CN111763332A - Pickering emulsion with synergistically stable lemon peel residue cellulose nanocrystals and nanofibrils and preparation method thereof - Google Patents
Pickering emulsion with synergistically stable lemon peel residue cellulose nanocrystals and nanofibrils and preparation method thereof Download PDFInfo
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J3/00—Processes of treating or compounding macromolecular substances
- C08J3/02—Making solutions, dispersions, lattices or gels by other methods than by solution, emulsion or suspension polymerisation techniques
- C08J3/03—Making solutions, dispersions, lattices or gels by other methods than by solution, emulsion or suspension polymerisation techniques in aqueous media
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- A—HUMAN NECESSITIES
- A23—FOODS OR FOODSTUFFS; TREATMENT THEREOF, NOT COVERED BY OTHER CLASSES
- A23L—FOODS, FOODSTUFFS, OR NON-ALCOHOLIC BEVERAGES, NOT COVERED BY SUBCLASSES A21D OR A23B-A23J; THEIR PREPARATION OR TREATMENT, e.g. COOKING, MODIFICATION OF NUTRITIVE QUALITIES, PHYSICAL TREATMENT; PRESERVATION OF FOODS OR FOODSTUFFS, IN GENERAL
- A23L29/00—Foods or foodstuffs containing additives; Preparation or treatment thereof
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- A—HUMAN NECESSITIES
- A23—FOODS OR FOODSTUFFS; TREATMENT THEREOF, NOT COVERED BY OTHER CLASSES
- A23L—FOODS, FOODSTUFFS, OR NON-ALCOHOLIC BEVERAGES, NOT COVERED BY SUBCLASSES A21D OR A23B-A23J; THEIR PREPARATION OR TREATMENT, e.g. COOKING, MODIFICATION OF NUTRITIVE QUALITIES, PHYSICAL TREATMENT; PRESERVATION OF FOODS OR FOODSTUFFS, IN GENERAL
- A23L33/00—Modifying nutritive qualities of foods; Dietetic products; Preparation or treatment thereof
- A23L33/20—Reducing nutritive value; Dietetic products with reduced nutritive value
- A23L33/21—Addition of substantially indigestible substances, e.g. dietary fibres
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- A—HUMAN NECESSITIES
- A23—FOODS OR FOODSTUFFS; TREATMENT THEREOF, NOT COVERED BY OTHER CLASSES
- A23V—INDEXING SCHEME RELATING TO FOODS, FOODSTUFFS OR NON-ALCOHOLIC BEVERAGES AND LACTIC OR PROPIONIC ACID BACTERIA USED IN FOODSTUFFS OR FOOD PREPARATION
- A23V2002/00—Food compositions, function of food ingredients or processes for food or foodstuffs
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2301/00—Characterised by the use of cellulose, modified cellulose or cellulose derivatives
- C08J2301/02—Cellulose; Modified cellulose
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2401/00—Characterised by the use of cellulose, modified cellulose or cellulose derivatives
- C08J2401/02—Cellulose; Modified cellulose
Abstract
The invention belongs to the technical field of Pickering emulsion preparation, and particularly designs Pickering emulsion with stable coordination of lemon peel residue cellulose nanocrystals and nanofibrils and a preparation method thereof. Uniformly mixing 0.5-2% of lemon peel residue cellulose nanocrystalline (LSCNC) and 0.5-2% of nanofibril (LSCNF) suspension (w/w) according to a ratio of (1: 0-1: 5), then adding different oil phase ratios (30-70% w/w), and obtaining the Pickering emulsion with LSCNC/LSCNF synergistic stability by high-speed shearing (8000-15000 rpm, 1-3 min). According to the invention, the Pickering emulsion is synergistically stabilized by LSCNF and LSCNC prepared from lemon peel residues which are byproducts of lemon processing for the first time, the structure and stability of the Pickering emulsion can be regulated and controlled by simply regulating the ratio of LSCNC to LSCNF, and the prepared emulsion has good stability. According to the invention, nanocelluloses with different sizes are adopted to construct the Pickering emulsion, so that on one hand, the emulsion can be synergistically stabilized by enhancing the network structure of the emulsion, on the other hand, the dietary fiber in the emulsion can be adjusted, and the Pickering emulsion can be used as food-grade Pickering emulsion and applied to the field of food.
Description
Technical Field
The invention relates to the technical field of Pickering emulsion preparation, and particularly relates to Pickering emulsion with stable coordination of lemon peel residue cellulose nanocrystals and nanofibrils and a preparation method thereof.
Background
The peel residue waste generated by processing fruits and vegetables easily causes resource waste and environmental pollution, and has important significance in researching the high-efficiency utilization of the peel residue waste. Lemon (Citrus lemon) is the third most important cultivated Citrus variety in the world, is widely planted in Sichuan, Chongqing and Yunnan areas in China, and the total yield of the lemon in China is about 75 million tons in 2018. In addition to the fresh sales and the dried lemon slices, more than 50% of the lemons are processed into products such as lemon wine, lemon vinegar, lemon juice and the like, and the peel residue (about 57% of the fresh weight) generated by the processing is mostly discarded. Studies have shown that lemon pomace is composed mainly of cellulose, hemicellulose and lignin, with the cellulose content being around 20% (w/w) by dry weight. The research on the high-efficiency utilization of the lemon peel residue cellulose has important significance for promoting the high-valued utilization of the lemon processing byproducts. At present, besides a small amount of dietary fiber research on lemon peel residue, research and utilization of nano-cellulose with a finer structure and a higher valued space are lacked. Nanocellulose refers to ultrafine fibers having at least one dimension of 100 nm or less in size, and is mainly classified into Cellulose Nanocrystals (CNC) and Cellulose Nanofibrils (CNF) according to the morphology and particle size of nanocellulose. CNC has high crystallinity, is a short rod-like structure, is generally less than 500 nm in length, and is mainly prepared by an acid hydrolysis method. The CNF consists of an amorphous area and a crystalline area, is in a mutually wound long line shape, has the length of several micrometers, and is mainly prepared by a mechanical method (such as high-pressure homogenization, ultrasound, ball milling and the like).
The Pickering emulsion stabilizes the emulsion by replacing a surfactant with solid particles, and has the characteristics of good stability, controllability, good environmental compatibility, austenite aging resistance and the like compared with the emulsion stabilized by the traditional surfactant. Among a plurality of Pickering stabilizers (such as clay, silicon dioxide, protein and the like), the nanocellulose shows great advantages in stabilizing Pickering emulsion due to the characteristics of unique nano structure, high aspect ratio, reproducibility, biocompatibility, no toxicity and the like, and has good application prospects in the aspects of food, cosmetics and medicines. The widely accepted mechanism of stabilizing the Pickering emulsion by the nano-cellulose is that the nano-cellulose can be irreversibly adsorbed on an oil/water interface, and the nano-cellulose can be self-assembled at the oil/water interface to form an interface film to wrap oil drops so as to stabilize the emulsion. Currently, nanocellulose-stabilized Pickering emulsions are mainly focused on single forms, such as CNC and CNF, but there is little research on their synergistically stabilized emulsions. The CNF is used as nano-cellulose with a high aspect ratio, can form a high-viscosity flexible fiber network in a water phase, can be used as a stabilizer and a thickening agent to stabilize Pickering emulsion, and can improve the instability phenomenon of the emulsion caused by the action of gravity. The CNC is small in length, can be well adsorbed and arranged on an oil drop interface, and can fill up interface gaps existing in CNF adsorption, so that the CNC/CNF synergetic stable Pickering emulsion has a good development prospect.
Disclosure of Invention
Aiming at the defects and shortcomings of the prior art, the invention aims to provide a Pickering emulsion with stable coordination of lemon peel residue cellulose nanocrystals and nanofibrils and a preparation method thereof.
The purpose of the invention is realized by the following technical scheme.
A Pickering emulsion with stable coordination of lemon peel residue cellulose nanocrystals and nanofibrils and a preparation method thereof specifically comprise the following steps.
(1) Mixing the lemon peel residue cellulose nanocrystalline (LSCNC) and the nanofibril (LSCNF) with certain concentration according to a certain proportion, adding a certain amount of NaCl, and mixing and stirring at room temperature for a period of time to obtain an LSCNC/LSCNF suspension.
(2) Adding the oil phase in a certain proportion into the LSCNC/LSCNF suspension, and shearing and homogenizing at a high speed for a period of time to obtain the Pickering emulsion with the LSCNC/LSCNF synergetic stability.
Further, in the step (1), the cellulose nanocrystals (LSCNC) and the nanofibrils (LSCNF) are derived from lemon peel pomace which is a byproduct of lemon processing.
Further, in the step (1), the concentration of the LSCNC/LSCNF suspension is 0.5-2% (w/w).
Further, in the step (1), the concentration of NaCl in the suspension is 20-50 mmol/L.
Further, in step (1), the LSCNC: the mixing ratio of LSCNF is 1: 0-1: 5 (w/w), a mixing and stirring speed of 200-400 rpm, and a stirring time of 0.5-2 h.
Further, in the step (2), the oil phase is at least one of sunflower seed oil, soybean oil, peanut oil and rapeseed oil.
Further, in the step (2), the oil phase in a certain proportion is 30-70% (w/w).
Further, in the step (2), the shearing homogenizing rotating speed is 8000-15000 rpm, and the shearing time is 1-3 min.
The Pickering emulsion with the lemon peel residue cellulose nanocrystal and the nanofibrils which are synergistically stable is prepared by the preparation method.
Compared with the prior art, the invention has the following beneficial effects.
(1) The nano-cellulose used in the invention is derived from lemon processing byproducts (lemon peel residues), the raw materials are easy to obtain and the cost is low, the problems of resource waste and environmental pollution of the lemon processing byproducts can be solved, and a thought is provided for high-value utilization of the fruit and vegetable processing byproducts rich in cellulose.
(2) The stable Pickering emulsion can be prepared by taking the nano-cellulose as the Pickering emulsion stabilizer through high-speed shearing, the operation is simple and convenient, the preparation process does not need any modification operation, and the preparation method does not contain any surfactant or organic cross-linking agent, has good biological safety, and can be suitable for green application in food.
(3) The structure and stability of the stable Pickering emulsion can be easily regulated and controlled by regulating and controlling the proportion of the cellulose nanocrystals to the nanofibrils, and meanwhile, the nanocellulose can be used as a dietary fiber supplement in the emulsion.
Drawings
FIG. 1 is a drawing of the abstract of the specification.
Fig. 2 is an Atomic Force Microscope (AFM) morphology of the lemon pomace cellulose nanocrystals and nanofibrils prepared in example 1.
Fig. 3 is a laser scanning confocal microscope (CLSM) picture of Pickering emulsion synergistically stabilized by different LSCNC/LSCNF in examples 2 and 3.
FIG. 4 is a thermal Field Emission Scanning Electron Microscope (FESEM) picture of Pickering emulsion synergistically stabilized by different LSCNC/LSCNF in examples 2 and 3.
FIG. 5 is the rheological profile of Pickering emulsions synergistically stabilized by different LSCNC/LSCNF of example 4.
Fig. 6 is a macroscopic and optical microscopy picture of LSCNC/LSCNF synergistically stabilized prepared Pickering emulsions prepared under different pH conditions of example 5.
FIG. 7 is a macroscopic and optical microscope picture of the LSCNC/LSCNF synergistically stabilized Pickering emulsions prepared in example 6 at different NaCl concentrations.
Detailed Description
The invention is illustrated and described in further detail below with reference to the figures and examples, but the embodiments of the invention are not limited thereto.
Example 1
Preparation of lemon peel residue cellulose nanocrystals (LSCNC) and nanofibrils (LSCNF).
The extraction of the lemon peel residue cellulose is carried out according to the following steps of drying and crushing the lemon peel residue, sieving by a sieve of 80 meshes, mixing and stirring the lemon peel residue and distilled water at 80 ℃ for 2 h according to a material-liquid ratio of 1:20 (g/mL), filtering, washing by distilled water, drying, continuously treating by a sodium chlorite solution (5%, w/v, pH 3.8-4.0) with a material-liquid ratio of 1:20 g/mL, stirring for 5 h at 75 ℃, washing by distilled water, drying again, stirring by a sodium hydroxide solution (10%, w/v) according to a material-liquid ratio of 1:10 g/mL (30 ℃, 12 h), repeatedly washing by distilled water and absolute ethyl alcohol in sequence until the filtrate becomes neutral, drying, crushing and sieving (100 meshes) to obtain the lemon peel residue cellulose.
The lemon peel residue cellulose nanocrystalline (LSCNC) is prepared by the following steps in sequence: the dried and ground lemon peel residues are mixed with sulfuric acid with the concentration of 64% (w/w) according to the feed-liquid ratio of 1:20 g/mL, then the mixture is continuously stirred and hydrolyzed at the temperature of 45 ℃ for 1.5 h, and then 10 times of distilled water is added to stop the reaction. After centrifugation at 5000rpm for 10 min, the precipitate was washed several times with distilled water until the appearance of the nanocellulose suspension. After 3 days of dialysis in distilled water at 4 ℃ and ultrasonic dispersion (300W, 30 min), LSCNC suspension was obtained.
The lemon peel residue cellulose nanofibrils (LSCNF) can be prepared by a ball milling method according to the following steps in sequence: selecting three zirconia balls with different diameters (7 mm:3 mm:1 mm) according to the ball milling requirement, wherein the mass ratio of the three balls is 5: 4: 3, simultaneously, the mass ratio of the balls to the lemon peel residue cellulose is 12: 1. at the room temperature of 25 ℃, 1 g of lemon peel residue cellulose, 20mL of [ BMIM ] Cl ionic liquid (prepared by distilled water) with the mass concentration of 10 percent and zirconia balls are put into a ball mill together, the ball milling speed is 400 r/min, and the ball milling time is 2 h. And after the ball milling is finished, performing centrifugal washing on the suspension for multiple times (8000 r/min, 15 min), dialyzing at 4 ℃ for 48 h, and performing ultrasonic treatment (300W, 30 min) after the dialysis is finished to obtain the LSCNF suspension.
The LSCNC and LSCNF of examples 2-6 below were obtained as in example 1.
Example 2
Taking 1% LSCNC/LSCNF (mixing ratio 1:0, 1: 1) nano-cellulose suspension, adding 50 mmol/L NaCl, mixing and stirring at 200rpm for 0.5 h, adding 50% oil phase ratio sunflower seed oil, and performing high-speed shearing homogenization treatment (9000 rpm, 1 min) to prepare the Pickering emulsion with LSCNC/LSCNF synergistic stabilization.
Example 3
Taking an LSCNC/LSCNF suspension (the mixing ratio is 1: 3) with the mass fraction of 1%, adding 50 mmol/L NaCl, mixing and stirring at 200rpm for 0.5 h, adding sunflower seed oil with the oil phase ratio of 50%, and performing high-speed shearing homogenization treatment (9000 rpm for 1 min) to prepare the Pickering emulsion with the LSCNC/LSCNF synergistic stability.
Example 4
Preparing LSCNC/LSCNF suspension with different proportions, wherein the concentration of LSCNC is 0.5%, the concentration of LSCNF is 0, 0.1, 0.3, 0.5 and 1.0%, adding 50 mmol/L NaCl, mixing and stirring for 1 h at 300rpm, adding sunflower seed oil with an oil phase proportion of 50%, and performing high-speed shearing homogenization treatment (10000 rpm, 1 min) to prepare the Pickering emulsion with LSCNC/LSCNF synergistic stabilization.
Example 5
Taking an LSCNC/LSCNF suspension with the mass fraction of 1% (the mixing ratio is 1: 1), adding 50 mmol/L NaCl, mixing and stirring at 300rpm for 1 h, adding 0.1M NaOH and 0.1M HCl to adjust the pH of the suspension to be 2, 4, 6, 8 and 10, adding sunflower seed oil with the oil phase ratio of 50%, and carrying out high-speed shearing homogenization treatment (10000 rpm, 1 min) to prepare the Pickering emulsion with the LSCNC/LSCNF synergistically stabilized under different pH conditions.
Example 6
Taking the suspension with the mass fraction of 1% of LSCNC/LSCNF (the mixing ratio is 1: 1), adding NaCl (0, 5, 10, 20, 30 and 50 mmol/L) with different concentrations, adding sunflower seed oil with the oil phase ratio of 50%, and performing high-speed homogenizing emulsification treatment (10000 rpm, 1 min) to prepare the Pickering emulsion with the LSCNC/LSCNF synergistic stability.
Fig. 2 is an Atomic Force Microscope (AFM) image of LSCNC and LSCNF prepared in example 1. As can be seen, the LSCNF has a length of 1-2 μm and a diameter of 35-50 nm, and the LSCNC has a length of 130-170 nm and a diameter of 12-25 nm.
Fig. 3 is a laser scanning confocal microscope (CLSM) picture of the Pickering emulsion prepared in examples 2 and 3. Wherein the oil phase is dyed with nile red to appear red; LSCNC/LSCNF suspension stained with fluorescent white and appeared blue. At a LSCNC/LSCNF of 1:0, i.e. no LSCNF was added, the LSCNC was distributed at the oil-water interface, forming smaller emulsion droplets. As the proportion of LSCNF increases, the emulsion size gradually increases, with a portion of the longer LSCNF distributed in the aqueous phase and a portion forming irregular floes.
FIG. 4 is a thermal Field Emission Scanning Electron Microscope (FESEM) picture of Pickering emulsion prepared in examples 2 and 3. When the ratio of the LSCNC to the LSCNF is 1:0, namely the LSCNF is not added, the sizes of the emulsion droplets of the single LSCNC emulsion are relatively consistent, while the emulsion droplets synergistically stabilized by the LSCNC/LSCNF in the examples 2 and 3 are connected into lumps due to the entangled part of the long fiber, one part of the LSCNF is contacted with oil drops adsorbed by the LSNCS, and one part of the LSCNF is dissociated in the water phase and intertwined with each other to form a compact fiber network to effectively block aggregation among the oil drops, so that the LSCNC/LSCNF can form relatively stable Pickering emulsion.
FIG. 5 is the results of rheological characterization of the Pickering emulsion prepared in example 4. As can be seen from the figure, the viscosity of the Pickering emulsion layer increases with the addition of LSCNF, indicating that longer LSCNF is beneficial for enhancing the viscosity of the emulsion. In addition, during frequency scanning, G 'is always greater than G', mainly the elastic characteristic is stronger than the viscous characteristic, and meanwhile, the larger the mass fraction of LSCNF is, the storage modulus and the loss modulus are obviously higher, the two are basically independent of the change of stress, the stress is further increased, the two are both reduced and cross points appear, and the point is a flow point, which indicates that the emulsion starts to have flow behavior, possibly caused by the fact that the structure of the emulsion is damaged.
FIG. 6 is an appearance and light microscopy image of Pickering emulsions prepared under different pH conditions for example 5. The LSCNC/LSCNF can synergistically and stably prepare Pickering emulsion under different pH conditions, wherein emulsion droplets have larger and sparse particle sizes under an acidic condition, and the particle sizes of the droplets are reduced to be denser under an alkaline condition. After being stored for 1 day, the emulsion can be kept stable from the appearance of the emulsion, which shows that the LSCNC/LSCNF synergy can improve the good pH stability of the emulsion.
FIG. 7 is an appearance and light microscopy image of Pickering emulsions prepared under different NaCl concentrations in example 6. The LSCNC/LSCNF can be used for preparing Pickering emulsion in a synergistic and stable manner under the conditions of different NaCl concentrations. Generally, LSCNC prepared by sulfuric acid hydrolysis requires NaCl addition for charge shielding when preparing an emulsion due to the presence of surface charge, otherwise the emulsion cannot be stabilized due to excessive electrostatic repulsion. And the LSCNF synergy can improve the formation and stability of the emulsion without NaCl. With the increase of the NaCl concentration, the emulsion liquid drops are denser, the emulsion layer is obviously increased, and the emulsion is relatively more stable.
The above-described embodiments are merely examples for illustrating the present invention, but the present invention is not limited to the above-described embodiments. Any modification, equivalent replacement, and improvement made within the spirit and principle of the present invention within the knowledge of those skilled in the art should be considered as the protection scope of the present invention.
Claims (7)
1. A Pickering emulsion with stable coordination of lemon peel residue cellulose nanocrystals and nanofibrils and a preparation method thereof are characterized by comprising the following steps:
(1) mixing LSCNC and LSCNF with certain concentration according to a certain proportion, adding a certain amount of NaCl, and mixing and stirring at room temperature for a period of time to obtain LSCNC/LSCNF suspension;
(2) adding the oil phase in a certain proportion into the LSCNC/LSCNF suspension, and shearing and homogenizing at a high speed for a period of time to obtain the Pickering emulsion with the LSCNC/LSCNF synergetic stability.
2. The Pickering emulsion with the synergistic stabilization of cellulose nanocrystals and nanofibrils of lemon pomace and the preparation method thereof according to claim 1, characterized in that in the step (1), the cellulose nanocrystals (LSCNC) and nanofibrils (LSCNF) are derived from lemon pomace which is a byproduct of lemon processing.
3. The Pickering emulsion with the lemon peel residue cellulose nanocrystals and nanofibrils synergistically stabilized and the preparation method thereof as claimed in claim 1, wherein in the step (1), the concentration of the LSCNC/LSCNF suspension is 0.5-2% (w/w), and the concentration of NaCl in the suspension is 0-50 mmol/L.
4. The Pickering emulsion with the lemon pomace cellulose nanocrystals and nanofibrils synergistically stabilized and the preparation method thereof according to claim 1, are characterized in that in the step (1), the LSCNC: the mixing ratio of the LSCNF is 1: 0-1: 5 (w/w), the mixing and stirring speed is 200-400 rpm, and the stirring time is 0.5-2 h.
5. The Pickering emulsion with the lemon pomace cellulose nanocrystals and the nanofibrils synergistically stabilized and the preparation method thereof according to claim 1 are characterized in that in the step (2), the oil phase in a certain proportion is 30-70% (w/w), and the oil phase is at least one of sunflower seed oil, soybean oil, peanut oil and rapeseed oil.
6. The Pickering emulsion with the lemon peel residue cellulose nanocrystals and the nanofibrils synergistically stabilized and the preparation method thereof as claimed in claim 1 are characterized in that in the step (2), the shearing homogenizing rotation speed is 8000-15000 rpm, and the shearing time is 1-3 min.
7. Pickering emulsion with the lemon pomace cellulose nanocrystals and nanofibrils synergistically stabilized by the preparation method of any one of claims 1 to 6.
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