WO2022165877A1 - Microsphère d'hydrogel à nanopores de chitosane-acide malique, son procédé de préparation et son application - Google Patents

Microsphère d'hydrogel à nanopores de chitosane-acide malique, son procédé de préparation et son application Download PDF

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WO2022165877A1
WO2022165877A1 PCT/CN2021/077774 CN2021077774W WO2022165877A1 WO 2022165877 A1 WO2022165877 A1 WO 2022165877A1 CN 2021077774 W CN2021077774 W CN 2021077774W WO 2022165877 A1 WO2022165877 A1 WO 2022165877A1
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chitosan
malic acid
preparation
silica
nano
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PCT/CN2021/077774
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English (en)
Chinese (zh)
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解万翠
杨锡洪
宋琳
车红霞
董秀芳
李红燕
呼晓群
郭浩
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青岛科技大学
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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
    • B01J20/02—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material
    • B01J20/10—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising silica or silicate
    • B01J20/103—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising silica or silicate comprising silica
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
    • B01J20/22—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising organic material
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
    • B01J20/22—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising organic material
    • B01J20/24—Naturally occurring macromolecular compounds, e.g. humic acids or their derivatives
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
    • B01J20/28—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties
    • B01J20/28014—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties characterised by their form
    • B01J20/28016—Particle form
    • B01J20/28021—Hollow particles, e.g. hollow spheres, microspheres or cenospheres
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
    • B01J20/28—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties
    • B01J20/28014—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties characterised by their form
    • B01J20/28047—Gels
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F1/00—Treatment of water, waste water, or sewage
    • C02F1/28—Treatment of water, waste water, or sewage by sorption
    • C02F1/286—Treatment of water, waste water, or sewage by sorption using natural organic sorbents or derivatives thereof
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F1/00—Treatment of water, waste water, or sewage
    • C02F1/28—Treatment of water, waste water, or sewage by sorption
    • C02F1/288—Treatment of water, waste water, or sewage by sorption using composite sorbents, e.g. coated, impregnated, multi-layered
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F2303/00—Specific treatment goals
    • C02F2303/04—Disinfection

Definitions

  • the invention relates to the technical field of ensuring the safety of aquatic food and preparing paralytic shellfish toxin biological adsorbents, in particular to malic acid-chitosan nanoporous hydrogel microspheres and a preparation method and application thereof.
  • Paralytic shellfish toxins are mainly derived from dinoflagellates, freshwater cyanobacteria or symbiotic bacteria of harmful algae. They are a class of marine biofilm neurotoxins that specifically block Na + channels on nerve cell membranes, causing paralysis and even death. Filter-feeding shellfish, some fish, etc. ingest poisonous algae, and the toxins accumulate in the body and can be transmitted to humans through the food chain, posing a serious threat to public safety, human health and marine economy. There is currently no effective antidote or medication for paralytic shellfish poisoning. In order to reduce the harm of paralytic shellfish poisoning to humans, it is particularly important to develop high-efficiency adsorbents with large adsorption capacity and low cost.
  • Chitosan contains amino and hydroxyl groups, making it a macromolecular candidate for biosorbents to remove heavy metal ions or toxins.
  • Chitosan is non-toxic, does not produce secondary pollution, and can be decomposed through biological catabolism.
  • this material also has the problems of poor acid stability, low porosity, and low specific surface area, which greatly limit its application.
  • physical and chemical cross-linking modification methods are applied to increase the porosity of materials and the number of adsorption sites, which have great potential to remove toxins. Malic acid is present in the metabolism of most organisms.
  • the purpose of the present invention is to provide malic acid-chitosan nanoporous hydrogel microspheres and preparation method and application thereof, so as to solve the problems existing in the above-mentioned prior art.
  • the present invention provides following scheme:
  • the invention provides a preparation method of malic acid-chitosan nanoporous hydrogel microspheres, the specific steps include:
  • step (2) nano-silica and glycerol are added to the hydrosol prepared in step (1), after the nano-silica is completely dissolved, the malic acid-chitosan nanopores are prepared by washing, freeze-drying, grinding and sieving Hydrogel Microspheres.
  • the obtained mixture is first added with pure water to prepare a dispersion, and then vigorously stirred at room temperature to form a uniform hydrosol.
  • the mass ratio of the malic acid to the chitosan is 1:3-1:6.
  • the mass fraction of the mixture of malic acid and chitosan in the dispersion liquid is 0.5-2.5%.
  • the mass fraction of the nano-silica in step (2) is 0.2-0.8%, and the mass fraction of glycerol is 0.5-1.5%.
  • the specification of the sieve used during the sieving described in step (2) is a 100-mesh sieve.
  • Nano-silica and glycerin are added to the hydrosol prepared in step (1), and after stirring and ultrasonic treatment, the obtained uniform sol is added dropwise to a NaOH solution with a temperature of 60-100° C. to dissolve the nano-silica.
  • the ultrasonic treatment time is 1-3 hours.
  • the mass fraction of the NaOH solution is 8-12%.
  • the present invention also provides malic acid-chitosan nanoporous hydrogel microspheres prepared by the preparation method of the malic acid-chitosan nanoporous hydrogel microspheres.
  • the present invention also provides an application of the malic acid-chitosan nanoporous hydrogel microspheres in removing paralytic shellfish toxins in water bodies.
  • the detoxification rate of the malic acid-chitosan nanoporous hydrogel microspheres (SiO 2 -MA-CS) prepared by the present invention to the paralytic shellfish toxin reaches 92.71%, and the MA-CS is effective for the paralytic shellfish toxin.
  • the detoxification rate was 54.31%, and the detoxification effect of SiO 2 -MA-CS was obviously better than that of MA-CS.
  • the malic acid-chitosan nanoporous hydrogel microspheres prepared by the invention can be used as high-efficiency adsorbents to adsorb and remove paralytic shellfish toxins in water; the preparation method disclosed by the invention is simple, easy to use, and easy to use after drying. Preservation can be applied to the removal of shellfish toxins in aqueous solutions, and has great application significance for the pollution of shellfish toxins and the improvement of product safety.
  • Fig. 1 is the synthesis schematic diagram of malic acid-chitosan nanoporous hydrogel microsphere of the present invention
  • Fig. 2 is the infrared spectrum of CS, MA-CS, SiO 2 -MA-CS;
  • Fig. 3 is the scanning electron microscope image of CS, MA-CS and SiO 2 -MA-CS magnified by 10000 times;
  • Figure 4 is the XRD patterns of CS, MA-CS and SiO 2 -MA-CS; wherein A is CS, B is MA-CS, and C is SiO 2 -MA-CS;
  • Figure 5 shows the adsorption results of hydrogel microspheres on paralytic shellfish toxin in aqueous solution.
  • step (2) Add 0.4% nano-silica and 1.0% glycerol to the hydrosol in step (1), stir at room temperature for 2 hours, ultrasonically treat for 2 hours, and drop the obtained uniform sol into a The mass fraction of 10% NaOH solution was kept at 80 °C for 2 h to dissolve the silica particles and generate a porous structure. Finally, washed with distilled water to remove the remaining NaOH, grinded through a 100-mesh sieve after freeze-drying, collected and stored in a desiccator, as shown in Figure 1 is the synthesis schematic diagram of malic acid-chitosan nanoporous hydrogel microspheres .
  • step (2) Add 0.2% nano-silica and 0.5% glycerol to the hydrosol in step (1), stir at room temperature for 2 hours, ultrasonically treat for 1 hour, and drop the obtained uniform sol into a The mass fraction of 8% NaOH solution was kept at 60 °C for 2 h to dissolve the silica particles and generate a porous structure. Finally, washed with distilled water to remove the remaining NaOH, lyophilized and ground through a 100-mesh sieve, collected and stored in a desiccator.
  • step (2) adding 0.6% nano-silica and 1.0% glycerol to the hydrosol described in step (1), stirring at room temperature for 3 hours, ultrasonically treating for 2 hours, and adding the obtained uniform sol dropwise to a
  • the mass fraction of 10% NaOH solution was kept at 80 °C for 1 h to dissolve the silica particles and generate a porous structure.
  • step (1) (2) adding 0.8% mass fraction of nano-silica and 1.5% mass fraction of glycerol to the hydrosol in step (1), stirring at room temperature for 4 hours, ultrasonically treating for 3 hours, and adding the obtained uniform sol dropwise to The mass fraction of 12% NaOH solution was kept at 100 °C for 3 h to dissolve the silica particles and generate a porous structure. Finally, washed with distilled water to remove residual NaOH, lyophilized and ground through a 100-mesh sieve, collected and stored in a desiccator.
  • Example 1 The untreated chitosan (Chitosan, CS, deacetylation degree above 80%, food grade) in Example 1 and the MA-CS (malic acid-chitosan water) prepared in the step (1) described in Example 1 sol, MA-CS) and the SiO 2 -MA-CS (malic acid-chitosan nanoporous hydrogel microspheres) finally prepared in Example 1 were respectively tested for structural characterization.
  • the stretching vibration absorption peaks of -OH and -NH2 are at 3442 cm-1, and the stretching vibration absorption peak of -CH is at 2920 cm- 1 , the amide band at 1637 cm -1 , the bending vibration absorption peak of -NH2 at 1616 cm-1, the bending vibration absorption peak of -CH at 1383 cm -1 , the stretching vibration absorption peak of CO in C3 - OH
  • the peak is at 1078 cm -1
  • the stretching vibration absorption peak of CO in C 6 -OH is at 1030 cm -1
  • the stretching vibration absorption peak of glucosamine ring is at 895 cm -1 .
  • the surface roughness of SiO 2 -MA-CS increases, and a clear network structure can be seen.
  • the addition of nano-silica makes the adsorbent (malic acid-chitosan)
  • the porosity of nanoporous hydrogel microspheres is further enhanced, and the specific surface area of adsorption is increased.
  • the first peak of CS is about 20, which is attributed to the thick crystalline conformation of chitosan.
  • the XRD patterns of MA-CS and SiO 2 -MA-CS have no obvious peaks, only one center at A broad peak at 20° usually accompanies the diffraction of polysaccharides.
  • the difference in the diffraction angle of the peak at 20 may be related to the difference in the degree of deacetylation of the CS/MA/SiO 2 blends and the difference in the recombination mode.
  • the detection of paralytic shellfish toxins adopts GB5009.213-2016 enzyme-linked immunosorbent assay.
  • Add 10 grams of homogeneous toxin-storing oyster meat samples add 70 mL of 0.1 mol/L hydrochloric acid solution, boil and stir for 5 minutes, 6000 r/min Centrifuge for 10 minutes and take the supernatant for detection.
  • the detoxification rate of SiO 2 -MA-CS to paralytic shellfish toxin reached 92.71%
  • the detoxification rate of MA-CS to paralytic shellfish toxin was 54.31%
  • SiO 2 -MA-CS The detoxification effect was significantly better than that of MA-CS.
  • malic acid-chitosan nanoporous hydrogel microspheres prepared by the present invention can be used as high-efficiency adsorbents to adsorb and remove paralytic shellfish toxins in aqueous solutions.

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Analytical Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Engineering & Computer Science (AREA)
  • Hydrology & Water Resources (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Environmental & Geological Engineering (AREA)
  • Water Supply & Treatment (AREA)
  • Dispersion Chemistry (AREA)
  • Inorganic Chemistry (AREA)
  • Solid-Sorbent Or Filter-Aiding Compositions (AREA)
  • Pharmaceuticals Containing Other Organic And Inorganic Compounds (AREA)
  • Polysaccharides And Polysaccharide Derivatives (AREA)

Abstract

L'invention concerne une microsphère d'hydrogel à nanopores de chitosane-acide malique, son procédé de préparation et une application de celle-ci, se rapportant aux domaines techniques de la garantie de la sécurité des aliments aquatiques et la préparation d'adsorbants biologiques de toxines de crustacés paralysantes. Le procédé de préparation de la microsphère d'hydrogel à nanopores de chitosane-acide malique comprend spécifiquement : la préparation d'acide malique et de chitosane dans un hydrogel ; puis ajouter du dioxyde de silicium nanométrique et de la glycérine dans l'hydrogel préparé, l'ajout d'hydroxyde de sodium, la dissolution complète du dioxyde de silicium nanométrique dans des conditions alcalines pour former des nanopores uniformément répartis, le lavage, le lyophilisation, et le broyage et le tamisage pour obtenir la microsphère d'hydrogel à nanopores de chitosane-acide malique. La microsphère d'hydrogel à nanopores de chitosane-acide malique préparée peut être utilisée en tant qu'adsorbant efficace pour adsorber et éliminer les toxines paralysantes de crustacés dans un corps d'eau. Le procédé de préparation est simple, l'adsorbant préparé est pratique à utiliser et facile à stocker après séchage, et la présente invention présente une grande importance d'application dans la lutte contre la contamination de la toxine de crustacés et améliore la sécurité du produit.
PCT/CN2021/077774 2021-02-05 2021-02-25 Microsphère d'hydrogel à nanopores de chitosane-acide malique, son procédé de préparation et son application WO2022165877A1 (fr)

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CN113317314A (zh) * 2021-07-02 2021-08-31 苏州乾冠新纺织科技有限公司 一种纳米级微胶囊及其制备方法
CN114887557B (zh) * 2022-05-26 2023-07-11 江南大学 一种co2-温度双重响应型壳聚糖复合微胶囊的制备方法及其应用

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