WO2019095753A1 - Hydrogel composite à boîtes quantiques en cellulose/phosphore noir et son procédé de préparation - Google Patents

Hydrogel composite à boîtes quantiques en cellulose/phosphore noir et son procédé de préparation Download PDF

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WO2019095753A1
WO2019095753A1 PCT/CN2018/100243 CN2018100243W WO2019095753A1 WO 2019095753 A1 WO2019095753 A1 WO 2019095753A1 CN 2018100243 W CN2018100243 W CN 2018100243W WO 2019095753 A1 WO2019095753 A1 WO 2019095753A1
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cellulose
black phosphorus
phosphorus quantum
composite hydrogel
quantum dot
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PCT/CN2018/100243
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Chinese (zh)
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张晗
邢晨阳
陈世优
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深圳大学
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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
    • C08J3/075—Macromolecular gels
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K41/00—Medicinal preparations obtained by treating materials with wave energy or particle radiation ; Therapies using these preparations
    • A61K41/0052—Thermotherapy; Hyperthermia; Magnetic induction; Induction heating therapy
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K47/00—Medicinal preparations characterised by the non-active ingredients used, e.g. carriers or inert additives; Targeting or modifying agents chemically bound to the active ingredient
    • A61K47/30—Macromolecular organic or inorganic compounds, e.g. inorganic polyphosphates
    • A61K47/36—Polysaccharides; Derivatives thereof, e.g. gums, starch, alginate, dextrin, hyaluronic acid, chitosan, inulin, agar or pectin
    • A61K47/38—Cellulose; Derivatives thereof
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K9/00—Medicinal preparations characterised by special physical form
    • A61K9/0012—Galenical forms characterised by the site of application
    • A61K9/0019—Injectable compositions; Intramuscular, intravenous, arterial, subcutaneous administration; Compositions to be administered through the skin in an invasive manner
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K9/00—Medicinal preparations characterised by special physical form
    • A61K9/06—Ointments; Bases therefor; Other semi-solid forms, e.g. creams, sticks, gels
    • 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
    • C08J3/24—Crosslinking, e.g. vulcanising, of macromolecules
    • 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
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/02—Elements
    • C08K2003/026—Phosphorus

Definitions

  • the invention belongs to the field of preparation of black phosphorus-based nanomaterials, and particularly relates to a cellulose/black phosphorus quantum dot composite hydrogel and a preparation method thereof.
  • Black phosphorene is a new type of direct band gap two-dimensional material. Its band gap can be adjusted from 0.3eV (body state) to 1.5eV (single layer) through its number of layers, which can absorb visible light to communication infrared. Range wavelength light, combined with its high carrier mobility, high on-off ratio, and good photothermal conversion effect and biocompatibility, make it extremely large in the semiconductor field, optoelectronic field and biological field. Potential advantage.
  • the inorganic nanomaterial-black phosphorus has insufficient dispersibility in biological fluids and is prone to sedimentation, and its photothermal effect has obvious regional differences.
  • the structure of the black phosphorus-based material is too single, and the stability of black phosphorus in it is poor, and it is easy to be liberated, which cannot satisfy the targeting and durability required for the tumor treatment process. Therefore, it is necessary to expand the form of black phosphorus in the biomedical field.
  • Cellulose is the most abundant renewable resource on the earth. It has the advantages of complete biocompatibility and complete biodegradability. However, due to its high crystallinity and intramolecular/intermolecular hydrogen bonding, cellulose is difficult to dissolve and refractory. This has made it difficult to form and shape, which greatly limits the development of cellulose in biomedical materials.
  • the present invention provides a cellulose/black phosphorus quantum dot composite hydrogel having high stability in the composite hydrogel, the cellulose/black phosphorus quantum dot composite hydrogel. It has good dispersibility in biological fluids, exhibits excellent characteristics of high photothermal conversion efficiency, complete biodegradability, complete biocompatibility, biosafety, etc., and has good mechanical strength, and is expected to be applied in biomedicine. In the field.
  • the present invention provides a cellulose/black phosphorus quantum dot composite hydrogel comprising a three-dimensional network structure of cellulose, and a black phosphorus quantum supported on the three-dimensional network structure of the cellulose. point.
  • the black phosphorus quantum dots Due to the weak interaction between the black phosphorus quantum dots, it is impossible to construct a gel of pure black phosphorus quantum dots by self-assembly behavior.
  • the black phosphorus quantum dots are wound by the three-dimensional network structure formed by the cellulose molecules.
  • black phosphorus quantum dots are loaded into the system to form a cellulose/black phosphorus quantum dot composite hydrogel.
  • the composite hydrogel significantly improves the dispersibility of the black phosphorus quantum dots and prevents agglomeration between the black phosphorus quantum dots.
  • the three-dimensional network structure of cellulose comprises a three-dimensional network structure in which cellulose or a cellulose derivative itself is joined, or a three-dimensional network structure in which cellulose and/or a cellulose derivative is formed by a crosslinking agent.
  • the cellulose derivative comprises cellulose modified with at least one of graphene oxide, chitosan, cyclodextrin and gelatin, or carboxylated, silylated cellulose.
  • the crosslinking agent includes at least one of epichlorohydrin and isocyanate, but is not limited thereto.
  • the cellulose three-dimensional network structure has a pore structure with a pore diameter of 20-200 nm.
  • the pore structure has a pore diameter of 50 to 150 nm.
  • the composite hydrogel has a water content of 85%-98%.
  • the composite hydrogel has a large water content and is easily dispersed in an aqueous solution or a biological body fluid, and has excellent compatibility with body fluids, which can improve the adhesion of the black phosphorus quantum dots to biological cells and tissues.
  • the size of the black phosphorus quantum dots is 1-5 nm.
  • the mass ratio of the cellulose to the black phosphorus quantum dots in the three-dimensional network structure of the cellulose is 100: (0.0001-50), preferably 100: (0.001-10), further preferably 100: (0.001-5) More preferably, it is 100:0.05.
  • the three-dimensional network structure of cellulose is a three-dimensional network structure in which cellulose molecules and a crosslinking agent are crosslinked.
  • the mass ratio of the cellulose to the crosslinking agent in the three-dimensional network structure of the cellulose is 100: (1.372-13.71). It is preferably 100: (4.116 to 13.71), further preferably 100: (4.116 to 6.86).
  • the cellulose is one or more of lignocellulose, bamboo cellulose, wood cellulose pulp, cotton cellulose, microcrystalline cellulose, hydroxyethyl cellulose, carboxymethyl cellulose.
  • the cellulose/black phosphorus quantum dot composite hydrogel provided by the first aspect of the invention has a cellulose three-dimensional network structure as a carrier, and the black phosphorus quantum dot is stably loaded in the three-dimensional network structure, and the black phosphorus quantum dot is improved. Dispersion prevents the agglomeration between black phosphorus quantum dots and expands the product form of black phosphorus.
  • the cellulose/black phosphorus quantum dot composite hydrogel has good dispersibility in biological fluid, and exhibits excellent characteristics such as high photothermal conversion efficiency, complete biodegradability, complete biocompatibility, and biosafety. It has good mechanical strength and is expected to be used in the field of biomedicine, especially in the field of cancer treatment.
  • the present invention provides a method for preparing a cellulose/black phosphorus quantum dot composite hydrogel, comprising the steps of:
  • the cellulose/black phosphorus quantum dot composite hydrogel prepared by the above method comprises a cellulose three-dimensional network structure crosslinked by cellulose and a crosslinking agent, and further comprises black phosphorus supported in the three-dimensional network structure of the cellulose. Quantum dots. Further, the surface of the black phosphorus quantum dot is covered by the cellulose three-dimensional network structure.
  • the crosslinking agent is a substance that is not completely hydrophobic.
  • the crosslinking agent carries at least one of an epoxy group (COC) and an isocyanate group (NCO), such that the functional groups in the crosslinking agent can be combined with the cellulose molecular chain -OH cross-linking reaction occurs.
  • the crosslinking agent is selected from one or more of epichlorohydrin and isocyanate, but is not limited thereto. Further preferably, the crosslinking agent is epichlorohydrin.
  • the hydroxyl functional group (-OH) on the cellulose molecular chain undergoes a nucleophilic reaction with the carbon atom on the epoxy functional group (C-O-C) in the epichlorohydrin, and crosslinks to form a hydrogel system.
  • the mixed solvent is pre-cooled to -15 to -5 °C. This facilitates better dissolution of the cellulose powder.
  • the mixed solvent is pre-cooled to -12 °C.
  • the cellulose powder has a particle size of from 10 to 30 microns.
  • the rotational speed of the vigorous stirring is 7000 to 10000 rpm, and the time of the vigorous stirring is 1-3 minutes.
  • the high-speed stirring rotation speed is 7000 to 10000 rpm, and the high-speed stirring time is 1-3 minutes.
  • the stirring speed and the stirring time of the vigorous stirring and the high-speed stirring may be the same or different.
  • the ultrasonic treatment has a power of 300-500 W and a time of 10-30 minutes.
  • the temperature of the crosslinking reaction is 70 to 85 °C.
  • it can be 72, 75, 78, 80 or 82 °C.
  • the cellulose regeneration liquid is a dilute sulfuric acid solution having a mass fraction of 5% to 10%.
  • the volume ratio of the crosslinking reactant to the dilute sulfuric acid solution is 1: (2-3). Further, the volume of the dilute sulfuric acid solution used is 10-15 mL.
  • the cross-linking reactant is a hydrogel of cellulose/crosslinking agent/black phosphorus quantum dot/sodium hydroxide/urea.
  • the dialysis time is 3-7 days.
  • the purpose of dialysis is mainly to remove strong alkali, urea and regenerant.
  • the mass concentration of the strong base is 5-15%, and the mass concentration of urea is 10-15%.
  • the strong base is one or more of sodium hydroxide, potassium hydroxide and lithium hydroxide.
  • the mass ratio of the mixed solvent to the cellulose in the cellulose solution is 100: (1-4).
  • the volume ratio of the volume of the cellulose solution to the crosslinking agent is 100: (0.2-2.0).
  • the mass ratio of the volume of the cellulose solution to the crosslinking agent is 100: (0.236-2.36) mL/g.
  • the mass ratio of the mass of the cellulose solution to the crosslinking agent is 100: (0.212-2.12).
  • the mass ratio of the cellulose to the black phosphorus quantum dots is 100: (0.0001-50).
  • it may be 100:0.01, 100:0.03, 100:0.05, 100:0.1, 100:0.5, 100:1, 100:5, 100:10.
  • It is preferably 100: (0.001 to 10), further preferably 100: (0.001 to 5), more preferably 100: 0.05.
  • the black phosphorus quantum dot can generate heat under the illumination of near-infrared light (such as 808 nm), and the temperature can be raised from room temperature to up to 150 ° C, and the cancer can be killed by regulating the content in the composite hydrogel.
  • the desired temperature of the cells such as 43-60 ° C
  • black phosphorus quantum dots can biodegrade in vivo. Its degradation products are safe phosphates, showing good biocompatibility and biosafety.
  • the mass ratio of the cellulose to the black phosphorus quantum dots is 100: (0.0001-0.01).
  • the composite hydrogel can be irradiated with an 808 nm laser having an irradiation power of 0.5/cm 2 , and the photothermal equilibrium temperature reaches 43.5-60° C., so that the composite hydrogel can have an irradiation power of 1.0/ Under the illumination of cm 2 of 808 nm laser, the photothermal equilibrium temperature reached 48-75 ° C. It can be seen that when the black phosphorus quantum dots of lower quality are contained, the composite hydrogel can be given a good photothermal effect of killing tumor cells.
  • the preparation method of the black phosphorus quantum dots is not limited, and may be prepared in the following manner:
  • the reflux time is from 12 to 24 hours.
  • the quantum dots have a size of 1-5 nm.
  • the ratio of the mass of the black phosphorus to the total volume of the organic solvent is (0.25-1) mg/mL.
  • the milling time is 20-60 min and the milling is carried out under anaerobic conditions.
  • the surface energy of the organic solvent matches the surface energy of the two-dimensional black phosphorus, and there is a certain interaction between the two to balance the energy required to peel off the bulk black phosphorus.
  • the organic solvent is selected from the group consisting of N-methylpyrrolidone (NMP), dimethyl sulfoxide (DMSO), N,N-dimethylformamide (DMF), N-cyclohexyl-2-pyrrolidone (CHP), and One or more of isopropyl alcohol (IPA), but is not limited thereto.
  • the low speed centrifugation has a rotational speed of 5000-8000 rpm and a time of 20-40 min. Further preferably, the low speed centrifugal speed is 6000-8000 rpm.
  • the high speed centrifugation has a rotational speed of 15000-18000 rpm for a period of 30-60 min. Further preferably, the high speed centrifugation is 16000-18000 rpm.
  • the vacuum drying has a drying temperature of 50-80 ° C and a drying time of 12-24 h.
  • the formation mechanism of the cellulose/black phosphorus quantum dot composite hydrogel provided by the invention is as follows: 1) Firstly, the cellulose chain is dissolved by using a low-temperature alkaline mixed solvent of sodium hydroxide, urea and water to dissolve the cellulose. The hydrogen bond network is gradually opened to form the sodium and hydroxide ions of the hydrate, forming a new hydrogen bond network with the molecular chain of cellulose, and the urea molecular hydrate prevents the self-ligation of the cellulose molecular chain.
  • the final cellulose molecular chain is dissolved in an aqueous solution in the form of a tubular clathrate, which overcomes the high crystallinity and intramolecular/intermolecular strong hydrogen bonding of cellulose which is difficult to dissolve in common solvents including aqueous solvents.
  • the alkaline solution also helps to improve the stability of the black phosphorus quantum dots and protect the black phosphorus from oxidation. 2)
  • the aqueous cellulose solution is mixed with the black phosphorus quantum dots and the crosslinking agent under high-speed stirring, after ultrasonication, the cellulose molecular chain and the crosslinking agent undergo nucleophilic reaction at a certain temperature, and the black phosphorus quantum dots are simultaneously chiseled.
  • the black phosphorus quantum dots are in an extremely stable state, forming a three-dimensional network of cellulose/crosslinking agent/black phosphorus quantum dot/sodium hydroxide/urea hydrogel.
  • the cellulose/crosslinking agent/black phosphorus quantum dot/sodium hydroxide/urea hydrogel is regenerated after being immersed in a dilute sulfuric acid solution, that is, the cellulose molecular chain is precipitated and appears to be convenient.
  • the regenerated hydrogel is taken out, and after soaking in water, sodium hydroxide and urea can be removed to finally obtain a cellulose/black phosphorus quantum dot composite hydrogel.
  • the black phosphorus quantum dots are stably supported in a three-dimensional network structure in which cellulose and a crosslinking agent are crosslinked, and the black phosphorus quantum is blocked by the cellulose macromolecular chain.
  • the point is in an extremely stable state, and agglomeration sedimentation is not easy to occur, so that the composite hydrogel has a relatively uniform and stable photothermal effect, and the photothermal effect has almost no regional difference.
  • the composite hydrogel contains sufficient moisture to be easily dispersed in an aqueous solution or a biological body fluid, and has excellent compatibility with body fluids, which can improve the adhesion of the black phosphorus quantum dots to biological cells and tissues. Attached.
  • the composite hydrogel when used as an anticancer therapeutic system, it can be directly injected into a tumor site by means of "intratumoral injection".
  • the cellulose-based gel framework of the composite hydrogel can also fix other hydrophilic anticancer drugs, and provide multi-mode comprehensive treatment for targeted therapy, photothermal therapy and chemotherapy of tumor cells.
  • the composite hydrogel is also fully biodegradable, fully biocompatible, biosafe, etc. Excellent characteristics.
  • the preparation method of the cellulose/black phosphorus quantum dot composite hydrogel provided by the second aspect of the invention has the advantages of simple process, green environmental protection, excellent performance and stable uniformity of the obtained product.
  • TEM 1 is a transmission electron microscope (TEM) photograph of a black phosphorus quantum dot used in an embodiment of the present invention: (a) a low resolution photograph (scale is 100 nm); (b) a high resolution topography photograph (scale 10 nm).
  • TEM transmission electron microscope
  • FIG. 2 is an atomic force microscope (AFM) photograph of a black phosphorus quantum dot used in an embodiment of the present invention, wherein the scale is 1.0 ⁇ m.
  • AFM atomic force microscope
  • Figure 3 is a macroscopic photograph of a cellulose hydrogel (Comparative Example 4) and a cellulose/black phosphorus quantum dot composite hydrogel (Example 4).
  • Figure 4 is a scanning electron microscope (SEM) photograph of the aerogel obtained by freeze-drying a hydrogel: (a) aerogel corresponding to cellulose hydrogel (Comparative Example 4); (b) Cellulose/Black Aerogel corresponding to the phosphor quantum dot composite hydrogel (Example 4).
  • Step (1) A uniform size black phosphorus quantum dot solid is prepared by a liquid phase stripping method, and the specific steps are as follows:
  • NMP N-methylpyrrolidone
  • Step (2) Preparing an alkaline aqueous solution of transparent and uniform cellulose, the specific steps of which are as follows:
  • Step (3) Preparation of a composite hydrogel of cellulose/black phosphorus quantum dots, the specific steps of which are as follows:
  • the composite hydrogel of cellulose/black phosphorus quantum dots prepared in the embodiment of the invention comprises a three-dimensional network structure in which cellulose molecules and a crosslinking agent are crosslinked, and a black phosphorus quantum dot supported in the three-dimensional network structure.
  • a composite hydrogel for preparing cellulose/black phosphorus quantum dots differs from Example 1 in that the mass ratio of cellulose to black phosphorus quantum dot solids in step 3-a) is 100:0.01.
  • the composite hydrogel for preparing cellulose/black phosphorus quantum dots differs from Example 1 in that the mass ratio of cellulose to black phosphorus quantum dot solids in step 3-a) is 100:0.03.
  • the composite hydrogel for preparing cellulose/black phosphorus quantum dots differs from Example 1 in that the mass ratio of cellulose to black phosphorus quantum dot solids in step 3-a) is 100:0.05.
  • a composite hydrogel for preparing cellulose/black phosphorus quantum dots differs from Example 1 in that the mass ratio of cellulose to black phosphorus quantum dot solids in step 3-a) is 100:5.
  • a composite hydrogel for preparing cellulose/black phosphorus quantum dots differs from Example 1 in that the mass ratio of cellulose to black phosphorus quantum dot solids in step 3-a) is 100:10.
  • a composite hydrogel for preparing cellulose/black phosphorus quantum dots differs from Example 1 in that the mass ratio of cellulose to black phosphorus quantum dot solids in step 3-a) is 100:50.
  • the present invention also provides the following comparative examples:
  • Step (1) First, prepare an alkaline aqueous solution of transparent and uniform cellulose, and the specific steps are as follows:
  • Step (2) Preparation of a cellulose hydrogel, the specific steps of which are as follows:
  • Comparative Example 2 The difference from Comparative Example 1 was that the mass ratio of the mixed solvent to the cellulose was 100:2, and the ratio of the volume of the cellulose solution to the epichlorohydrin was 100:0.4.
  • Comparative Example 3 The difference from Comparative Example 1 was that the mass ratio of the mixed solvent to the cellulose was 100:3, and the volume ratio of the cellulose solution to the epichlorohydrin was 100:0.6.
  • Comparative Example 4 The difference from Comparative Example 1 was that the mass ratio of the mixed solvent to the cellulose was 100:4, and the ratio of the volume of the cellulose solution to the epichlorohydrin was 100:1.0.
  • Comparative Example 5 The difference from Comparative Example 1 was that the mass ratio of the mixed solvent to the cellulose was 100:4, and the ratio of the volume of the cellulose solution to the epichlorohydrin was 100:1.4.
  • Comparative Example 6 The difference from Comparative Example 1 was that the mass ratio of the mixed solvent to the cellulose was 100:4, and the ratio of the volume of the cellulose solution to the epichlorohydrin was 100:2.0.
  • FIG. 1 is a transmission electron microscope micromorphology diagram of a black phosphorus quantum dot used in an embodiment of the present invention, (a) being a low resolution photograph; and (b) being a high resolution photograph.
  • the microscopic morphology of the black phosphorus quantum dots was tested as follows: Instrumentation: High resolution transmission electron microscope; Model: FEI Tecnai G 2 F30; Test high voltage: 300 kV.
  • the size of the black phosphorus quantum dots is about 1-3 nm; as can be seen from (b) of FIG. 1, the black phosphorus quantum dots show obvious lattice fringes, indicating that the present invention
  • the black phosphorus quantum dot has a good crystal structure; its lattice size is 0.223 nm, which corresponds to the (014) diffractive surface.
  • FIG. 2 is an atomic force microscope photograph of a black phosphorus quantum dot used in the present invention.
  • the test conditions of the height map of the black phosphorus quantum dots are as follows: Instrumentation: High resolution atomic force microscope; Model: Brooke scanning probe microscope; Scan mode: Intelligent scanning mode. As can be seen from Fig. 2, the thickness of these black phosphorus quantum dots is in the range of 1-5 nm.
  • Figure 3 provides a macroscopic photograph of a cellulose hydrogel (Comparative Example 4) and a cellulose/black phosphorus quantum dot (Example 4). It can be seen from Fig. 3 that the pure cellulose hydrogel (Comparative Example 4) has a colorless and translucent "jelly-type" macroscopic morphology as a whole; and after the black phosphorus quantum dot is successfully introduced, the obtained cellulose/black phosphorus quantum dot is obtained.
  • the composite hydrogel (Example 4) was generally light brown in color and had a sharp color contrast.
  • Figure 4 provides a scanning electron micrograph of a corresponding aerogel obtained after freeze drying of a cellulose hydrogel (Comparative Example 4) and a cellulose/black phosphorus quantum dot composite hydrogel (Example 4).
  • the test conditions were as follows: To test the macromolecular porous structure in the cellulose hydrogel, the tested hydrogel (the cellulose hydrogel of Comparative Example 4 and the cellulose/black phosphorus quantum dot composite hydrogel of Example 4) First, the corresponding aerogel structure was obtained by freeze-drying, wherein the experimental conditions of freeze-drying were: temperature: -80 ° C; time: 72 hours. Then, the micromorphology was tested, and the instrument equipment used was: cold field emission scanning electron microscope; model: SEM-Hitachi SU8010; test voltage: 3 kV; silver plating time of sample surface: 20 seconds.
  • both types of aerogels exhibit significant porosity, which is determined by the three-dimensional gel network structure of cellulose.
  • the aerogel corresponding to the cellulose/epichlorohydrin/black phosphorus quantum dot composite hydrogel prepared by the invention has a uniform pore structure distribution, a pore diameter of 50-100 nm, and a porosity of about 50 nm. 75%.
  • Table 1 shows typical compositions and physical properties of Comparative Examples 1-6 and Examples 1-7 of the present invention. As is apparent from Table 1, in Comparative Examples 1 to 6, as the volume fraction of the crosslinking agent epichlorohydrin was increased, the mechanical strength of the finally obtained cellulose hydrogel was also remarkably increased.
  • the compression modulus is 18.2 kPa; when the volume ratio of cellulose solution to epichlorohydrin is increased to 100:1 (i.e., Comparative Example 4) and 100:2 (i.e., Comparative Example 6), their respective compressive moduli increased to 58.7 kPa and 78.2 kPa, respectively, due to the higher cross-linking agent content of the cellulose hydrogel.
  • the degree of chemical cross-linking is greatly increased.
  • pure cellulose hydrogel lacks any functionality and does not exhibit any photothermal effect, and its photothermal equilibrium temperature is 25 ° C, which is substantially the same as room temperature.
  • the final photothermal equilibrium temperature of the composite hydrogel can reach 43.2 ° C and 50.6 at 0.5 and 1.0 W/cm 2 , respectively.
  • °C compared with pure cellulose hydrogel, increased by 18.2 ° C and 25.6 ° C, respectively.
  • this photothermal equilibrium temperature greatly increases or exceeds the detection range of the thermal imager.
  • the mass ratio of cellulose to black phosphorus quantum dots is 100:5 (ie, Example 5)
  • the final photothermal equilibrium temperature of the composite hydrogel is 110.3 ° C and 129.3 ° C at 0.5 and 1.0 W/cm 2 , respectively;
  • the mass ratio of cellulose to black phosphorus quantum dots is 100:10 (ie, Example 6) and 100:50 (ie, Example 7)
  • the final photothermal equilibrium temperature of the composite hydrogel is higher than 150 ° C, exceeding thermal imaging. The scope of detection of the instrument.

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Abstract

L'invention concerne un hydrogel composite à boîtes quantiques en cellulose/phosphore noir comprenant une structure à matrice 3D de cellulose et des boîtes quantiques chargées dans celle-ci. Les boîtes quantiques phosphore noir susceptibles d'être chargées de manière stable dans le système hydrogel composite ne s'agglomèrent pas facilement. Avantages de l'hydrogel composite : haute efficacité en termes de conversion de la chaleur en lumière en raison de sa stabilité et uniformité, bonne biocompatibilité avec les liquides corporels, totalement biodégradable, bonne biosécurité et applications dans le domaine de la biomédecine. L'invention concerne en outre un procédé de préparation de l'hydrogel composite.
PCT/CN2018/100243 2017-11-15 2018-08-13 Hydrogel composite à boîtes quantiques en cellulose/phosphore noir et son procédé de préparation WO2019095753A1 (fr)

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CN108084460A (zh) * 2017-11-15 2018-05-29 深圳大学 一种纤维素/黑磷量子点复合水凝胶及其制备方法
CN110196511B (zh) * 2019-05-24 2021-11-12 武汉天马微电子有限公司 一种量子点膜及其制作方法、背光模组、显示装置
CN110862559B (zh) * 2019-11-29 2022-08-09 中国林业科学研究院林产化学工业研究所 一种高强度纤维素/膨润土复合水凝胶的制备方法
CN111265714A (zh) * 2020-03-11 2020-06-12 四川大学 黒磷功能化的可注射水凝胶及其制备方法和应用
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