AU2020102161A4 - Self-assembled nanosphere and preparation method and application method thereof - Google Patents

Self-assembled nanosphere and preparation method and application method thereof Download PDF

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AU2020102161A4
AU2020102161A4 AU2020102161A AU2020102161A AU2020102161A4 AU 2020102161 A4 AU2020102161 A4 AU 2020102161A4 AU 2020102161 A AU2020102161 A AU 2020102161A AU 2020102161 A AU2020102161 A AU 2020102161A AU 2020102161 A4 AU2020102161 A4 AU 2020102161A4
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self
assembled
graphene oxide
chitosan
nanosphere
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AU2020102161A
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Cunkun CHEN
Bei FAN
Li Li
Zisheng Luo
Fengzhong Wang
Wensheng Wang
Wentong Xue
Tiejin Ying
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Zhejiang University ZJU
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Zhejiang University ZJU
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    • AHUMAN NECESSITIES
    • A23FOODS OR FOODSTUFFS; TREATMENT THEREOF, NOT COVERED BY OTHER CLASSES
    • A23LFOODS, 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
    • A23L3/00Preservation of foods or foodstuffs, in general, e.g. pasteurising, sterilising, specially adapted for foods or foodstuffs
    • A23L3/34Preservation of foods or foodstuffs, in general, e.g. pasteurising, sterilising, specially adapted for foods or foodstuffs by treatment with chemicals
    • A23L3/3454Preservation of foods or foodstuffs, in general, e.g. pasteurising, sterilising, specially adapted for foods or foodstuffs by treatment with chemicals in the form of liquids or solids
    • A23L3/3463Organic compounds; Microorganisms; Enzymes
    • A23L3/3526Organic compounds containing nitrogen
    • AHUMAN NECESSITIES
    • A23FOODS OR FOODSTUFFS; TREATMENT THEREOF, NOT COVERED BY OTHER CLASSES
    • A23LFOODS, 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
    • A23L29/00Foods or foodstuffs containing additives; Preparation or treatment thereof
    • A23L29/015Inorganic compounds
    • AHUMAN NECESSITIES
    • A23FOODS OR FOODSTUFFS; TREATMENT THEREOF, NOT COVERED BY OTHER CLASSES
    • A23LFOODS, 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
    • A23L29/00Foods or foodstuffs containing additives; Preparation or treatment thereof
    • A23L29/20Foods or foodstuffs containing additives; Preparation or treatment thereof containing gelling or thickening agents
    • A23L29/275Foods or foodstuffs containing additives; Preparation or treatment thereof containing gelling or thickening agents of animal origin, e.g. chitin
    • AHUMAN NECESSITIES
    • A23FOODS OR FOODSTUFFS; TREATMENT THEREOF, NOT COVERED BY OTHER CLASSES
    • A23LFOODS, 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
    • A23L3/00Preservation of foods or foodstuffs, in general, e.g. pasteurising, sterilising, specially adapted for foods or foodstuffs
    • A23L3/34Preservation of foods or foodstuffs, in general, e.g. pasteurising, sterilising, specially adapted for foods or foodstuffs by treatment with chemicals
    • A23L3/3454Preservation of foods or foodstuffs, in general, e.g. pasteurising, sterilising, specially adapted for foods or foodstuffs by treatment with chemicals in the form of liquids or solids
    • A23L3/358Inorganic compounds
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B82NANOTECHNOLOGY
    • B82YSPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
    • B82Y30/00Nanotechnology for materials or surface science, e.g. nanocomposites
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B82NANOTECHNOLOGY
    • B82YSPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
    • B82Y40/00Manufacture or treatment of nanostructures
    • AHUMAN NECESSITIES
    • A23FOODS OR FOODSTUFFS; TREATMENT THEREOF, NOT COVERED BY OTHER CLASSES
    • A23VINDEXING SCHEME RELATING TO FOODS, FOODSTUFFS OR NON-ALCOHOLIC BEVERAGES AND LACTIC OR PROPIONIC ACID BACTERIA USED IN FOODSTUFFS OR FOOD PREPARATION
    • A23V2002/00Food compositions, function of food ingredients or processes for food or foodstuffs
    • CCHEMISTRY; METALLURGY
    • C01INORGANIC CHEMISTRY
    • C01BNON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B32/00Carbon; Compounds thereof
    • C01B32/15Nano-sized carbon materials
    • C01B32/182Graphene
    • C01B32/198Graphene oxide

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Food Science & Technology (AREA)
  • Nanotechnology (AREA)
  • Polymers & Plastics (AREA)
  • Nutrition Science (AREA)
  • Health & Medical Sciences (AREA)
  • General Physics & Mathematics (AREA)
  • General Chemical & Material Sciences (AREA)
  • Crystallography & Structural Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Inorganic Chemistry (AREA)
  • Physics & Mathematics (AREA)
  • Condensed Matter Physics & Semiconductors (AREA)
  • Composite Materials (AREA)
  • Carbon And Carbon Compounds (AREA)
  • Materials Engineering (AREA)
  • Manufacturing & Machinery (AREA)
  • Zoology (AREA)
  • Microbiology (AREA)
  • Dispersion Chemistry (AREA)

Abstract

A self-assembled nanosphere, a preparation method and an application on the sustained release of food preservative are disclosed, relateing to the field of food preservation. The self-assembled nanosphere includes: graphene oxide forms self-assembled spheres through electrostatic interaction and intermolecular hydrogen bonding with chitosan after loading small molecules; adjusting the pore size of graphene oxide by controlling ultrasound to perform selective release; adjusting the number of graphene chitosan layers to regulate the release rate of the loading material. The self-assembled nanospheres prepared by the present disclosure have loading and sustained release, so as to realize the selective release of small molecular loading material and the precise control of release rate. In addition, it can be hydrated to form a film in the process of use, so as to enhance its application range.

Description

SELF-ASSEMBLED NANOSPHERE AND PREPARATION METHOD AND APPLICATION METHOD THEREOF TECHNICAL FIELD
The present disclosure relates to the technical field of food preservation, in particular to a
self-assembled nanosphere and its preparation method and application in the sustained release
of food preservative.
BACKGROUND Graphene is a kind of monolayer planar film with hexagonal honeycomb lattice
composed of carbon atoms in sp2 hybrid orbitals, and the main chemical components are
carbon atoms and polar oxygen-containing functional groups, which is widely payed attention
as an excellent material. The specific surface area of graphene and graphene oxide is as high
as 2600m 2/g, which is about 1.5-2 times of that of conventional activated carbon, and
graphene and graphene oxide can be used as carriers of small molecules. Because of its special
structure and barrier effect, the selective release and sustained release of small molecules can
be controlled by adjusting the diameter of the internal pores.
Chitosan (CS), chemical name poly(1,4)-2-amino-2-deoxy-p-D-glucose, is natural
polysaccharide polymer obtained from a deacetylation derivative of chitin. Chitosan has the
advantages of excellent broad-spectrum antibacterial and good film-forming property, and
Chitosan is environment friendly, easy to degrade and non toxic and pollution-free. The
positive charge of chitosan in water can produce electrostatic interaction with negatively
charged graphene oxide. At the same time, the hydroxyl and carboxyl groups of porous
graphene oxide are easy to perform hydrogen-bonding interaction with the amino group of
nano chitosan, thus forming self-assembled structure. At the same time, the hydroxyl and
amino groups in chitosan molecular chain can also provide reduction stability for graphene
oxide nanomaterials. In addition, the good biocompatibility and biodegradability of chitosan
make it possible for chitosan based materials to be used in the field of biological agriculture.
SUMMARY The present disclosure is to provide a self-assembled nanosphere and its preparation
method and application in the sustained release of food preservative. The self-assembled
nanosphere has good sustained release effect on the small molecule preservative.
A self-assembled nanosphere and its preparation method and application method, characterized in that: immersing load into graphene oxide dispersion for 10 min under ultrasonic condition, and then drying with nitrogen to form nanoparticles, and then immersing the nanoparticles into chitosan solution for 10 min, then drying with nitrogen, and then repeated the above steps to prepare multilayer nanospheres; then immersing the multilayer nanospheres into 4,4'-Diaminostilbene-2,2'-disulfonic acid (DAS) solution for 30min and then taking the multilayer nanospheres out, drying with nitrogen, and irradiating by UV to prepare sustained-release self-assembled nanospheres. Preferably, the solid content of the homogeneous dispersion of the graphene oxide in water is 0.1-0.5mg/mL.
Graphene oxide can be used as material carrier because of its large specific surface area.
At the same time, its special structure has barrier effect and can control the sustained-release of small molecules. Ultrasonic treatment can increase the inner channel diameter of graphene
film, so as to selectively penetrate some small molecules. The release rate of small molecules
is controlled by adding the number of graphene oxide layers.
The chitosan ionized in water with positive charge can generate electrostatic interactions with the graphene oxide with negative charge. At the same time, the hydroxyl and carboxyl
groups of porous graphene oxide and the amino groups of nano-chitosan are prone to hydrogen bonding to form a self-assembled structure. In addition, the hydroxyl and amino
groups in the chitosan molecular chain can also provide reduction and stabilization for
graphene oxide nanomaterials.
The hydrophilic group of the chitosan makes the self-assembled nanospheres have film-forming property and biological adhesion property.
The present disclosure also provides an application method of self-assembled nanosphere,
including: Step 1: Adding the prepared loading material solution or emulsion to the graphene oxide
nanoparticle dispersion under ultrasound condition, and drying it with nitrogen to form
nanoparticles.
Step 2: Immersing the nanoparticles in the chitosan acetic acid solution, drying with nitrogen;
Step 3: Repeating Step 1 and Step 2;
Step 4: Immersing the nanospheres in 4,4'-diaminostilbene-2,2'-disulfonic acid solution
(DAS), drying with nitrogen, and irradiating with UV.
Graphene oxide can be used for loading because of its large specific surface area, and its
special structure has barrier effect, which can control the sustained-release of small molecules.
Ultrasonic treatment can increase the inner channel diameter of graphene film, so as to selectively penetrate some small molecules with a diameter of about 1 nm. The release rate of
small molecules is controlled by adding the number of graphene oxide layers.
Due to the solubility and instability of graphene, its application is limited. However, chitosan, as a natural cationic polymer polysaccharide, can form self-assembled spheres with
graphene oxide with negative charge in nano particle dispersion through intermolecular
hydrogen bonding and electrostatic interaction. The hydroxyl and amino groups in the chitosan
molecular chain can provide reduction stabilization for graphene oxide, and the hydrophilic groups of chitosan make the self-assembled nanospheres have film-forming and bioadhesive
properties.
Preferably, the preparation of loading material solution or emulsion is used the bottom-up anti-solvent precipitation method or the ionic gelation method in Step 1.
Preferably, the mass concentration of the graphene oxide is 0.1-0.5g/L due to the good
adsorption property of the graphene oxide. Preferably, since ultrasonic treatment can change the pore size of the graphene oxide, the
ultrasonic treatment time is 20 to 60 min.
Preferably, the positive charge of the chitosan acetic acid solution and the graphene oxide
with negative charge form a polyelectrolyte complex through electrostatic interaction, and the mass concentration of the chitosan acetic acid solution is 6 to 20 mg/L in Step 2.
Preferably, the immersion time of photosensitive crosslinker DAS is 15 to 45 min, and a
cross-linking reaction takes place 20 to 40 min under ultraviolet lamp irradiation, to form a covalent cross-linked network in multilayer film, so as to enhance the stability of the
nanosphere.
The advantageous effects of the present disclosure are as follows: The self-assembled nanospheres have the functions of loading and sustained-release, and can realize the selective release and the precise control of release rate of of small molecular loading material. Besides, it can be hydrated into a film during use.
DETAILED DESCRIPTION OF THE EMBODIMENTS Hereinafter, the present disclosure will be further described in detail through embodiments, the objective of which is to more specifically and clearly illustrate the content of the present disclosure without limiting the protection scope of the present disclosure. Embodiment 1 Step 1: Sodium nitroprusside is added into 0.3g/L graphene oxide nanoparticles dispersion solution, ultrasonic wave is performed for 20 minutes, and then dried with nitrogen, so as to prepare the nanoparticles; Step 2: The nanoparticles are immersed in 30 mg/L chitosan acetic acid solution for 10 min, and then dried with nitrogen; Step 3: Repeat Step 1 and Step 2 for 10 times; Step 4: The nanospheres are immersed in 4,4'-diaminostilbene-2,2'-disulfonic acid solution (DAS) for 20 min, dried with nitrogen, and irradiated by UV for 30 min; Step 5: The strawberries are placed in a closed container at 1 for storage; sodium nitroprusside self-assembled nanospheres are put into nylon bag and suspended above the container to release NO and inhibit the occurrence of chilling injury. Embodiment 2 Step 1: Clove essential oil emulsion is prepared by the ionic gel method; Step 2: The emulsion obtained in step 1 is added to the 0.5g/L graphene oxide nanoparticle dispersions, ultrasound is performed for 30min, and then dried with nitrogen to prepare nanoparticles; Step 3: The nanoparticles are immersed in 20 mg/L chitosan acetic acid solution for 10 min, and then dried with nitrogen; Step 4: Repeat step 1 and step 2 for 5 times; Step 5: The nanospheres are immersed in 4,4'-diaminostilbene-2,2'-disulfonic acid solution (DAS) for 15 min, dried with nitrogen, and irradiated by UV for 20 min; Step 6: the grapes are placed in the sealed container, and the clove essential oil self-assembled nanospheres are put into nylon cloth bag and suspended above the container to release clove essential oil slowly and inhibit bacteria. Embodiment 3 Step 1: Melatonin nanoparticles are prepared by a bottom-up anti-solvent precipitation method; Step 2: The melatonin nanoparticles obtained in step 1 are added into 0.4g/LA graphene oxide dispersion solution, ultrasound is performed for 20 minutes, and dried with nitrogen to prepare curcumin-graphene nanospheres; Step 3: The curcumin-graphene nanoparticles are immersed in 20 mg/L chitosan acetic acid solution for 10 min, and then dried with nitrogen; Step 4: Repeat step 1 and step 2 for 5 times Step 5: The nanospheres are immersed in 4,4'-diaminostilbene-2,2'-disulfonic acid solution (DAS) for 30 min, dried with nitrogen, and irradiated by UV for 30 min. Step 6: The prepared melatonin self-assembled nanospheres are hydrated to form an anti-oxidation film and preservative film for increasing plant stress resistance. Embodiment 4 Step 1: Natamycin nanoparticles are prepared by a bottom-up anti-solvent precipitation method; Step 2: 0.5g/L graphene oxide dispersion is added into natamycin nanoparticles obtained in step 1, ultrasound is performed for 20 minutes, and then dried with nitrogen to prepare curcumin-graphene nanospheres; Step 3: The natamycin-graphene nanoparticles are immersed in 30 mg/L chitosan acetic acid solution for 10 min, and then dried with nitrogen; Step 4: Repeat steps 1 and 2 for 3 times; Step 5: The nanospheres are immersed in 4,4'-diaminostilbene-2,2'-disulfonic acid solution (DAS) for 30 min, dried with nitrogen, and irradiated by UV for 30 min; Step 6: The prepared natamycin self-assembled nanospheres are hydrated to form an antibacterial film.

Claims (8)

  1. Editorial Note 2020102161 There is only one page of the claim
    What is claimed is: 1. A self-assembled nanosphere and its prparation method and application method, characterized in that: immersing loading material into dispersion of graphene oxide for 10 min under ultrasonic condition, and then drying with nitrogen to form nanoparticles, and then immersing the nanoparticles into chitosan solution for 10 min, then drying with nitrogen, and then rpeated the above steps to prpam multilayer nanospheres; then immersing the multilayer nanospheres into 4,4'-diaminostilbene-2,2'-disulfonic acid solution (DAS) for 30min and then taking the multilayer nanospheres out, drying with nitrogen, and irradiating by UV to prepare sustained-release self-assembled nanospheres.
  2. 2. The self-assembled nanosphem according to claim 1, characterized in that a solid content of homogeneous dispersion ofthe graphene oxide in water is 0.1-0.5g/L.
  3. 3. The self-assembled nanosphere according to claim 1, characterized in that a nano pore size of the graphene oxide is adjusted by changing ultrasonic time, so as to control a selective release of the loading material.
  4. 4. The self-assembled nanosphere according to claim 1, characterized in that a lease rate of the loading materialis pocisely controlled by accurately controlling the number oflayers ofgraphene.
  5. 5. The self-assembled nanosphere according to claim 1, characterized in that the chitosan with positive charge ionized in water is able to self-assemble with the graphene oxide with negative charge though electrostatic interaction and hydrogen bonding.
  6. 6. The self-assembled nanosphere according to claim 1, characterized in that a immersion time of photosensitive crosslinker DAS is 15 to 45 min, and a cross-linking reaction takes place 20 to 40 min under ultraviolet lamp irradiation, to form a covalent cross-linked network in multilayer film and enhance a stability of the nanosphere.
  7. 7. The self-assembled nanosphere according to claim 1, characterized in that the self-assembled nanosphere are prpared into spheres for controlling the sustained-oelease of small molecules; further, an outer layer is chitosan, and the chitosan is configured to be hydrated into a film when used.
  8. 8. The self-assembled nanosphere according to claim 1, characterized in that the loading material is added into the graphene oxide by ionic gelation method or bottom-up anti-solvent prcipitation method.
AU2020102161A 2020-09-07 2020-09-07 Self-assembled nanosphere and preparation method and application method thereof Ceased AU2020102161A4 (en)

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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN114197088A (en) * 2021-11-09 2022-03-18 华南理工大学 Method for preparing nano-fiber or nano-microsphere by ultrasonic induction and film formed by nano-material

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN114197088A (en) * 2021-11-09 2022-03-18 华南理工大学 Method for preparing nano-fiber or nano-microsphere by ultrasonic induction and film formed by nano-material

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