CN113680289A - 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 a stable Pickering high internal phase emulsion thereof, belonging to the technical field of Pickering emulsions. 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 oil 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 oil 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 a prolamin-phenol antioxidant nanoparticle and a Pickering emulsion prepared from the prolamin-phenol antioxidant nanoparticle, and the prolamin-phenol composite nanoparticle is prepared by an anti-solvent precipitation method; chinese patent 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-bayberry 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 ] reported that the cellulose particles had a certain adsorption capacity for catechins, the adsorption capacity was limited and the maximum adsorption amount was only 2.82 mg/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 microparticles 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 the 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 white fruit shells), purified by 4% of sodium hydroxide and 1.5% of sodium chlorite solution, and hydrolyzed in a water bath environment at 45 ℃ for 30-90 min by adopting 62-64% of sulfuric acid. 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 a micron cellulose suspension with the pH value of 5-7 and the concentration of 1-5%.
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 water 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 20 kHz.
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.
A fourth object of the present invention is to provide a Pickering high internal phase emulsion having excellent physical stability and oxidation stability of fats and oils, which is formed by mixing an aqueous phase with 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 water phase further comprises water, wherein the addition amount of the nano cellulose-phenol type antioxidant gel system is 40-80% of the mass of the water 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: and mixing the ginkgo seed husk cellulose suspension with the polyphenol solution to ensure that the cellulose concentration in a final mixed system is 0.8-2% and the polyphenol concentration is 0.05-0.5%. After being uniformly stirred, the mixture is placed in a cell ultrasonic crusher and is subjected to ultrasonic treatment for 10-90 min at the ultrasonic frequency of 20kHz and the power of 150-600W. In the ultrasonic process, the ultrasonic duration is 1-5 s, the ultrasonic intermittent time is 1-5 s, and the temperature of a 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: adding deionized water into a certain mass of nanocellulose-phenol gel to form a water phase, mixing the water phase and the nano cellulose-phenol gel according to a 75-85% oil phase ratio, and shearing for 1-3 min under the high-speed dispersing shearing action of 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 emulsion water phase in the step (2) is composed of nanocellulose-phenol gel and water, wherein the addition amount of the nanocellulose-phenol gel is 40-80% of the mass of the water 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 mineral oil, glycerin, propylene glycol, ethylhexyl palmitate, or other cosmetic raw materials.
A fifth object of the present invention is to provide a food, pharmaceutical or cosmetic product comprising the aforementioned Pickering high internal phase emulsion.
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 to be used 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 the nanocellulose gel formed after the ultrasonic treatment (comparative example 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 appearance 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 and 424, the oxidation degree of the oil and fat in the emulsion is judged by measuring the content of the hydroperoxide 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 (a mixture ratio of isooctane to isopropanol of 3: 1, v/v) was added thereto, the mixture was shaken thoroughly, and then centrifuged at 1000g for 2min, 200. mu.L of the supernatant (organic layer) was added to 2.8mL of a mixture of methanol and butanol (a mixture ratio of methanol to butanol of 2: 1, v/v), 15. mu.L of 3.94M ammonium thiocyanate and 15. mu.L of a divalent iron ion solution (obtained by mixing 0.134M barium chloride and 0.144M ferrous sulfate at a ratio of 1:1 and filtering) were added thereto, after 20min of reaction, the absorbance was measured at 510nm, and the peroxide concentration of the sample was calculated from the cumene hydroperoxide labeling curve.
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 stored at 50 ℃ for 24 days) 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: mixing crushed white fruit shells according to a feed-liquid ratio of 1:20(g/mL) and 4% sodium hydroxide, continuously stirring for 2h in a water bath at 90 ℃, then filtering, washing with deionized water, drying at 50 ℃, and then rinsing the dried cellulose with 20 times of volume of a rinsing liquid (containing 1.5% sodium chlorite, 2.5% sodium hydroxide and 7% acetic acid): 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 in an oven at 50 ℃ overnight. Mixing the dried cellulose and a 64% sulfuric acid solution according to a feed-liquid ratio of 1:15(g/mL), reacting for 60min in a water bath environment at 45 ℃, immediately adding 10 times of deionized water to terminate the reaction after the reaction is finished, and then centrifuging (8000rpm, 15min) to collect precipitates. And (3) dispersing the collected precipitate by deionized water again, then dialyzing by using a dialysis bag with the molecular weight cutoff of 8-14 kDa to remove inorganic salt ions, and collecting the cellulose crystal suspension until the pH value is stable. 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 30 min. 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 elongated nanocellulose, the length is 500-1000 nm, and some round small particles exist in the figure, and analysis shows that the nanocellulose can adsorb certain polyphenol substances, namely gallic acid.
In addition, FIG. 2 shows Fourier infrared spectra of different samples, and comparing the spectrum of the nanocellulose-gallic acid gel (labeled as cellulose-gallic acid gel system) with the spectrum of the nanocellulose and gallic acid directly physically mixed (labeled as cellulose and gallic acid directly mixed) shows that there are many obvious differences, such as broad peak 3300--1The spectrum of the nanocellulose-gallic acid gel has only one broad peak, while the direct mixed spectrum of the cellulose and the gallic acid has two peaks as same as the spectrum of the pure gallic acid (marked as gallic acid), and the broad peak of the spectrum of the nanocellulose-gallic acid gel has a shift compared with the broad peak of the spectrum of the pure cellulose (marked as cellulose), which means that the nanocellulose and the gallic acid have hydrogen bond interaction 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 cellulose morphology in the pure cellulose gel system is shown in fig. 1B, and similar to fig. 1C (example 1), the 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, 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 CaCl2So 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 50 min. 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 by different gel systems exhibit different droplet sizes, and that gel systems with phenol generally reduce emulsion particle size, especially tannin systems.
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 a very significant increase in the peroxide value of the emulsion occurred (P < 0.05): the peroxide value of comparative example 1 increased to 210.41mmol/kg oil, indicating that more severe grease oxidation of the emulsion occurred; 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 (132.49mmol/kg oil) was significantly greater than that of the nanocellulose-gallic acid gel system (78.24mmol/kg oil), indicating that the ultrasound-induced nanocellulose-gallic acid gel system was more likely to anchor gallic acid at the two-phase interface of the emulsion 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 nanocellulose-phenol gel system-stabilized emulsion exhibited a slow emulsion oxidation trend as shown in figure 6.
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 50 min. 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 emulsion according to the proportion of 80% of oil phase, wherein the total mass of the emulsion is 200g, weighing 160g of soybean oil as the emulsion oil phase, weighing 30g of nano-cellulose-phenolic gel and 10g of water as the 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 the rotating 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 very 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 tannin 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%, wherein the total mass of the emulsion is 200g, weighing 170g of soybean oil as the emulsion oil phase, adding the gel system according to the 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 then 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 40-80%, the emulsion has smaller particle size and lower peroxide value with the increase of the addition amount.
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-cyclobutanedicarboxylato-platinum (main active ingredient 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/MI)×100
Wherein M is7A drug release amount of 7 h; mIIs the amount of drug in the drug-loaded hydrogel.
The test shows that the drug release amount is 45.72 +/-2.67% after 7h in the simulated gastric environment with the pH value of 1.2, and the drug release amount is 81.48 +/-4.88% after 7h in the neutral simulated intestinal environment with the pH value of 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 technical effect of sustained release of the drug, 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 a Pickering high internal phase emulsion according to the invention in the preparation of a food, pharmaceutical or cosmetic product
Referring to example 2, epigallocatechin gallate was selected as a polyphenol material, and nanocellulose-epigallocatechin gallate gel was prepared.
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. 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 (10)
1. A method for preparing a nano-cellulose-phenol type antioxidant gel system is characterized in that a micro-cellulose suspension and a plant polyphenol water solution are mixed and subjected to ultrasonic treatment to construct the nano-cellulose-phenol type antioxidant gel system.
2. The method for preparing the nanocellulose-phenol type antioxidant gel system according to claim 1, wherein 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%.
3. The method for preparing a nanocellulose-phenol type antioxidant gel system as claimed in claim 1, wherein the ultrasonic treatment conditions are: the ultrasonic power is 150-600W, the ultrasonic time is 10-90 min, and the ultrasonic frequency is 20 kHz.
4. The method for preparing the nanocellulose-phenol type antioxidant gel system as claimed in claim 1 or 3, wherein the ultrasonic treatment is by means of 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 ℃.
5. A nanocellulose-phenol type antioxidant gel system prepared by the method of any one of claims 1 to 4.
6. The use of the nanocellulose-phenol antioxidant gel system of claim 5 for diagnostic and therapeutic purposes in the preparation of emulsions or in the delivery of pharmaceuticals, other than disease.
7. A Pickering high internal phase emulsion is characterized in that a Pickering emulsion is formed by mixing a water phase and an oil phase; wherein the aqueous phase comprises at least the nanocellulose-phenol type antioxidant gel system of claim 6.
8. The Pickering high internal phase emulsion according to claim 7, wherein the aqueous phase further comprises water, and the amount of the nano-cellulose-phenol antioxidant gel system added is 40-80% of the mass of the aqueous phase.
9. A food, pharmaceutical or cosmetic product comprising a Pickering high internal phase emulsion as claimed in any of claims 7 to 8.
10. Use of a Pickering high internal phase emulsion according to any of claims 7 to 8 in the food field or in the cosmetic field.
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