antibacterial agent has good antibacterial performance in both light reaction and dark reaction. The antibacterial rate is very high whether it is under dark reaction or porous chitosan is used as wall material and composite antibacterial agent is used as core material. The large specific surface area and porosity of porous chitosan are utilized to make it have excellent carrier performance, which promotes its loading and embedding of composite antibacterial agent. Microfluidic control process is then used to prepare antibacterial microcapsules, and the composite antibacterial agent is embedded in porous chitosan to form gel microspheres with complete capsule wall and good embedding structure. Microfluidics is used to accurately realize the controllable preparation of gel microsphere particle size and morphology, which is conducive to the stable and uniform preparation of the antibacterial microcapsules The antibacterial microcapsules are evenly loaded on the wrapping paper, and the introduction of the antibacterial microcapsules can also extend the release time of the composite antibacterial agent on the wrapping paper. The pre-treated Chuanxiong is packaged with the cling paper containing microcapsules, which can not only achieve a long-term sustained-release antibacterial effect during long-term storage, but also after being packaged with the cling paper, a second electron beam irradiation treatment is carried out, which can protect Chuanxiong, reduce the impact of irradiation on the quality of Chuanxiong, and avoid Chuanxiong with a significant irradiation taste. At the same time, the second electron beam irradiation can further enhance the effect of irradiation preservation, thereby fully sterilizing Chuanxiong. This application is based on two electron beam irradiation treatments and combined with microcapsule-loaded wrapping paper, so that the sterilization is more thorough, and even during the storage process, the antibacterial components in the microcapsules can play a long-term sustained-release antibacterial effect, avoiding the reduction of the effective components of Chuanxiong during the storage period, thereby improving the antibacterial, antiseptic, and insect-proof effects on Chuanxiong, which is conducive to extending the storage period of Chuanxiong. BRIEF DESCRIPTION OF THE DRAWINGS

[0032] In order to more clearly illustrate the embodiments of the present application or the technical solutions in the prior art, the drawings required for use in the embodiments or the description of the prior art will be briefly introduced below. It is obvious that the drawings described below are only some embodiments of the present application. For ordinary technicians in this field, other drawings can be obtained based on the structures shown in these drawings without paying any creative work.

[0033] Figure 1 This is a process flow chart of the irradiation preservation of Chuanxiong described in the examples of this application.

[0034] The realization of the purpose, functional features and advantages of this application will be further explained in conjunction with embodiments and with reference to the accompanying drawings. DETAILED DESCRIPTION

[0035] The following will be combined with the drawings in the embodiments of the present application to clearly and completely describe the technical solutions in the embodiments of the present application. Obviously, the described embodiments are only part of the embodiments of the present application, not all of the embodiments. Based on the embodiments in the present application, all other embodiments obtained by ordinary technicians in this field without creative work are within the scope of protection of this application.

[0036] In view of the technical problems existing in the prior art, the embodiment of the present application provides a process for irradiation preservation of Chuanxiong, comprising the following steps:

[0037] After the chuanxiong is pretreated, the chuanxiong is subjected to a first electron beam irradiation treatment to obtain a pretreated chuanxiong;

[0038] In gC 3 N 4 In situ deposition of CuO and CaMoO on the surface 4 , preparation of CuO / CaMoO 4 / gC 3 N 4 Composite antibacterial agent; using porous chitosan as the wall material and the composite antibacterial agent as the core material, and adopting a microfluidic control process to prepare antibacterial microcapsules;

[0039] The antibacterial microcapsules are loaded on packaging paper to obtain fresh-keeping paper containing microcapsules;

[0040] The pre-treated Chuanxiong is packaged with modified atmosphere by the fresh-keeping paper containing microcapsules, and then subjected to a second electron beam irradiation treatment before being stored.

[0041] The present invention firstly performs electron beam irradiation treatment on Chuanxiong after pretreatment, and uses high-energy electron beam rays generated by an electron accelerator to irradiate Chuanxiong, so that a series of physical and chemical reactions occur on the microorganisms on its surface through the direct action of high-energy pulses, inhibiting the respiratory activity and enzyme activity of the microorganisms, thereby achieving a preliminary antibacterial effect; and gC 3 N 4 The superoxide free radicals generated under light excitation have strong redox properties and can oxidize the unsaturated phospholipid molecular layer in the bacterial cell membrane, causing cell leakage and ultimately killing bacteria. They have strong antibacterial properties, but gC 3 N 4 The antibacterial performance was poor under dark conditions. 3 N 4 In situ deposition of CuO and CaMoO on the surface 4 Finally, the composite antibacterial agent has a very high antibacterial rate regardless of light reaction or dark reaction; porous chitosan is used as the wall material and the composite antibacterial agent is used as the core material, and the large specific surface area and porosity of porous chitosan are utilized to make it have excellent carrier performance, which promotes its loading and embedding of the composite antibacterial agent; then the microfluidic control process is used to prepare the antibacterial microcapsules, and the composite antibacterial agent is embedded in the porous chitosan to form gel microspheres with complete capsule walls and good embedding structure; the particle size and morphology of the gel microspheres are precisely prepared through microfluidics, which is conducive to the stable preparation of the antibacterial microcapsules The antibacterial microcapsules are evenly loaded on the packaging paper, and the introduction of the antibacterial microcapsules can also prolong the release time of the composite antibacterial agent on the packaging paper. The pretreated Chuanxiong is packaged with the cling paper containing microcapsules, which can not only achieve a long-term sustained-release antibacterial effect during long-term storage, but also after being packaged with the cling paper, a second electron beam irradiation treatment is carried out, which can protect the Chuanxiong and reduce the impact of irradiation on the quality of Chuanxiong, avoiding the obvious irradiation taste of Chuanxiong. At the same time, the second electron beam irradiation can further enhance the effect of irradiation preservation, thereby fully sterilizing the Chuanxiong, which is beneficial to the long-term storage of Chuanxiong.

[0042] As an implementable method of the present application, the step of pretreating Chuanxiong comprises:

[0043] After washing and removing impurities, the rhizome of Chuanxiong is soaked in a preservative solution for 30-60 minutes, then taken out and dried at 40-50°C for 1-4 hours; wherein the preservative solution comprises cinnamaldehyde, eugenol and oligofructose.

[0044] Specifically, the mass fraction of cinnamaldehyde in the fresh-keeping liquid is 4%-6%, the mass fraction of eugenol is 3%-5%, the mass fraction of oligofructose is 6%-8%, and the balance is water.

[0045] Cinnamaldehyde is the main component of cinnamon essential oil, which has strong antibacterial properties and shows significant antibacterial activity against bacteria and molds. Eugenol is the active ingredient in cloves and can be used as an insecticide and preservative. It has strong antibacterial, anti-mildew and anti-insect activities and has inhibitory effects on pathogenic fungi. Oligofructose has strong free radical scavenging ability and antioxidant activity, and can effectively slow down the oxidation rate of Chuanxiong. After Chuanxiong is first soaked in the preservative solution, the discoloration caused by the enzymatic reaction and oxidation reaction of Chuanxiong itself can be slowed down, and it can play a certain antibacterial, anti-mildew and anti-insect role.

[0046] As an implementable method of the present application, in the step of performing the first electron beam irradiation treatment, the energy of the electron beam is 5MeV-6MeV, and the irradiation dose absorbed by Chuanxiong is controlled to be 0.6kGy-1kGy.

[0047] Specifically, the first electron beam irradiation treatment uses a 5MeV-6MeV electron beam, and the irradiation dose absorbed by Chuanxiong is controlled by the irradiation time. For example, when the energy of the electron beam is 5MeV and the irradiation dose absorbed by Chuanxiong is controlled to be 0.6kGy, irradiation is required for 80 minutes; when the energy of the electron beam is 6MeV and the irradiation dose absorbed by Chuanxiong is controlled to be 1kGy, irradiation is required for 180 minutes.

[0048] As an implementation method of the present application, the steps of preparing antibacterial microcapsules using porous chitosan as the wall material and the composite antibacterial agent as the core material by adopting a microfluidic control process include:

[0049] preparing porous chitosan wall materials;

[0050] Adding sodium carboxymethyl cellulose to the porous chitosan wall material and mixing to obtain a mixture; then mixing the composite antibacterial agent with water and ball milling for 20 hours to 28 hours, and then adding the composite antibacterial agent to the mixture to obtain a dispersed phase;

[0051] After mixing dimethyl silicone oil with carbon tetrachloride, a continuous phase is obtained;

[0052] The dispersed phase and the continuous phase are placed in a microfluidic control device to form droplets, which are then solidified into gel microspheres in a 68-72° C. coagulation bath. After suction filtration, washing and drying, antibacterial microcapsules are obtained.

[0053] Among them, the mass ratio of porous chitosan wall material to sodium carboxymethyl cellulose is (1-2):1; the mass ratio of dimethyl silicone oil to carbon tetrachloride is (3-4):1; the mass ratio of the composite antibacterial agent, porous chitosan wall material, and sodium carboxymethyl cellulose in the dispersed phase is 5:4:(1-2).

[0054] Specifically, the porous wall material based on chitosan can significantly increase the specific surface area and porosity of the material, expose more active group binding sites, and have a higher loading capacity and embedding rate. In order to increase the loading capacity and embedding rate of the porous chitosan wall material for the composite antibacterial agent, the present application uses porous chitosan as the wall material, and adds sodium carboxymethyl cellulose for cross-linking, disperses the composite antibacterial agent in the gel system, and prepares a dispersed phase. When the composite antibacterial agent-porous chitosan-sodium carboxymethyl cellulose as the dispersed phase flows into the continuous phase in the microfluidic control device, at the outflow end Under the action of surface tension and viscosity of the continuous phase, droplets with controllable particle size are formed and flow into the coagulation bath along with the continuous phase. The porous chitosan and sodium carboxymethyl cellulose inside the droplets are cross-linked to form a gel system, realizing the transition from an amorphous liquid to a semi-solid state with a certain shape, and the composite antibacterial agent is embedded inside. After solidification, gel microspheres with complete capsule walls and good embedding structure are formed. The microfluidic-controlled liquid droplet solidification method can accurately realize the controllable preparation of the particle size and morphology of the gel microspheres, which is conducive to the stable and uniform loading of the antibacterial microcapsules on the packaging paper.

[0055] As an implementable method of the present application, the step of preparing the porous chitosan wall material comprises:

[0056] The γ-polyglutamic acid solution and Tween-20 are stirred and mixed at room temperature, and a porogen is added to obtain a mixed solution;

[0057] Acetic acid is added to the chitosan solution and then dripped into the mixed solution. After the reaction, the mixture is centrifuged and hydrochloric acid solution is added to allow the gas to escape. Then, concentrated ammonia water is added and adjusted to a pH of 7. The mixture is washed with deionized water and ethanol in turn and dried at room temperature to a constant weight to obtain the porous chitosan wall material.

[0058] Specifically, the porogen is K 2 CO 3 , K 2 CO 3 The mass fraction in the mixed solution is 6%; γ-polyglutamic acid and Tween-20 are mixed in a ratio of 1g:10mL.

[0059] The present invention adopts the gas porogen method, and adds a porogen K capable of generating gas into the reaction system. 2 CO 3 , which generates CO after encountering acid in the reaction system 2 Gas, which in turn forms a porous channel structure on the surface of chitosan, and then K is removed by adding concentrated ammonia to adjust the pH and washing. 2 CO 3After that, a porous chitosan wall material with a porous surface and relatively uniform pore size can be obtained, thereby significantly improving the specific surface area and porosity of chitosan, making it have excellent carrier properties, promoting the loading and embedding of the composite antibacterial agent by the porous chitosan, and facilitating the slow release of the composite antibacterial agent by the antibacterial microcapsule during long-term storage, thereby improving the antibacterial effect.

[0060] As an implementation method of the present application, the 3 N 4 In situ deposition of CuO and CaMoO on the surface 4 , preparation of CuO / CaMoO 4 / gC 3 N 4 The steps of compounding the antimicrobial agent include:

[0061] After grinding and mixing thiourea and urea, the temperature was raised to 540-560°C at a rate of 2°C / min under a nitrogen atmosphere, kept constant for 3h-5h, and then naturally cooled to room temperature. After grinding, gC 3 N 4 ;

[0062] The gC 3 N 4 and CaMoO 4 ,CuSO 4 Add them together into the reaction kettle, then add sodium borohydride solution, stir, and perform hydrothermal reaction at 180℃-200℃ for 20h-26h. After the reaction, cool to room temperature, collect the product after centrifugation, wash with anhydrous ethanol, and vacuum dry at 75℃-85℃ for 5h-7h to obtain CuO / CaMoO 4 / gC 3 N 4 Composite antimicrobial agent.

[0063] In this application, urea and thiourea were used as precursors to synthesize S-doped gC 3 N 4 , to improve gC 3 N 4 The specific surface area of ​​CuO and CaMoO 4 In gC 3 N 4 In-situ deposition on the surface, and then on gC 3 N 4 Surface deposition of CuO and CaMoO 4 , thus obtaining CuO / CaMoO 4 / gC 3 N 4 Composite antibacterial agent. 3 N 4It has good antibacterial performance under light conditions, but poor antibacterial performance under dark conditions. 3 N 4 Surface deposition of CuO and CaMoO 4 After that, in the dark reaction, the organic components of the bacteria can directly react with CuO / CaMoO 4 A cavitation reaction occurs, leading to cell apoptosis; in the light reaction, gC 3 N 4 It can produce superoxide free radicals, has strong redox properties, can oxidize the unsaturated phospholipid molecular layer in the cell membrane, causing cell leakage, and ultimately kill bacteria, thus having a very high antibacterial rate under both light and dark reactions.

[0064] As an implementation method of the present application, the step of loading the antibacterial microcapsules on packaging paper to obtain a fresh-keeping paper containing microcapsules includes:

[0065] Soak the wrapping paper in the m-phenylenediamine solution for 3-8 minutes;

[0066] The antibacterial microcapsules are ultrasonically dispersed in an ethanol solution, the ultrasonic frequency is 50 MHz-180 MHz, the ultrasonic time is 10 min-25 min, and then 1,3,5-triphenylethylene trimesoyl chloride is added, stirred and mixed, and then the soaked wrapping paper is added, and stirred at a speed of 100 r / min-140 r / min for 5 min-10 min, and then the wrapping paper is taken out and dried at 60° C.-70° C. for 1 h-4 h to obtain a cling paper containing microcapsules.

[0067] The mass ratio of the antibacterial microcapsules to 1,3,5-trimethylbenzenecarboxylic acid chloride is 1:(5-6).

[0068] Specifically, the present application adopts the interfacial polymerization method to load the antibacterial microcapsules on the packaging paper, and the antibacterial microcapsules are combined with the paper-based material to prepare the fresh-keeping paper with sustained-release antibacterial effect. After using it to package Chuanxiong, it is subjected to a second electron beam irradiation treatment. It can not only protect Chuanxiong, reduce the impact of irradiation on the quality of Chuanxiong, and avoid Chuanxiong with a distinct irradiation taste, but also further enhance the effect of irradiation preservation and make the sterilization more thorough. At the same time, the introduction of microcapsules can also prolong the release time of the antibacterial ingredients on the packaging paper, achieve a long-acting sustained-release antibacterial effect, and improve the antibacterial and preservative effect on Chuanxiong during long-term storage.

[0069] As an implementation method of the present application, the step of performing modified atmosphere packaging on the pretreated Chuanxiong by using the cling paper containing microcapsules comprises:

[0070] The preservative paper containing the microcapsules is used as a packaging bag to package the pretreated Chuanxiong, and a mixed gas consisting of oxygen and carbon dioxide is filled into the bag; wherein the volume ratio of the mixed gas is O 2 ∶CO 2 It is 8%-10%.

[0071] The present invention creates an environment that is unfavorable for the growth and reproduction of microorganisms and pests by controlling the content ratio of oxygen and carbon dioxide, thereby extending the storage period of Chuanxiong and reducing the loss of its active ingredients.

[0072] As an implementable method of the present application, in the step of performing the second electron beam irradiation treatment, the energy of the electron beam is 7MeV-10MeV, and the irradiation dose absorbed by Chuanxiong is controlled to be 3.5kGy-4.5kGy.

[0073] Specifically, the second electron beam irradiation treatment uses a 7MeV-10MeV electron beam, and the irradiation dose absorbed by Chuanxiong is controlled by the irradiation time. For example, when the energy of the electron beam is 9MeV and the irradiation dose absorbed by Chuanxiong is controlled to be 4.0kGy, irradiation is required for 480min; when the energy of the electron beam is 7MeV and the irradiation dose absorbed by Chuanxiong is controlled to be 3.5kGy, irradiation is required for 330min.

[0074] As an implementable method of the present application, the step of storing includes:

[0075] The chuanxiong treated by the second electron beam irradiation is stored in an environment with a temperature of 5-25° C. and a relative humidity of 35%-60%.

[0076] By storing the chuanxiong after two electron beam irradiation treatments in an environment with a temperature of 5°C-25°C and a relative humidity of 35%-60%, it is more conducive to the long-term preservation of the chuanxiong without causing deterioration.

[0077] The above technical solution of the present application is described in detail below in conjunction with specific embodiments.

[0078] Example 1

[0079] A process for irradiation preservation of chuanxiong comprises the following steps:

[0080] After washing and removing impurities, the Chuanxiong was soaked in a preservative solution for 45 minutes, taken out and dried at 45°C for 2.5 hours, and then subjected to the first electron beam irradiation treatment. The energy of the electron beam was 6MeV, and the irradiation dose absorbed by the Chuanxiong was controlled to be 0.8kGy. The first electron beam irradiation treatment time was 130 minutes, thereby obtaining the pretreated Chuanxiong.

[0081] Wherein, in the fresh-keeping liquid, the mass fraction of cinnamaldehyde is 5%, the mass fraction of eugenol is 4%, the mass fraction of oligofructose is 7%, and the balance is water;

[0082] 300 mL of 0.01 g / mL γ-polyglutamic acid solution and 30 mL of Tween-20 were stirred and mixed at room temperature, and the pore-forming agent K was added. 2 CO 3 , and obtain a mixed solution, K 2 CO 3 The mass fraction in the mixed liquid is 6%;

[0083] 300 mL of a 0.01 g / mL chitosan solution containing 1% acetic acid was added dropwise to the mixed solution, and after the reaction, the mixture was centrifuged and separated. 80 mL of a 1 mol / L hydrochloric acid solution was added to allow the gas to fully escape, and concentrated ammonia was added and adjusted to a pH of 7. The mixture was then washed with deionized water and ethanol in sequence, and dried at room temperature to a constant weight to obtain a porous chitosan wall material.

[0084] 10 g of thiourea and 5 g of urea were ground and mixed, and then heated to 550 °C at a rate of 2 °C / min under a nitrogen atmosphere, kept at this temperature for 4 h, and then naturally cooled to room temperature. After grinding, gC 3 N 4 ;

[0085] 3g of gC 3 N 4 and 2 g CaMoO 4 , 0.2 g CuSO 4 Add them together into the reactor, then add 1 mol / L sodium borohydride solution, stir, and perform hydrothermal reaction at 190°C for 23h. After the reaction, cool to room temperature, collect the product after centrifugation, wash with anhydrous ethanol, and vacuum dry at 80°C for 6h to obtain CuO / CaMoO 4 / gC 3 N 4 Composite antimicrobial agents;

[0086] Adding sodium carboxymethyl cellulose to the porous chitosan wall material and mixing to obtain a mixture, wherein the mass ratio of the porous chitosan wall material to the sodium carboxymethyl cellulose in the mixture is 1.5:1; then mixing the composite antibacterial agent with water and ball milling for 24 hours, and then adding the composite antibacterial agent to the mixture to obtain a dispersed phase; in the dispersed phase, the mass ratio of the composite antibacterial agent, the porous chitosan wall material, and the sodium carboxymethyl cellulose is 5:4:1.5;

[0087] Dimethyl silicone oil and carbon tetrachloride were mixed in a mass ratio of 3.5:1 to obtain a continuous phase;

[0088] The dispersed phase and the continuous phase are placed in a microfluidic control device respectively, and after shearing to form droplets, they are solidified into gel microspheres in a 70° C. coagulation bath, and the crude product is filtered, washed with isoamyl alcohol, extracted with Soxhlet for 12 hours, and then vacuum dried at 50° C. for 24 hours to obtain antibacterial microcapsules;

[0089] Soak the wrapping paper in a 20g / L m-phenylenediamine solution for 5 minutes;

[0090] 0.5 g of antibacterial microcapsules were ultrasonically dispersed in an ethanol solution at an ultrasonic frequency of 120 MHz for 17 min, and 3 g of 1,3,5-triphenylamine chloride was added. After stirring and mixing, the soaked wrapping paper was added and stirred at a speed of 120 r / min for 7 min. The wrapping paper was taken out and dried at 65°C for 2.5 h to obtain a cling paper containing microcapsules.

[0091] The preservative paper containing the microcapsules is used as a packaging bag to package the pretreated Chuanxiong, and a mixed gas consisting of oxygen and carbon dioxide is filled into the bag. 2 :CO 2 The energy of the electron beam is 9MeV, and the radiation dose absorbed by Chuanxiong is controlled to be 4.0kGy. The time of the second electron beam irradiation treatment is 480min. Chuanxiong is then stored in an environment with a temperature of 15°C and a relative humidity of 47%, thus completing the preservation of Chuanxiong.

[0092] Example 2

[0093] A process for irradiation preservation of chuanxiong comprises the following steps:

[0094] After washing and removing impurities, the Chuanxiong was soaked in a preservative solution for 30 minutes, taken out and dried at 40°C for 4 hours, and then subjected to the first electron beam irradiation treatment. The energy of the electron beam was 5MeV, and the irradiation dose absorbed by the Chuanxiong was controlled to be 0.6kGy. The first electron beam irradiation treatment time was 80 minutes, thereby obtaining the pretreated Chuanxiong.

[0095] Wherein, in the fresh-keeping liquid, the mass fraction of cinnamaldehyde is 4%, the mass fraction of eugenol is 3%, the mass fraction of oligofructose is 6%, and the balance is water;

[0096] 300 mL of 0.01 g / mL γ-polyglutamic acid solution and 30 mL of Tween-20 were stirred and mixed at room temperature, and the pore-forming agent K was added. 2 CO 3 , and obtain a mixed solution, K 2 CO 3 The mass fraction in the mixed liquid is 6%;

[0097] 300 mL of a 0.01 g / mL chitosan solution containing 1% acetic acid was added dropwise to the mixed solution, and after the reaction, the mixture was centrifuged and separated. 80 mL of a 1 mol / L hydrochloric acid solution was added to allow the gas to fully escape, and concentrated ammonia was added and adjusted to a pH of 7. The mixture was then washed with deionized water and ethanol in sequence, and dried at room temperature to a constant weight to obtain a porous chitosan wall material.

[0098] 10 g of thiourea and 5 g of urea were ground and mixed, and then heated to 540 °C at a rate of 2 °C / min under a nitrogen atmosphere, kept at this temperature for 5 h, and then naturally cooled to room temperature. After grinding, gC 3 N 4 ;

[0099] 3g of gC 3 N 4 and 2 g CaMoO 4 , 0.2 g CuSO 4 Add them together into the reactor, then add 1 mol / L sodium borohydride solution, stir, and perform hydrothermal reaction at 180°C for 26 hours. After the reaction, cool to room temperature, collect the product after centrifugation, wash with anhydrous ethanol, and vacuum dry at 75°C for 7 hours to obtain CuO / CaMoO 4 / gC 3 N 4 Composite antimicrobial agents;

[0100] Adding sodium carboxymethyl cellulose to the porous chitosan wall material and mixing, wherein the mass ratio of the porous chitosan wall material to the sodium carboxymethyl cellulose in the mixture is 1:1, to obtain a mixture; then mixing the composite antibacterial agent with water and ball milling for 20 hours, and then adding the composite antibacterial agent to the mixture to obtain a dispersed phase; in the dispersed phase, the mass ratio of the composite antibacterial agent, the porous chitosan wall material, and the sodium carboxymethyl cellulose is 5:4:1;

[0101] Dimethyl silicone oil and carbon tetrachloride were mixed in a mass ratio of 3:1 to obtain a continuous phase;

[0102] The dispersed phase and the continuous phase are placed in a microfluidic control device respectively, and after shearing to form droplets, they are solidified into gel microspheres in a 68° C. coagulation bath, and the crude product is filtered, washed with isoamyl alcohol, extracted with Soxhlet for 12 h, and then vacuum dried at 50° C. for 24 h to obtain antibacterial microcapsules;

[0103] Soak the wrapping paper in a 20g / L m-phenylenediamine solution for 3 minutes;

[0104] 0.5 g of antibacterial microcapsules were ultrasonically dispersed in an ethanol solution at an ultrasonic frequency of 50 MHz for 25 min, and 3 g of 1,3,5-triphenylamine chloride was added. After stirring and mixing, the soaked wrapping paper was added and stirred at a speed of 100 r / min for 10 min. The wrapping paper was taken out and dried at 60°C for 4 h to obtain a cling paper containing microcapsules.

[0105] The preservative paper containing the microcapsules is used as a packaging bag to package the pretreated Chuanxiong, and a mixed gas consisting of oxygen and carbon dioxide is filled into the bag. 2 :CO 2 The energy of the electron beam is 7MeV, and the radiation dose absorbed by Chuanxiong is controlled to be 3.5kGy. The time of the second electron beam irradiation treatment is 330min. Chuanxiong is then stored in an environment with a temperature of 15°C and a relative humidity of 47%, thus completing the preservation of Chuanxiong.

[0106] Example 3

[0107] A process for irradiation preservation of chuanxiong comprises the following steps:

[0108] After washing and removing impurities, the Chuanxiong was soaked in a preservative solution for 60 minutes, taken out and dried at 50°C for 1 hour, and then subjected to the first electron beam irradiation treatment, the energy of the electron beam was 6MeV, the irradiation dose absorbed by the Chuanxiong was controlled to be 1kGy, and the first electron beam irradiation treatment time was 180 minutes, thereby obtaining the pretreated Chuanxiong;

[0109] Wherein, in the fresh-keeping liquid, the mass fraction of cinnamaldehyde is 6%, the mass fraction of eugenol is 5%, the mass fraction of oligofructose is 8%, and the balance is water;

[0110] 300 mL of 0.01 g / mL γ-polyglutamic acid solution and 30 mL of Tween-20 were stirred and mixed at room temperature, and the pore-forming agent K was added. 2 CO 3 , and obtain a mixed solution, K 2 CO 3 The mass fraction in the mixed liquid is 6%;

[0111] 300 mL of a 0.01 g / mL chitosan solution containing 1% acetic acid was added dropwise to the mixed solution, and after the reaction, the mixture was centrifuged and separated. 80 mL of a 1 mol / L hydrochloric acid solution was added to allow the gas to fully escape, and concentrated ammonia was added and adjusted to a pH of 7. The mixture was then washed with deionized water and ethanol in sequence, and dried at room temperature to a constant weight to obtain a porous chitosan wall material.

[0112] 10 g of thiourea and 5 g of urea were ground and mixed, and then heated to 560 °C at a rate of 2 °C / min under a nitrogen atmosphere, kept at this temperature for 3 h, and then naturally cooled to room temperature. After grinding, gC 3 N 4 ;

[0113] 3g of gC 3 N 4 and 2 g CaMoO 4 , 0.2 g CuSO 4 Add them together into the reactor, then add 1 mol / L sodium borohydride solution, stir, and perform hydrothermal reaction at 200°C for 20 hours. After the reaction is completed, cool to room temperature, collect the product after centrifugation, wash with anhydrous ethanol, and vacuum dry at 85°C for 5 hours to obtain CuO / CaMoO 4 / gC 3 N 4 Composite antimicrobial agents;

[0114] Adding sodium carboxymethyl cellulose to the porous chitosan wall material and mixing, wherein the mass ratio of the porous chitosan wall material to the sodium carboxymethyl cellulose in the mixture is 2:1, to obtain a mixture; then mixing the composite antibacterial agent with water and ball milling for 28 hours, and then adding the composite antibacterial agent to the mixture to obtain a dispersed phase; in the dispersed phase, the mass ratio of the composite antibacterial agent, the porous chitosan wall material, and the sodium carboxymethyl cellulose is 5:4:2;

[0115] Dimethyl silicone oil and carbon tetrachloride were mixed in a mass ratio of 4:1 to obtain a continuous phase;

[0116] The dispersed phase and the continuous phase are placed in a microfluidic control device respectively, and after shearing to form droplets, they are solidified into gel microspheres in a 72° C. coagulation bath, and the crude product is filtered, washed with isoamyl alcohol, extracted with Soxhlet for 12 h, and then vacuum dried at 50° C. for 24 h to obtain antibacterial microcapsules;

[0117] Soak the wrapping paper in a 20g / L m-phenylenediamine solution for 8 minutes;

[0118] 0.5 g of antibacterial microcapsules were ultrasonically dispersed in an ethanol solution at an ultrasonic frequency of 180 MHz for 10 min, and then 3 g of 1,3,5-triphenylamine chloride was added. After stirring and mixing, the soaked wrapping paper was added and stirred at a speed of 140 r / min for 5 min. The wrapping paper was taken out and dried at 70°C for 1 h to obtain a cling paper containing microcapsules.

[0119] The preservative paper containing the microcapsules is used as a packaging bag to package the pretreated Chuanxiong, and a mixed gas consisting of oxygen and carbon dioxide is filled into the bag. 2 :CO 2The energy of the electron beam is 10MeV, and the radiation dose absorbed by Chuanxiong is controlled to be 4.5kGy. The time of the second electron beam irradiation treatment is 600min. Chuanxiong is then stored in an environment with a temperature of 15°C and a relative humidity of 47%, thus completing the preservation of Chuanxiong.

[0120] Comparative Example 1

[0121] Compared with Example 1, the first electron beam irradiation treatment was not performed, and the remaining steps were the same.

[0122] Comparative Example 2

[0123] Compared with Example 1, the composite antibacterial agent is replaced by a silver ion antibacterial agent, and the remaining steps are the same.

[0124] Comparative Example 3

[0125] Compared with Example 1, in the step of preparing the composite antibacterial agent, gC 3 N 4 In situ deposition of CuO and CaMoO on the surface 4 , the rest of the steps are the same.

[0126] Experimental example

[0127] After the fresh-keeping processes of the examples and comparative examples of the present application were used to preserve and store Chuanxiong for 90 days, the hardness and main active ingredient (ferulic acid) of the Chuanxiong were tested, and the physical and chemical indicators were tested.

[0128] Among them, the hardness was measured by a texture analyzer on the equatorial part of Chuanxiong, and the ferulic acid content was determined by high performance liquid chromatography (General Rules 0512 of Part IV of the 2020 Edition of the Chinese Pharmacopoeia). The results are shown in Table 1 below.

[0129] The physical and chemical indexes were tested according to the methods specified in the 2020 edition of the "Chinese Pharmacopoeia", and moisture, ash and volatile oil were tested. The test results are shown in Table 2 below.

[0130] Table 1

[0131]

[0132] Table 2

[0133]

[0134] As can be seen from Tables 1 and 2, after the preservation process of the present application was used to preserve the Chuanxiong for 90 days, there was no obvious deterioration phenomenon, the moisture, total ash and volatile oil content met the content standard requirements for Chuanxiong in the "Chinese Pharmacopoeia", the ferulic acid content did not decrease significantly, and the texture was relatively hard, while in Comparative Example 1, the first electron beam irradiation treatment was not performed, which reduced the preservation effect of Chuanxiong, and the hardness and ferulic acid content of Chuanxiong were both lower than those in Example 1, which was not conducive to the long-term storage of Chuanxiong; the antibacterial component in the antibacterial microcapsule in Comparative Example 2 was a silver ion antibacterial agent, and its antibacterial effect was reduced compared with the composite antibacterial agent of the present application, causing the volatile oil compounds in Chuanxiong to volatilize and easily mildew; the antibacterial component in Comparative Example 3 was only gC 3 N 4 , does not contain CuO and CaMoO 4 , resulting in a decrease in the antibacterial properties of the antibacterial agent, a significant decrease in the hardness and ferulic acid content of Chuanxiong, and the volatilization of volatile oil compounds, indicating the occurrence of deterioration phenomena such as mildew and oil loss, which is not conducive to the long-term storage of Chuanxiong.

[0135] The above description is only an optional embodiment of the present application, and does not limit the patent scope of the present application. All equivalent structural transformations made by using the contents of the present application specification and drawings under the inventive concept of the present application, or directly / indirectly applied in other related technical fields are included in the patent protection scope of the present application.

Claims

1. A process for irradiation preservation of Chuanxiong, characterized in that: The following steps are involved: After the chuanxiong is pretreated, the chuanxiong is subjected to a first electron beam irradiation treatment to obtain pretreated chuanxiong; In situ depositing CuO and CaMoO4 on the surface of g-C3N4 to prepare a CuO / CaMoO4 / g-C3N4 composite antibacterial agent; using porous chitosan as a wall material and the composite antibacterial agent as a core material, and adopting a microfluidic control process to prepare antibacterial microcapsules; The antibacterial microcapsules are loaded on packaging paper to obtain fresh-keeping paper containing microcapsules; The pre-treated Chuanxiong is packaged with modified atmosphere by the fresh-keeping paper containing microcapsules, and then subjected to a second electron beam irradiation treatment before being stored.

2. The process for irradiation preservation of Chuanxiong according to claim 1, characterized in that: The step of pre-treating Chuanxiong comprises: After washing and removing impurities, the rhizome of Chuanxiong is soaked in a preservative solution for 30-60 minutes, then taken out and dried at 40-50°C for 1-4 hours; wherein the preservative solution comprises cinnamaldehyde, eugenol and oligofructose.

3. The process for irradiation preservation of Chuanxiong according to claim 1, characterized in that: In the step of performing the first electron beam irradiation treatment, the energy of the electron beam is 5MeV-6MeV, and the irradiation dose absorbed by Chuanxiong is controlled to be 0.6kGy-1kGy.

4. The process for irradiation preservation of Chuanxiong according to claim 1, characterized in that: The step of preparing the antibacterial microcapsules by using porous chitosan as the wall material and the composite antibacterial agent as the core material and adopting a microfluidic control process comprises: preparing porous chitosan wall materials; Adding sodium carboxymethyl cellulose to the porous chitosan wall material and mixing to obtain a mixture; then mixing the composite antibacterial agent with water and ball milling for 20 hours to 28 hours, and then adding the composite antibacterial agent to the mixture to obtain a dispersed phase; After mixing dimethyl silicone oil with carbon tetrachloride, a continuous phase is obtained; The dispersed phase and the continuous phase are placed in a microfluidic control device to form droplets, which are then solidified into gel microspheres in a 68-72° C. coagulation bath. After suction filtration, washing and drying, antibacterial microcapsules are obtained.

5. The process for irradiation preservation of Chuanxiong according to claim 4, characterized in that: The step of preparing the porous chitosan wall material comprises: The γ-polyglutamic acid solution and Tween-20 are stirred and mixed at room temperature, and a porogen is added to obtain a mixed solution; Acetic acid is added to the chitosan solution and then dripped into the mixed solution. After the reaction, the mixture is centrifuged and hydrochloric acid solution is added to allow the gas to escape. Then, concentrated ammonia water is added and adjusted to a pH of 7. The mixture is washed with deionized water and ethanol in turn and dried at room temperature to a constant weight to obtain the porous chitosan wall material.

6. The process for irradiation preservation of Chuanxiong according to claim 1, characterized in that: The step of in-situ depositing CuO and CaMoO4 on the surface of g-C3N4 to prepare the CuO / CaMoO4 / g-C3N4 composite antibacterial agent comprises: After grinding and mixing thiourea and urea, the temperature was raised to 540-560°C at a rate of 2°C / min under a nitrogen atmosphere, kept constant for 3h-5h, and then naturally cooled to room temperature. After grinding, g-C3N4 was obtained; The g-C3N4, CaMoO4 and CuSO4 are added into a reaction kettle together, and then sodium borohydride solution is added. After stirring, a hydrothermal reaction is carried out at 180°C-200°C for 20h-26h. After the reaction is completed, it is cooled to room temperature, and the product is collected after centrifugation. After washing with anhydrous ethanol, it is vacuum dried at 75°C-85°C for 5h-7h to obtain a CuO / CaMoO4 / g-C3N4 composite antibacterial agent.

7. The process for irradiation preservation of Chuanxiong according to claim 1, characterized in that: The step of loading the antibacterial microcapsules on packaging paper to obtain fresh-keeping paper containing microcapsules comprises: Soak the wrapping paper in the m-phenylenediamine solution for 3-8 minutes; The antibacterial microcapsules are ultrasonically dispersed in an ethanol solution, the ultrasonic frequency is 50 MHz-180 MHz, the ultrasonic time is 10 min-25 min, and then 1,3,5-triphenylethylene trimesoyl chloride is added, stirred and mixed, and then the soaked wrapping paper is added, and stirred at a speed of 100 r / min-140 r / min for 5 min-10 min, and then the wrapping paper is taken out and dried at 60° C.-70° C. for 1 h-4 h to obtain a cling paper containing microcapsules.

8. The process for irradiation preservation of Chuanxiong according to claim 1, characterized in that: The step of performing modified atmosphere packaging on the pretreated Chuanxiong by using the fresh-keeping paper containing microcapsules comprises: The preservative paper containing microcapsules is used as a packaging bag to package the pretreated Chuanxiong, and a mixed gas consisting of oxygen and carbon dioxide is filled into the bag; wherein the volume ratio of the mixed gas is 8%-10% of O2:CO2.

9. The process for irradiation preservation of Chuanxiong according to claim 1, characterized in that: In the step of performing the second electron beam irradiation treatment, the energy of the electron beam is 7MeV-10MeV, and the irradiation dose absorbed by Chuanxiong is controlled to be 3.5kGy-4.5kGy.

10. The process for irradiation preservation of Chuanxiong according to claim 1, characterized in that: The step of storing comprises: The chuanxiong treated by the second electron beam irradiation is stored in an environment with a temperature of 5-25° C. and a relative humidity of 35%-60%.

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