CN113680289B - Nano-cellulose-phenol type antioxidant gel and stable Pickering high internal phase emulsion thereof - Google Patents
Nano-cellulose-phenol type antioxidant gel and stable Pickering high internal phase emulsion thereof Download PDFInfo
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Abstract
The invention relates to a nanocellulose-phenol type antioxidant gel and stable Pickering high internal phase emulsion thereof, belonging to the technical field of Pickering emulsion. The invention provides a method for preparing a nano-cellulose-phenol type antioxidant gel system, which is to mix a micro-cellulose suspension and a plant polyphenol water solution and construct the nano-cellulose-phenol type antioxidant gel system by ultrasonic treatment. The emulsion disclosed by the invention is simple to prepare, and the high internal phase Pickering emulsion with excellent physical stability and oxidation stability can be prepared under the condition of less polyphenol adding amount (0.05%).
Description
Technical Field
The invention relates to a nanocellulose-phenol type antioxidant gel and a stable Pickering high internal phase emulsion thereof, belonging to the technical field of Pickering emulsions.
Background
Pickering emulsion is an emulsion stabilized with solid particles. Due to the irreversible adsorption properties of solid particles, pickering emulsions exhibit better physical stability than conventional emulsions, which are widely used for embedding, delivering active substances and drugs, improving the quality of food and cosmetics, etc. The emulsion consists of a water phase and an oil phase, and the oil phase is very easy to oxidize in the storage process, so that the sensory quality and the nutritional quality of the product are seriously influenced. The Pickering high internal phase emulsion refers to Pickering emulsion with volume fraction of dispersed phase (oil phase) being more than 74%. The problem of grease oxidation is more severe for high internal phase emulsions and is an urgent problem to be solved. Many studies have shown that the oil-water interface of emulsions is the starting point and diffusion point for lipid oxidation. If the oxidation of the grease at the interface can be effectively prevented, the oxidation stability of the emulsion can be significantly improved. The polyphenol is a natural antioxidant, and can effectively slow down the oxidation of grease in the emulsion. But the polyphenols distributed at the interface of the two phases exhibit superior grease-protecting ability compared to the polyphenols distributed in the aqueous or oil phase. Therefore, how to effectively anchor the antioxidant at the interface of two phases and increase the concentration of the antioxidant at the interface has important and practical significance for relieving the grease oxidation of Pickering emulsion (especially high internal phase emulsion) and prolonging the shelf life of commodities.
The Chinese invention patent CN111534110A discloses an alcohol soluble protein-phenol antioxidant nanoparticle and a Pickering emulsion prepared from the same, and the alcohol soluble protein-phenol composite nanoparticle is prepared by an anti-solvent precipitation method; chinese patent No. CN111838396A discloses a preparation process of polyphenol-soybean protein particle self-assembly Pickering emulsion, and tea polyphenol soybean protein microsphere particles mediated by thermal aggregation are obtained; chinese patent CN110583972A discloses a gelatin-waxberry leaf proanthocyanidin complex, which can be used for preparing pickering emulsion. These patents are based on the interaction of proteins and polyphenols to form nanoparticles, eventually anchoring the polyphenols to the two-phase interface. Unlike proteins, cellulose particles are relatively stable and do not readily interact with phenols. Although the SCI article [ Food Research International 112 (2018) 225-232] reports that cellulose particles have a certain adsorption capacity for catechins, the adsorption capacity is limited and the maximum adsorption amount is only 2.82mg/g. Therefore, for cellulose, a method of forming nanoparticles by an interaction similar to that of proteins and polyphenols is not suitable.
Disclosure of Invention
[ problem ] to provide a method for producing a semiconductor device
The oil oxidation stability of the high internal phase Pickering emulsion is an important problem to be solved, and the invention aims to provide a nano cellulose-phenol type antioxidant gel system and a high internal phase Pickering emulsion which is prepared based on the gel and has particularly excellent physical stability and oxidation stability.
[ technical solution ] A
The technical conception of the invention is as follows: cellulose micro-particles and plant polyphenol are used as raw materials, and a nano-cellulose-phenol type antioxidant gel system is formed through ultrasonic induction. Based on the adsorption of polyphenols by cellulose and the gel properties of the cellulose gel, the cellulose gel 'fixes' the polyphenols in a network structure. In the process of stabilizing the emulsion, the nanocellulose is adsorbed on an oil-water interface to form an interface layer, and meanwhile, the polyphenol is anchored on the oil-water interface, so that the concentration of the antioxidant near the oil-water interface is increased. The emulsion disclosed by the invention is simple to prepare, and the high internal phase Pickering emulsion with excellent physical stability and oxidation stability can be prepared under the condition of less polyphenol adding amount (0.05%).
The technical scheme of the invention is as follows:
the first purpose of the invention is to provide a method for preparing a nano-cellulose-phenol type antioxidant gel system, which takes micro-cellulose suspension and polyphenol as raw materials, and induces a mixed system of the micro-cellulose suspension and plant polyphenol water solution to form the nano-cellulose-phenol type antioxidant gel system through ultrasonic treatment.
In one embodiment of the invention, the plant polyphenol comprises one or more of tea polyphenol, gallic acid, catechin, tannic acid, epigallocatechin gallate, caffeic acid, and ferulic acid.
In one embodiment of the present invention, the method for preparing the micro-cellulose suspension may refer to a cellulose purification method disclosed in chinese patent No. CN 110591117B. The method comprises the following specific steps: plant cellulose powder is used as a raw material (such as crushed ginkgo shells) and is subjected to purification by 4 percent of sodium hydroxide and 1.5 percent of sodium chlorite solution, and then sulfuric acid with the concentration of 62 to 64 percent is adopted for hydrolysis for 30 to 90min in a water bath environment at the temperature of 45 ℃. After the hydrolysis was completed, the reaction was terminated with 10 times deionized water, followed by centrifugation to remove the supernatant and collecting the precipitate. And dispersing the precipitate in deionized water again, and performing dialysis treatment by using an 8-14 kDa dialysis bag to remove redundant inorganic salt ions to finally obtain the 1-5% micron cellulose suspension with the pH = 5-7.
In one embodiment of the invention, the microcrystalline cellulose suspension is a suspension of cellulose microcrystals of ginkgo biloba shells.
In one embodiment of the invention, in a mixed system obtained by mixing a micro-cellulose suspension and a plant polyphenol aqueous solution, the concentration of the micro-cellulose suspension is 0.8-2%; the concentration of the polyphenol solution is 0.05-0.5%.
In one embodiment of the present invention, the ultrasonic treatment conditions are: the ultrasonic power is 150-600W, the ultrasonic time is 10-90 min, and the ultrasonic frequency is 20kHz.
In one embodiment of the invention, the ultrasonic treatment is by intermittent ultrasound: the ultrasonic duration is 1-5 s, and the ultrasonic intermittent time is 1-5 s; in the whole ultrasonic process, the temperature of the mixed system is not more than 30 ℃.
The second purpose of the invention is to provide a nano-cellulose-phenol type antioxidant gel system prepared by the method.
The third purpose of the invention is to provide the application of the nano-cellulose-phenolic antioxidant gel system in preparing emulsion or delivering drugs for diagnosis and treatment of non-diseases.
The fourth purpose of the invention is to provide a Pickering high internal phase emulsion with excellent physical stability and grease oxidation stability, wherein the Pickering emulsion is formed by mixing a water phase and an oil phase; wherein the water phase at least comprises the nano-cellulose-phenol type antioxidant gel system.
In one embodiment of the present invention, the Pickering emulsion is a Pickering emulsion formed by mixing the nanocellulose-phenol gel system as an aqueous phase with an oil phase and shearing.
In one embodiment of the invention, the aqueous phase further comprises water, wherein the amount of the nano-cellulose-phenol antioxidant gel system added is 40-80% of the mass of the aqueous phase.
In one embodiment of the present invention, the proportion of the oil phase is 75 to 85%.
In one embodiment of the invention, the oil phase comprises a lipid and an oil-soluble inclusion.
In one embodiment of the present invention, the oil phase may be edible oil such as corn oil, soybean oil, peanut oil, algae oil, fish oil, or cosmetic raw material such as mineral oil, glycerin, propylene glycol, ethylhexyl palmitate.
In one embodiment of the present invention, the oil-soluble encapsulated substance is at least one of an oil-soluble nutrient substance, a drug, a food additive and a cosmetic.
In one embodiment of the present invention, there is provided a high internal phase Pickering emulsion stabilized with a nanocellulose-phenol gel system and a method for preparing the same, the method comprising the steps of:
(1) Preparing a nano-cellulose-phenol type antioxidant gel system: mixing the ginkgo seed husk cellulose suspension and the polyphenol solution to ensure that the cellulose concentration in the final mixed system is between 0.8 and 2 percent and the polyphenol concentration is between 0.05 and 0.5 percent. After being stirred evenly, the mixture is placed in a cell ultrasonic crusher and is subjected to ultrasonic treatment for 10 to 90min at the ultrasonic frequency of 20kHz and the power of 150 to 600W. In the ultrasonic process, the ultrasonic duration is 1-5 s, the ultrasonic intermittent time is 1-5 s, and the temperature of the mixed system is not more than 30 ℃ in the whole ultrasonic process. After the ultrasonic treatment is finished, a nano cellulose-phenol gel system can be obtained;
(2) Preparation of high internal phase Pickering emulsion: taking a certain mass of nano cellulose-phenol gel, adding deionized water to form a water phase, mixing the water phase and the nano cellulose-phenol gel according to the proportion of 75-85% of an oil phase, and shearing for 1-3 min under the action of high-speed dispersion shearing at 8000-12000 rpm to prepare the high internal phase Pickering emulsion.
In one embodiment, the polyphenol in step (1) is at least one of: tea polyphenols, gallic acid, catechin, tannic acid, epigallocatechin gallate, caffeic acid, and ferulic acid.
In one embodiment, the aqueous phase of the emulsion in the step (2) is composed of nanocellulose-phenol gel and water, wherein the amount of nanocellulose-phenol gel added is 40-80% of the mass of the aqueous phase.
In one embodiment, the oil phase in step (2) may be edible oil such as corn oil, soybean oil, peanut oil, fish oil, or cosmetic raw material such as mineral oil, glycerin, propylene glycol, ethylhexyl palmitate.
A fifth object of the present invention is to provide a food, pharmaceutical or cosmetic product comprising the Pickering high internal phase emulsion described above.
A sixth object of the present invention is to provide a use of the aforementioned Pickering high internal phase emulsion in the food field or the cosmetic field.
The invention has the beneficial effects that:
1. the invention creatively provides a strategy for improving the grease oxidation stability of a high internal phase Pickering emulsion, namely a nano-cellulose-phenol type antioxidant gel system is constructed as an emulsion water phase. The preparation method of the nano-cellulose-phenol type antioxidant gel system takes cellulose microparticles and polyphenol as raw materials, the cellulose with micron size at first is broken into slender nano-cellulose through ultrasonic treatment, and under the condition of sufficient concentration, the nano-cellulose is entangled with each other to form the gel system. Based on the adsorption of the nanocellulose to the polyphenols and the gel properties of the cellulose gel, the cellulose gel 'fixes' the polyphenols in a network structure. In the process of stabilizing the emulsion, the nanocellulose is adsorbed on an oil-water interface to form an interface layer, and meanwhile, the polyphenol is anchored on the oil-water interface, so that the concentration of the antioxidant near the oil-water interface is increased.
2. The emulsion disclosed by the invention is simple to prepare, and the high internal phase Pickering emulsion with excellent physical stability and oxidation stability can be prepared under the condition of less polyphenol adding amount (0.05%).
Drawings
Fig. 1 is a microscopic morphology picture of cellulose particles. Wherein A is cellulose particles in a cellulose suspension; b is cellulose in nanocellulose gel formed after sonication (control 1); c is cellulose in the nanocellulose-gallic acid gel system (example 1).
FIG. 2 is a Fourier infrared spectrum of cellulose, gallic acid, a mixture of cellulose and gallic acid, and a cellulose-gallic acid gel system;
FIG. 3 is an external view of different cellulose gel systems;
FIG. 4 is a confocal laser microscopy picture of Pickering emulsions of different high internal phases;
FIG. 5 is an appearance diagram of different high internal phase Pickering emulsions;
fig. 6 is a graph of the change in peroxide values during storage of different high internal phase Pickering emulsions.
Detailed Description
The following description of the preferred embodiments of the present invention is provided for the purpose of better illustrating the invention and is not intended to limit the invention thereto.
1.Method for measuring oxidation stability of emulsion grease
Referring to the method of [ Journal of AOAC INTERNATIONAL, volume 77, issue 2,1 March 1994, pages 421-424], the degree of oxidation of fats and oils in an emulsion was judged by measuring the hydroperoxide content in the emulsion. After the fresh emulsion is prepared, the fresh emulsion is immediately put into a centrifuge tube and is placed in a constant temperature incubator at 50 ℃ for an accelerated oxidation experiment, and samples are taken out periodically to determine the content of the hydroperoxide.
0.3mL of the emulsion was put into a 2mL centrifuge tube, 1.5mL of a mixture of isooctane and isopropanol (the mixing ratio of isooctane and isopropanol was 3.
2.Method for measuring physical stability of emulsion
The physical stability of the emulsion was judged by measuring the change in particle size of the emulsion before and after storage. Referring to the method in [ Food Hydrocolloids 112 (2021) 106279], the particle size of the high internal phase emulsion was measured by diluting 1mL of the high internal phase emulsion (fresh emulsion and emulsion after 24 days storage at 50 ℃) with 5mL of deionized water, mixing uniformly, and measuring the particle size of the emulsion by using a laser particle size analyzer.
Example 1
(1)Preparation of cellulose suspension of ginkgo biloba shell: the crushed white shells were mixed with 4% sodium hydroxide at a feed-to-liquid ratio of 1: stirring was carried out for 2h at 80 ℃ water bath, followed by filtration, which was repeated 2 times, and finally washed to neutrality with deionized water, followed by drying overnight in an oven at 50 ℃. Mixing the dried cellulose with a 64% sulfuric acid solution according to a material-liquid ratio of 1,immediately after the reaction was completed, 10 times deionized water was added to terminate the reaction, followed by centrifugation (8000rpm, 15min) to collect the precipitate. The collected precipitate is dispersed again by deionized water, and then inorganic salt ions are removed by dialysis by a dialysis bag with the molecular weight cutoff of 8-14 kDa, and after the pH is stabilized, the cellulose crystal suspension is collected. The microscopic morphology of the cellulose in the suspension can be seen in fig. 1A, the cellulose particles having a micron size and exhibiting an irregular, multi-sided blocky morphology.
(2)Preparation of nanocellulose-phenol type gel system: the gallic acid is used as polyphenol raw material, and the cellulose suspension and gallic acid aqueous solution are mixed, so that the final cellulose concentration of the mixed system reaches 1.0%, and the gallic acid concentration reaches 0.1%. 100mL of mixed solution is taken and placed in ultrasonic equipment, an ultrasonic generator (a metal probe) is immersed in the mixed solution, the ultrasonic power is set to be 300W, and the total ultrasonic time is 30min. In the ultrasonic process, the ultrasonic lasts for 1s, the ultrasonic is suspended for 1s, and the temperature alarm is set to be 30 ℃. And obtaining the nano-cellulose-phenol type gel system after the ultrasonic treatment.
The form of the nanocellulose-phenol type gel system is shown in fig. 1C, after ultrasonic treatment, original micron-sized cellulose particles are changed into slender nanocellulose, the length is 500-1000 nm, and it can be seen that some round small particles exist in the figure, and analysis shows that gallic acid exists, which indicates that the nanocellulose can adsorb certain polyphenol substances.
In addition, fig. 2 shows the fourier infrared spectra of different samples, and by comparing the spectrum of nanocellulose-gallic acid gel (labeled as cellulose-gallic acid gel system) with the spectrum of direct physical mixture of nanocellulose and gallic acid (labeled as direct mixture of cellulose and gallic acid), it can be seen that there are many significant differences, such as broad peak 3300-3800cm -1 Here, the nanocellulose-gallic acid gel spectrum is only one broad peak, whereas the cellulose and gallic acid direct mixture spectrum exhibits a double peak as the spectrogram of pure gallic acid (labeled gallic acid), and the broad peak of the nanocellulose-gallic acid gel spectrum here is compared to the spectrogram of pure cellulose (labeled cellulose)The broad peak of (a) is shifted, which means that hydrogen bond interaction exists between the nanocellulose and the gallic acid in the nanocellulose-gallic acid gel system.
(3) Preparation of high internal phase Pickering emulsion: preparing emulsion according to the proportion of 75% of oil phase, wherein the total mass of the emulsion is 200g, weighing 150g of soybean oil as the emulsion oil phase, weighing 30g of nano cellulose-phenolic gel and 20g of water as the water phase (the gel accounts for 60% of the mass of the water phase), adding the oil phase into the water phase, and then shearing for 2min at the rotating speed of 10000rpm to prepare the high internal phase Pickering emulsion.
Comparative example 1 (pure nanocellulose gel)
(1) Preparing the nano-cellulose hydrogel: the ginkgo biloba hull cellulose suspension obtained in example 1 was taken, without adding a phenol solution, the cellulose concentration was adjusted to 1.0%, and a pure cellulose gel system was prepared by the same ultrasonic treatment conditions as in example 1.
The morphology of cellulose in the pure cellulose gel system is shown in fig. 1B, and similar to fig. 1C (example 1), micron-sized cellulose particles are sonicated to become nanocellulose, but no small round particles are observed because the system is composed of pure nanocellulose.
(2) Preparation of high internal phase Pickering emulsion: a high internal phase Pickering emulsion was prepared under the same conditions as in example 1.
Comparative example 2 (CNCs hydrogel + phenol)
Adopting a commercially available CNCs product (cotton CNCs obtained by sulfuric acid hydrolysis, the length of the CNCs is 100-300 nm and the diameter of the CNCs is 15-40 nm) as a cellulose raw material, taking gallic acid as a polyphenol raw material, mixing the cellulose suspension with a gallic acid aqueous solution to ensure that the final cellulose concentration of a mixed system reaches 1.0 percent and the gallic acid concentration reaches 0.1 percent, and then adding a certain amount of CaCl 2 So that the ion concentration in the system reaches 20mM, uniformly stirring and standing for 5min to obtain a CNCs nano-cellulose-phenol gel system (hydrogel formed by electrostatic shielding caused by cations).
Preparing emulsion according to the proportion of 75% of oil phase, wherein the total mass of the emulsion is 200g, weighing 150g of soybean oil as the emulsion oil phase, weighing 30g of nano cellulose-phenolic gel and 20g of water as the water phase (the gel accounts for 60% of the mass of the water phase), adding the oil phase into the water phase, and then shearing for 2min at the rotating speed of 10000rpm to prepare the high internal phase Pickering emulsion.
Example 2 Effect of different phenol species
The cellulose suspension obtained in example 1 was used as a cellulose raw material, tea polyphenol, tannic acid, catechin, and ferulic acid were used as polyphenol raw materials, and the cellulose suspension was mixed with a polyphenol aqueous solution so that the final cellulose concentration of the mixed system reached 1.0% and the polyphenol concentration reached 0.1%. 100mL of mixed solution is taken and placed in ultrasonic equipment, an ultrasonic generator (a metal probe) is immersed in the mixed solution, the ultrasonic power is set to be 450W, and the total ultrasonic time is 50min. In the ultrasonic process, the ultrasonic lasts for 2s, the ultrasonic is suspended for 2s, and the temperature alarm is set to be 30 ℃.
Fig. 3 shows the appearance of the nanocellulose-phenol type gel systems of different phenol species of example 1 and example 2 and the gel systems of comparative examples 1-2 (designated as gallic acid, tea polyphenol, tannic acid, catechin, ferulic acid, comparative examples 1 and 2, respectively), and no sign of flow of the samples was observed when the sample bottles were inverted, indicating that the better gel systems were formed using the method of the present invention with tea polyphenol, tannic acid, catechin, ferulic acid as the polyphenol raw materials.
(3) Preparation of high internal phase Pickering emulsion: preparing emulsion according to the proportion of 75% of oil phase, wherein the total mass of the emulsion is 200g, weighing 150g of soybean oil as the emulsion oil phase, weighing 30g of nano-cellulose-phenolic gel and 20g of water as the water phase (the gel accounts for 60% of the mass of the water phase), adding the oil phase into the water phase, and then shearing at the rotating speed of 12000rpm for 1min to prepare the high internal phase Pickering emulsion.
The microstructure (confocal laser microscopy) of the emulsions of comparative examples 1-2 and examples 1-2 is shown in fig. 4, where it can be seen that emulsions stabilized with different gel systems exhibit different emulsion droplet sizes, and that gel systems with phenol generally reduce the emulsion particle size, especially the tannic acid system.
The physical stability of the emulsion during storage is shown in Table 1 and FIG. 5, and the oxidative stability of the emulsion is shown in FIG. 6.
TABLE 1 particle size variation and peroxide number for Pickering high internal phase emulsions stabilized with different gel systems
Table 1 shows that the cellulose-phenol system stabilized emulsions of the present invention exhibit smaller particle size compared to comparative examples 1-2, indicating that the addition of polyphenols facilitates improved preparation of smaller size emulsions. After storage, pickering high internal phase emulsions stabilized by different gel systems showed little change in particle size, indicating that these emulsions had good physical stability, but the peroxide value of the emulsion increased very significantly (P < 0.05): the peroxide value of comparative example 1 increased to 210.41mmol/kg oil, indicating that the emulsion underwent more severe grease oxidation; the peroxide value of the emulsion added with polyphenol is obviously smaller than that of the comparative example 1, which shows that the addition of the phenol obviously improves the grease oxidation of the emulsion. However, for comparative example 2 with the same gallic acid concentration added, the peroxide value (132.49 mmol/kg oil) is significantly greater than that of the nanocellulose-gallic acid gel system (78.24 mmol/kg oil), indicating that the ultrasound-induced nanocellulose-gallic acid gel system anchors gallic acid at the two phase interface of the emulsion more easily than the ionic electrostatic shielding-induced gel system. This is probably because the bubble cavitation effect generated during the ultrasonic treatment process is beneficial to promoting the action of the cellulose particles and the polyphenol substances, and the generated cellulose has longer shape and size, more action sites are provided for the polyphenol, and the long nanocellulose is also easy to be entangled with each other to form a network structure to further fix the polyphenol substances. When these nanocelluloses adsorb at the emulsion droplet interface, the polyphenol concentration at the two phase interface of the emulsion increases. Thus, the ultrasound-induced stable emulsion of nanocellulose-phenol gel system, shown in figure 6, exhibited a slow tendency for emulsion oxidation.
EXAMPLE 3 Effect of different phenol concentrations
The cellulose suspension obtained in example 1 was used as a cellulose raw material, tannic acid was used as a polyphenol raw material, and the cellulose suspension and the aqueous solution of tannic acid were mixed so that the final cellulose concentration of the mixed system became 2.0%, and the concentrations of polyphenol (tannic acid) became 0.03%,0.05%,0.1%,0.2%,0.3%, and 0.5%, respectively. 100mL of mixed solution is taken and placed in ultrasonic equipment, an ultrasonic generator (a metal probe) is immersed in the mixed solution, the ultrasonic power is set to be 450W, and the total ultrasonic time is 50min. In the ultrasonic process, the ultrasonic lasts for 2s, the ultrasonic is suspended for 2s, and the temperature alarm is set to be 30 ℃.
(3) Preparation of high internal phase Pickering emulsion: preparing an emulsion according to an oil phase proportion of 80%, wherein the total mass of the emulsion is 200g, weighing 160g of soybean oil as an emulsion oil phase, weighing 30g of nano-cellulose-phenolic gel and 10g of water as a water phase (the gel accounts for 75% of the mass of the water phase), adding the oil phase into the water phase, and then shearing for 2min at a rotation speed of 10000rpm to prepare the high internal phase Pickering emulsion.
As can be seen from Table 2, as the concentration of phenol increased, the particle size of the emulsion decreased first and then remained unchanged; the particle size of the emulsions did not increase dramatically upon storage, indicating that these emulsions have good physical stability. In addition, the peroxide value of the emulsion after storage is also reduced due to the increase of the phenol concentration, wherein the tannin concentration of 0.05% shows better antioxidant effect.
TABLE 2 Effect of different tannic acid concentrations on emulsion particle size variation and peroxide number
Example 4 addition of different nanocellulose-phenol gel systems
Taking the nanocellulose-catechin gel system in the example 2, preparing an emulsion according to an oil phase proportion of 85%, weighing 170g of soybean oil as an emulsion oil phase when the total mass of the emulsion is 200g, adding the gel system according to proportions of 20%, 40%, 60%, 80% and 100% of the weight of the water phase, namely 6g, 12g, 18g, 24g and 30g, complementing the rest water phase with deionized water, adding the oil phase into the water phase, and shearing for 2min at a rotation speed of 10000rpm to prepare the high internal phase Pickering emulsion.
Table 3 shows the effect of the amount of nanocellulose-catechin gel system added on the variation of the emulsion particle size and the peroxide value. 20% gel does not stabilize the emulsion and 100% hydrogel addition does not stabilize the high internal phase emulsion because the gel has poor flow properties and if the aqueous phase is a gel system, the shear process does not effectively disperse the aqueous phase, resulting in failure to form a high internal phase emulsion. In the addition amount of 40 to 80%, the emulsion has a smaller particle size and a lower peroxide value as the addition amount increases.
TABLE 3 influence of the amount of nanocellulose-catechin gel system added on the variation of the emulsion particle size and the peroxide value
Example 5 application of the Nanocellulose-phenol antioxidant gel System of the invention to drug delivery (preparation of sustained Release drug)
Preparing a medicine solution: cis-diammine-1, 1-cyclobutanedicarboxylates platinic acid (main effective component of carboplatin solution) was dissolved in 0.01M phosphate buffer pH7.4 to prepare carboplatin solution with concentration of 1 mg/mL.
Loading of the drug:
(1) Freeze-drying of the gel: using the nanocellulose-phenol type gel system obtained in example 3 as a raw material, the nanocellulose-phenol type gel system was first freeze-dried to obtain a freeze-dried nanocellulose-phenol type gel.
(2) Soaking of the drug solution: weighing 300mg of the freeze-dried nano-cellulose-phenol gel, adding the carboplatin solution to completely immerse the freeze-dried nano-cellulose-phenol gel in the carboplatin solution, soaking (statically adsorbing) the gel at room temperature for 24h, taking out the gel, performing vacuum freeze drying to obtain the freeze-dried drug-loaded nano-cellulose-phenol gel (drug-loaded hydrogel freeze-drying), and storing the freeze-dried drug-loaded nano-cellulose-phenol gel at room temperature for later use.
Freeze-drying the drug-loaded hydrogel, slowly releasing the drug-loaded hydrogel in simulated gastrointestinal digestive juice in vitro for 7 hours, and measuring the cumulative release rate of the drug released from the digestive juice. The measurement formula is as follows:
cumulative drug release rate = (M) 7 /M I )×100
Wherein M is 7 A drug release amount of 7 h; m is a group of I Is the amount of drug in the drug-loaded hydrogel.
The drug release after 7h was tested to be 45.72 ± 2.67% in a simulated gastric environment at pH =1.2, and 81.48 ± 4.88% in a neutral simulated intestinal environment at pH = 7.0.
It should be noted that, as will be understood by those skilled in the art based on the description of the present invention, the carboplatin solution in the present embodiment may be replaced by another water-soluble drug solution, which also has a considerable technical effect of drug release, and is not described herein again.
The experimental results of the application of the aforementioned nanocellulose-phenol type antioxidant gel system in the delivery of drugs demonstrate that: the nano-cellulose-phenol type antioxidant gel system shows pH-sensitive release behavior and releases less in an acidic gastric environment, so that the drug can be effectively prevented from being damaged in the acidic gastric environment. The nano cellulose-phenol gel has the function of slowing down the release rate of the drug.
Example 6 use of Pickering high internal phase emulsions according to the invention in the preparation of food, pharmaceutical or cosmetic products
Referring to example 2, epigallocatechin gallate was selected as a polyphenol material to prepare nanocellulose-epigallocatechin gallate gel.
The nano-cellulose-epigallocatechin gallate gel is used as one of ingredients of the hand cream, and specifically comprises the following steps:
the hand cream comprises the following main components in percentage by weight: 10 parts of aloe extract, 12 parts of shea butter, 5 parts of hyaluronic acid, 1 part of sorbitan olive oil ester, 2 parts of pearl powder, 0.5 part of amino acid, 8 parts of medical vaseline, 20 parts of nano-cellulose-epigallocatechin gallate gel and the balance of water.
The preparation process of the hand cream is approximately as follows: firstly, deionized water is heated to about 50 ℃, medical vaseline is added and stirred to melt, then, the sorbitan olive oil ester, the aloe extract, the shea butter, the hyaluronic acid and the amino acid are sequentially added, and the materials are fully mixed and stirred. And adding the nano-cellulose-epigallocatechin gallate gel, and performing high-speed shearing treatment to obtain the hand cream.
On one hand, the nano-cellulose-epigallocatechin gallate gel provided by the invention can be used as a substitute of the surfactant sorbitan olive oil ester, so that the dosage of the surfactant sorbitan olive oil ester is reduced. On the other hand, the nano-cellulose-epigallocatechin gallate gel contains epigallocatechin gallate, has the effects of activating cell activity and delaying cell aging, and is favorable for delaying skin aging.
Claims (7)
1. A method for preparing a nano-cellulose-phenol type antioxidant gel system is characterized in that firstly, a micro-cellulose suspension and a plant polyphenol water solution are mixed to obtain a mixed system, wherein in the mixed system, the concentration of the micro-cellulose is 2.0%, and the concentration of the plant polyphenol is 0.05%; then treating the mixed system by ultrasonic waves to construct a nano-cellulose-phenol type antioxidant gel system; wherein:
the plant polyphenol is tannic acid;
the conditions of the ultrasonic treatment were: the ultrasonic power is 450W, and the total ultrasonic time is 50min; in the ultrasonic process, the ultrasonic lasts for 2s, the ultrasonic is suspended for 2s, and the temperature alarm is set to be 30 ℃.
2. A nanocellulose-phenol type antioxidant gel system prepared by the process of claim 1.
3. The use of the nanocellulose-phenol type antioxidant gel system of claim 2 for diagnostic and therapeutic purposes in the preparation of emulsions or in the delivery of pharmaceuticals.
4. A Pickering high internal phase emulsion is characterized in that a Pickering high internal phase emulsion is formed by shearing a water phase and an oil phase for 1-2 min at the rotating speed of 10000-12000 rpm, wherein the oil phase accounts for 75-85%; wherein the aqueous phase contains the nanocellulose-phenol antioxidant gel system of claim 2; wherein the addition amount of the nano-cellulose-phenol type antioxidant gel system is 60-80% of the mass of the water phase.
5. The Pickering high internal phase emulsion of claim 4, wherein the oil phase is soybean oil,
6. a food, pharmaceutical or cosmetic product comprising the Pickering high internal phase emulsion of claim 4 or 5.
7. Use of a Pickering high internal phase emulsion as claimed in claim 4 or 5 in the food field or in the cosmetic field.
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