CN111035770B - Caramelized hollow nano material and preparation method and application thereof - Google Patents
Caramelized hollow nano material and preparation method and application thereof Download PDFInfo
- Publication number
- CN111035770B CN111035770B CN201911189810.5A CN201911189810A CN111035770B CN 111035770 B CN111035770 B CN 111035770B CN 201911189810 A CN201911189810 A CN 201911189810A CN 111035770 B CN111035770 B CN 111035770B
- Authority
- CN
- China
- Prior art keywords
- caramelized
- hollow
- nano material
- nanomaterial
- solution
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
- 239000002086 nanomaterial Substances 0.000 title claims abstract description 94
- 238000002360 preparation method Methods 0.000 title claims abstract description 19
- BCKXLBQYZLBQEK-KVVVOXFISA-M Sodium oleate Chemical compound [Na+].CCCCCCCC\C=C/CCCCCCCC([O-])=O BCKXLBQYZLBQEK-KVVVOXFISA-M 0.000 claims abstract description 39
- 238000006243 chemical reaction Methods 0.000 claims abstract description 26
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 23
- WQZGKKKJIJFFOK-GASJEMHNSA-N Glucose Natural products OC[C@H]1OC(O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-GASJEMHNSA-N 0.000 claims abstract description 19
- 239000008103 glucose Substances 0.000 claims abstract description 19
- 239000000463 material Substances 0.000 claims abstract description 17
- 239000000843 powder Substances 0.000 claims abstract description 12
- 238000010438 heat treatment Methods 0.000 claims abstract description 9
- 238000002156 mixing Methods 0.000 claims abstract description 9
- 238000003756 stirring Methods 0.000 claims abstract description 9
- 159000000000 sodium salts Chemical class 0.000 claims abstract description 7
- 239000000243 solution Substances 0.000 claims description 29
- 239000011259 mixed solution Substances 0.000 claims description 16
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical group [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 claims description 14
- 238000011282 treatment Methods 0.000 claims description 11
- 239000003814 drug Substances 0.000 claims description 9
- 238000000926 separation method Methods 0.000 claims description 9
- 239000007787 solid Substances 0.000 claims description 9
- 239000002245 particle Substances 0.000 claims description 8
- 229910021538 borax Inorganic materials 0.000 claims description 7
- 239000006185 dispersion Substances 0.000 claims description 7
- 239000011780 sodium chloride Substances 0.000 claims description 7
- 235000010339 sodium tetraborate Nutrition 0.000 claims description 7
- BSVBQGMMJUBVOD-UHFFFAOYSA-N trisodium borate Chemical compound [Na+].[Na+].[Na+].[O-]B([O-])[O-] BSVBQGMMJUBVOD-UHFFFAOYSA-N 0.000 claims description 7
- 238000012285 ultrasound imaging Methods 0.000 claims description 6
- 238000005119 centrifugation Methods 0.000 claims description 5
- 238000001816 cooling Methods 0.000 claims description 5
- 238000001035 drying Methods 0.000 claims description 5
- 238000005406 washing Methods 0.000 claims description 5
- 238000004519 manufacturing process Methods 0.000 claims 2
- 239000012216 imaging agent Substances 0.000 claims 1
- 229940124597 therapeutic agent Drugs 0.000 claims 1
- 238000000034 method Methods 0.000 abstract description 6
- 206010018910 Haemolysis Diseases 0.000 abstract description 3
- 230000008588 hemolysis Effects 0.000 abstract description 3
- 102000004190 Enzymes Human genes 0.000 abstract description 2
- 108090000790 Enzymes Proteins 0.000 abstract description 2
- 206010057249 Phagocytosis Diseases 0.000 abstract description 2
- 230000002349 favourable effect Effects 0.000 abstract description 2
- 230000008782 phagocytosis Effects 0.000 abstract description 2
- 238000003917 TEM image Methods 0.000 description 12
- 238000003384 imaging method Methods 0.000 description 12
- 230000000694 effects Effects 0.000 description 8
- 206010028980 Neoplasm Diseases 0.000 description 7
- 229940079593 drug Drugs 0.000 description 7
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 6
- 238000003745 diagnosis Methods 0.000 description 6
- 239000008367 deionised water Substances 0.000 description 5
- 229910021641 deionized water Inorganic materials 0.000 description 5
- 229920000620 organic polymer Polymers 0.000 description 5
- 241000699670 Mus sp. Species 0.000 description 4
- 238000011068 loading method Methods 0.000 description 4
- 239000000693 micelle Substances 0.000 description 4
- 239000002105 nanoparticle Substances 0.000 description 4
- WQZGKKKJIJFFOK-VFUOTHLCSA-N beta-D-glucose Chemical compound OC[C@H]1O[C@@H](O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-VFUOTHLCSA-N 0.000 description 3
- 201000011510 cancer Diseases 0.000 description 3
- 238000011161 development Methods 0.000 description 3
- 230000002209 hydrophobic effect Effects 0.000 description 3
- 238000007626 photothermal therapy Methods 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- 210000004881 tumor cell Anatomy 0.000 description 3
- 206010006187 Breast cancer Diseases 0.000 description 2
- 208000026310 Breast neoplasm Diseases 0.000 description 2
- 230000006907 apoptotic process Effects 0.000 description 2
- BLUAFEHZUWYNDE-NNWCWBAJSA-N artemisinin Chemical compound C([C@](OO1)(C)O2)C[C@H]3[C@H](C)CC[C@@H]4[C@@]31[C@@H]2OC(=O)[C@@H]4C BLUAFEHZUWYNDE-NNWCWBAJSA-N 0.000 description 2
- 229960004191 artemisinin Drugs 0.000 description 2
- 229930101531 artemisinin Natural products 0.000 description 2
- 239000011248 coating agent Substances 0.000 description 2
- 238000000576 coating method Methods 0.000 description 2
- 238000002591 computed tomography Methods 0.000 description 2
- 239000002872 contrast media Substances 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 239000000032 diagnostic agent Substances 0.000 description 2
- 229940039227 diagnostic agent Drugs 0.000 description 2
- 238000011049 filling Methods 0.000 description 2
- 230000002147 killing effect Effects 0.000 description 2
- 230000035484 reaction time Effects 0.000 description 2
- 239000000523 sample Substances 0.000 description 2
- 229910001220 stainless steel Inorganic materials 0.000 description 2
- 239000010935 stainless steel Substances 0.000 description 2
- 241000699666 Mus <mouse, genus> Species 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 238000013459 approach Methods 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 229960000074 biopharmaceutical Drugs 0.000 description 1
- 238000001815 biotherapy Methods 0.000 description 1
- 210000004027 cell Anatomy 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 238000002512 chemotherapy Methods 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 238000002405 diagnostic procedure Methods 0.000 description 1
- 238000012631 diagnostic technique Methods 0.000 description 1
- 125000001165 hydrophobic group Chemical group 0.000 description 1
- 238000001027 hydrothermal synthesis Methods 0.000 description 1
- 238000001727 in vivo Methods 0.000 description 1
- 230000010354 integration Effects 0.000 description 1
- 239000002502 liposome Substances 0.000 description 1
- 238000002595 magnetic resonance imaging Methods 0.000 description 1
- 231100000512 nanotoxicity Toxicity 0.000 description 1
- 238000011275 oncology therapy Methods 0.000 description 1
- 238000012634 optical imaging Methods 0.000 description 1
- 239000012221 photothermal agent Substances 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 238000002600 positron emission tomography Methods 0.000 description 1
- 230000005855 radiation Effects 0.000 description 1
- 238000001959 radiotherapy Methods 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000000527 sonication Methods 0.000 description 1
- 238000001356 surgical procedure Methods 0.000 description 1
- 230000001225 therapeutic effect Effects 0.000 description 1
- 238000002560 therapeutic procedure Methods 0.000 description 1
- 230000001988 toxicity Effects 0.000 description 1
- 231100000419 toxicity Toxicity 0.000 description 1
Images
Classifications
-
- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
- A61K49/00—Preparations for testing in vivo
- A61K49/22—Echographic preparations; Ultrasound imaging preparations ; Optoacoustic imaging preparations
- A61K49/222—Echographic preparations; Ultrasound imaging preparations ; Optoacoustic imaging preparations characterised by a special physical form, e.g. emulsions, liposomes
- A61K49/223—Microbubbles, hollow microspheres, free gas bubbles, gas microspheres
-
- 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
- A61K47/06—Organic compounds, e.g. natural or synthetic hydrocarbons, polyolefins, mineral oil, petrolatum or ozokerite
- A61K47/08—Organic compounds, e.g. natural or synthetic hydrocarbons, polyolefins, mineral oil, petrolatum or ozokerite containing oxygen, e.g. ethers, acetals, ketones, quinones, aldehydes, peroxides
- A61K47/12—Carboxylic acids; Salts or anhydrides thereof
-
- 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
- A61K47/06—Organic compounds, e.g. natural or synthetic hydrocarbons, polyolefins, mineral oil, petrolatum or ozokerite
- A61K47/26—Carbohydrates, e.g. sugar alcohols, amino sugars, nucleic acids, mono-, di- or oligo-saccharides; Derivatives thereof, e.g. polysorbates, sorbitan fatty acid esters or glycyrrhizin
-
- 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
- A61K9/48—Preparations in capsules, e.g. of gelatin, of chocolate
- A61K9/50—Microcapsules having a gas, liquid or semi-solid filling; Solid microparticles or pellets surrounded by a distinct coating layer, e.g. coated microspheres, coated drug crystals
- A61K9/51—Nanocapsules; Nanoparticles
- A61K9/5107—Excipients; Inactive ingredients
- A61K9/5123—Organic compounds, e.g. fats, sugars
Abstract
The invention relates to a caramelized hollow nano material and a preparation method and application thereof, wherein the caramelized hollow nano material is an elastic complete hollow sphere or an elastic incomplete hollow sphere, and the preparation method comprises the steps of adding glucose powder and sodium oleate into water and slowly stirring to obtain a transparent solution; adding sodium salt into the transparent solution, uniformly mixing and heating to 160-200 ℃, and reacting for 2-6h to obtain the caramelized hollow nano material. In the invention, the caramelized nano material is prepared by a food science method (caramelization reaction) in the presence of sodium oleate, the hollow structure of the obtained material is relatively stable, the material can stably exist in ultrasonic waves, and the hemolysis phenomenon does not exist; the nano material has extremely low crystallinity, can be effectively degraded by various enzymes while realizing long circulation in a living body, is discharged out of the body in time, and has higher safety; in addition, the nanometer material has elasticity, and is more favorable for phagocytosis of cells.
Description
The technical field is as follows:
the invention relates to a caramelized hollow nano material and a preparation method and application thereof, belonging to the technical field of inorganic nano materials.
Background art:
nowadays, the incidence of cancer is increasing year by year, and more effective medical means are continuously developed to improve the curative effect of cancer. The major diagnostic techniques at present include: magnetic Resonance Imaging (MRI), optical imaging, Positron Emission Tomography (PET), Computed Tomography (CT), ultrasound imaging (USI), and the like. The major current treatment techniques include: surgery, radiotherapy, chemotherapy, biotherapy and the like. Among these new diagnostic and therapeutic techniques, a diagnosis and treatment integrated technique that combines imaging and treatment of a tumor into one has recently received great attention. Nanomedicine approaches have a great potential for clinical convertibility in cancer therapy, can positively impact the overall diagnostic and therapeutic process and improve the quality of life of cancer patients. With the development of scientific technology and the higher requirements of people on the tumor treatment effect, the development of an application means integrating tumor diagnosis and treatment is a main research target of current scientists. In order to solve the medical problem, the nano-drug diagnosis and treatment agent is produced at the same time.
The advent of nanotechnology and biotechnology has prompted the development of multifunctional nanoparticles (imaging and drug-loaded) as biopharmaceuticals. The currently developed nano diagnostic agents are mainly divided into inorganic nanoparticles and organic polymer nanoparticles. The inorganic nano material has higher crystallinity, is difficult to degrade in organisms, stays in the organisms for a long time and has harm to the health and the growth of the bodies. After the inorganic nano material is modified or functionalized, although the toxicity is reduced, the hemolysis phenomenon is easy to generate; although organic polymers can be degraded in organisms, the existing organic polymers for realizing diagnosis and treatment integration also need to load other diagnostic agents for realizing diagnosis or treatment. And when the organic polymer is used for ultrasonic imaging in a living body, the organic polymer can be quickly decomposed under the action of ultrasonic waves, so that the long-acting release of the medicine is difficult to realize.
The invention content is as follows:
aiming at the defects of the prior art, the invention provides the caramelized hollow nano material and the preparation method and the application thereof, the caramelized hollow nano material provided by the invention can not be decomposed quickly under the action of ultrasonic waves, and can not cause nano toxicity because the caramelized hollow nano material can not be degraded in vivo, the long-acting release of the drug in the organism can be realized, the defects of the prior art are overcome, and the ultrasonic diagnosis application of the caramelized hollow nano material in the organism is improved. In addition, the caramelized nano material provided by the invention has amphipathy and photo-thermal performance, so that the application of the material in drug-loading treatment is further improved.
The invention is realized by the following technical scheme:
the caramelized hollow nano material is in a hollow sphere shape with complete elasticity or an incomplete elasticity, and the particle size is 30-1500 nm.
Preferably, the particle size of the complete hollow spherical nano material is 800-1000nm, and the particle size of the incomplete hollow spherical nano material is 600-800 nm.
Preferably, according to the invention, the incomplete hollow sphere is a hollow hemisphere.
The invention also provides a preparation method of the caramelized hollow nano material.
A preparation method of a caramelized hollow nano material comprises the following steps:
(1) adding glucose powder and sodium oleate into water, and slowly stirring to obtain a transparent solution; adding sodium salt into the transparent solution, and uniformly mixing to obtain a mixed solution;
(2) transferring the mixed solution into a reaction kettle, heating to 160-200 ℃, and reacting for 2-6 h;
(3) after the reaction is finished, cooling the solution to room temperature for centrifugal treatment, washing the solid obtained by centrifugal separation, and drying in vacuum to obtain the caramelized hollow nano-material.
Preferably, in step (1), the mass-to-volume ratio of glucose to water is: (2-6): (20-40), unit: g/mL.
Preferably according to the invention, in step (1), the molar volume ratio of sodium oleate to water is: (1.5-6): (20-40), unit: mmol/mL.
Preferably, in step (1), the sodium salt is NaCl or sodium borate.
According to the invention, in the step (1), the mass-to-volume ratio of the added amount of NaCl to the water is (0.5-5): (20-40) mg/mL; the mass-volume ratio of the sodium borate to the water is (50-500): (20-40) mg/mL.
Preferably, in step (2), the reaction temperature is 170-180 ℃ and the reaction time is 3-4 h.
Preferably, in step (3), the centrifugation speed is 6000-12000 rpm.
According to a preferred technical scheme of the invention, the preparation method of the caramelized hollow nano material comprises the following steps:
(1) adding 3g of glucose powder and 3mmol of sodium oleate into 30mL of water, and slowly stirring to obtain a transparent solution; adding 0.1g of sodium borate into the transparent solution, and uniformly mixing to obtain a mixed solution;
(2) transferring the mixed solution into a reaction kettle, heating to 170 ℃, and reacting for 4 hours;
(3) after the reaction is finished, the solution is cooled to room temperature for 6000rpm centrifugation, the solid obtained by centrifugal separation is washed and then dried in vacuum, and the high-dispersion caramelized hollow nano-material with the size of 800-1500 nm is obtained.
According to a preferred technical scheme of the invention, the preparation method of the caramelized hollow nano material comprises the following steps:
(1) adding 3g of glucose powder and 3mmol of sodium oleate into 30mL of water, and slowly stirring to obtain a transparent solution; adding 0.1mL of 0.1M NaCl into the transparent solution, and uniformly mixing to obtain a mixed solution;
(2) transferring the mixed solution into a reaction kettle, heating to 170 ℃, and reacting for 4 hours;
(3) after the reaction is finished, the solution is cooled to room temperature for 6000rpm centrifugation, and the solid obtained by centrifugal separation is washed and then dried in vacuum, so that the 800nm high-dispersion caramelized hollow nano-material with the particle size of 600 plus materials is obtained.
The preparation method of the invention dissolves glucose and sodium oleate in water, micelles are formed in aqueous solution due to the association of hydrophobic groups of the sodium oleate, and in the hydrothermal process, smaller nano-particles generated by caramelization reaction of the glucose are polymerized on hydrophilic groups of the micelles. By changing the proportion of the added sodium oleate to the added glucose, the reaction time and the temperature, the complete structure of the micelle can be changed, the size of a cavity of the caramelized hollow nano material and the size of the nano material are influenced, the appearance of the generated nano material can be changed, the type and the adding amount of sodium salt can reduce the viscosity of the reaction solution, and the obtained caramelized hollow nano material has high dispersibility.
An application of the caramelized hollow nano material is used for ultrasonic imaging or loading of hydrophobic drugs and photothermal therapy, and the application concentration of the caramelized hollow nano material is 0.0625-1.0 mg/mL.
The invention has the following advantages and effects:
1. in the invention, the caramelized nano material is prepared by a food science method (caramelization reaction) in the presence of sodium oleate, the hollow structure of the obtained material is relatively stable, the material can stably exist in ultrasonic waves, and the hemolysis phenomenon caused by easy ultrasonic decomposition of the existing inorganic nano material (materials such as liposome, micelle and the like) is avoided; the nano material has extremely low crystallinity, can be effectively degraded by various enzymes while realizing long circulation in a living body, is discharged out of the body in time, and has higher safety; in addition, the nanometer material has elasticity, and is more favorable for phagocytosis of cells.
2. According to the invention, by controlling the proportion of sodium oleate and glucose and the type of sodium salt, nano materials with different cavity sizes, different sizes and different appearances can be obtained, and the controllability of the material is strong.
Description of the drawings:
FIG. 1 is a TEM image of a caramelized hollow nanomaterial prepared in example 1;
FIG. 2 is an ultrasonic image of a caramelized hollow nanomaterial prepared in example 1;
FIG. 3 is a TEM image of a caramelized hollow nanomaterial prepared in example 2;
FIG. 4 is an ultrasonic image of a caramelized hollow nanomaterial prepared in example 2;
FIG. 5 is a graph of apoptosis of caramelized hollow nanomaterials of example 2 irradiated with laser light to kill tumor cells;
FIG. 6 is a graph of ultrasound imaging of breast cancer sonication of mice using caramelized hollow nanomaterials of example 2.
FIG. 7 is a graph comparing the effects of photothermal therapy of mice using caramelized hollow nanomaterials of example 2.
FIG. 8 is a TEM image of caramelized hollow nanomaterial obtained by changing the addition amount of sodium oleate in Experimental example 1(1), wherein a is 0.5mmol of sodium oleate, b is 1mmol of sodium oleate, c is 1.5mmol of sodium oleate, d is 2mmol of sodium oleate, and e is 3mmol of sodium oleate.
FIG. 9 is a TEM image of caramelized hollow nanomaterial obtained by changing the addition amount of sodium oleate in Experimental example 1(2), wherein a is 0.5mmol of sodium oleate, b is 1mmol of sodium oleate, c is 1.5mmol of sodium oleate, d is 2mmol of sodium oleate, and e is 3mmol of sodium oleate.
FIG. 10 is a TEM image of caramelized hollow nanomaterial obtained by changing the addition amount of sodium oleate in Experimental example 1(3), wherein a is 0.5mmol of sodium oleate, b is 1mmol of sodium oleate, c is 1.5mmol of sodium oleate, d is 2mmol of sodium oleate, and e is 3mmol of sodium oleate.
FIG. 11 is a TEM image of caramelized hollow nanomaterial obtained by varying the reaction temperature in Experimental example 2.
The specific implementation mode is as follows:
in order to make the technical problems, technical solutions and advantages of the present invention more apparent, the following detailed description is given with reference to the accompanying drawings and specific examples, but not limited thereto, and the present invention is not described in detail, and is implemented by the conventional techniques in the art
The materials and reagents used in the examples are commercially available.
Example 1
A preparation method of a caramelized hollow nano material comprises the following steps:
(1) adding 3g of glucose powder and 3mmol of sodium oleate into 30mL of water, and slowly stirring to obtain a transparent solution; adding 0.1g of sodium borate into the transparent solution, and uniformly mixing to obtain a mixed solution;
(2) transferring the mixed solution into a stainless steel reaction kettle, heating to 170 ℃, and reacting for 4 hours;
(3) after the reaction is finished, cooling the solution to room temperature, centrifuging at 6000rpm, washing the solid obtained by centrifugal separation with deionized water and ethanol, and drying in vacuum to obtain the high-dispersion caramelized hollow nano-material.
The TEM image of the obtained caramelized hollow nano material is shown in FIG. 1, and as can be seen from FIG. 1, the material is of a complete spherical structure and has a cavity inside.
The application of the obtained spherical caramelized nano material in an ultrasonic imaging contrast agent is as follows:
and (3) dispersing the spherical caramelized nano material in deionized water, then filling the dispersed solution into a centrifugal tube, and coating ultrasonic gel on the outer side of the centrifugal tube. And finally, carrying out imaging test by the ultrasonic probe. The ultrasound imaging results are shown in figure 2.
Example 2
A preparation method of a caramelized hollow nano material comprises the following steps:
(1) adding 3g of glucose powder and 3mmol of sodium oleate into 30mL of water, and slowly stirring to obtain a transparent solution; adding 0.1mL of 0.1M NaCl into the transparent solution, and uniformly mixing to obtain a mixed solution;
(2) transferring the mixed solution into a stainless steel reaction kettle, heating to 170 ℃, and reacting for 4 hours;
(3) after the reaction is finished, cooling the solution to room temperature, centrifuging at 6000rpm, washing the solid obtained by centrifugal separation with deionized water and ethanol, and drying in vacuum to obtain the high-dispersion caramelized hollow nano-material.
The TEM image of the obtained caramelized hollow nanomaterial is shown in FIG. 3, and it can be seen from FIG. 1 that the material has a hemispherical structure with a cavity inside. Changing the type of the added raw materials also affects the morphology of the caramelized nanomaterial, thereby affecting the effect of ultrasonic imaging.
The application of the obtained bowl-shaped caramelized nano material in an ultrasonic imaging contrast agent is as follows:
and (3) dispersing the spherical caramelized nano material in deionized water, then filling the dispersed solution into a centrifugal tube, and coating ultrasonic gel on the outer side of the centrifugal tube. And finally, carrying out imaging test by the ultrasonic probe. The ultrasound imaging results are shown in figure 4.
Application example:
1. the caramelized hollow nanomaterial of example 2 is irradiated with laser, and the caramelized hollow nanomaterial of example 2 is used as a photothermal agent, so that a good killing effect on tumor cells can be realized by using a 150 μ g/mL material, such as an apoptosis graph shown in FIG. 5; the material of the invention has good ultraviolet absorption, when the laser is used for radiation, the light can be converted into heat, thereby achieving the effect of killing tumor cells,
2. when the caramelized hollow nanomaterial of example 2 is used for carrying out breast cancer ultrasonic imaging on a mouse, as shown in fig. 6, it is demonstrated that the hollow nanomaterial of the present invention has stability and can achieve a good imaging effect.
3. When the caramelized hollow nanomaterial of example 2 is used for photothermal therapy of mice, tumors in the mice can be effectively ablated, as shown in fig. 7.
Example 3
The preparation method of the caramelized hollow nanomaterial is the same as that in example 1, except that:
and (4) after the reaction in the step (3) is finished, cooling the solution to room temperature, centrifuging at 12000rpm, washing the solid obtained by centrifugal separation with deionized water and ethanol, and drying in vacuum to obtain the high-dispersion caramelized hollow nano material.
The caramelized hollow nano-material prepared in example 3 is used as a carrier, and artemisinin is used as a representative of a hydrophobic drug to perform tests, and the drug loading rate of artemisinin is found to be 198.8mg/g, so that the caramelized nano-material has amphipathy and rich pore structure, and can be used for loading the hydrophobic drug.
Experimental example 1
1. A preparation method of caramelized hollow nanomaterial was carried out as in example 1, except that 2g of glucose powder was used, and the amounts of sodium oleate added were changed to 0.5mmol, 1mmol, 1.5mmol, 2mmol, and 3mmol, respectively, and a TEM image of the caramelized hollow nanomaterial was as shown in FIG. 8.
2. A preparation method of caramelized hollow nanomaterial was carried out as in example 1, except that the amount of glucose powder was 3g, and the amounts of sodium oleate added were varied to 0.5mmol, 1mmol, 1.5mmol, 2mmol, and 3mmol, respectively, and a TEM image of the caramelized hollow nanomaterial was as shown in FIG. 9.
3. A preparation method of caramelized hollow nanomaterial was carried out as in example 1, except that the amount of glucose powder was changed to 4g, and the amounts of sodium oleate added were 0.5mmol, 1mmol, 1.5mmol, 2mmol, and 3mmol, respectively, and a TEM image of the caramelized hollow nanomaterial was as shown in FIG. 10.
It can be seen from fig. 8, 9 and 10 that changing the addition amounts of glucose and sodium oleate affects the cavity size of the caramelized hollow nanomaterial and the size of the nanomaterial, thereby affecting the effect of ultrasonic imaging.
Experimental example 2
A process for producing a caramelised hollow nanomaterial which is carried out in the same manner as in example 1, except that the reaction temperature in step (2) is changed to 150 ℃, 160 ℃, 170 ℃, 180 ℃, 190 ℃ and 200 ℃ respectively, and the TEM image of the caramelised hollow nanomaterial obtained is shown in FIG. 11, and it can be seen from FIG. 11 that the higher the reaction temperature is, the greater the degree of polymerisation of the material is, and that the maximum degree of polymerisation is obtained at a reaction temperature of 170 ℃.
Claims (6)
1. A caramelized hollow nanomaterial, wherein the caramelized hollow nanomaterial is a hollow sphere with complete elasticity or a hollow sphere with incomplete elasticity, and the particle size is 30-1500 nm; the particle size of the complete hollow spherical nano material is 800-1000nm, the particle size of the incomplete hollow spherical nano material is 600-800nm, and the incomplete hollow spherical nano material is a hollow hemisphere;
the preparation method of the caramelized hollow nano material comprises the following steps:
(1) adding glucose powder and sodium oleate into water, and slowly stirring to obtain a transparent solution; adding sodium salt into the transparent solution, and uniformly mixing to obtain a mixed solution; the mass-volume ratio of glucose to water is as follows: (2-6): (20-40), unit: g/mL; the molar volume ratio of the sodium oleate to the water is as follows: (1.5-6): (20-40), unit: mmol/mL;
(2) transferring the mixed solution into a reaction kettle, heating to 170-180 ℃, and reacting for 3-4 h;
(3) after the reaction is finished, cooling the solution to room temperature for centrifugal treatment, wherein the centrifugal rotation speed is 6000-12000rpm, washing the solid obtained by centrifugal separation, and then drying in vacuum to obtain the caramelized hollow nano-material.
2. The caramelized hollow nanomaterial of claim 1, wherein in step (1), the sodium salt is NaCl or sodium borate.
3. The caramelized hollow nanomaterial according to claim 1, wherein in step (1), the mass-to-volume ratio of the added amount of NaCl to water is (0.5-5): (20-40) mg/mL; the mass-volume ratio of the sodium borate to the water is (50-500): (20-40) mg/mL.
4. The caramelized hollow nanomaterial according to claim 1, characterized in that the method for producing a caramelized hollow nanomaterial comprises the steps of:
(1) adding 3g of glucose powder and 3mmol of sodium oleate into 30mL of water, and slowly stirring to obtain a transparent solution; adding 0.1g of sodium borate into the transparent solution, and uniformly mixing to obtain a mixed solution;
(2) transferring the mixed solution into a reaction kettle, heating to 170 ℃, and reacting for 4 hours;
(3) after the reaction is finished, the solution is cooled to room temperature for 6000rpm centrifugation, the solid obtained by centrifugal separation is washed and then dried in vacuum, and the high-dispersion caramelized hollow nano-material with the size of 800-1500 nm is obtained.
5. The caramelized hollow nanomaterial according to claim 1, characterized in that the method for producing a caramelized hollow nanomaterial comprises the steps of:
(1) adding 3g of glucose powder and 3mmol of sodium oleate into 30mL of water, and slowly stirring to obtain a transparent solution; adding 0.1mL of 0.1M NaCl into the transparent solution, and uniformly mixing to obtain a mixed solution;
(2) transferring the mixed solution into a reaction kettle, heating to 170 ℃, and reacting for 4 hours;
(3) after the reaction is finished, the solution is cooled to room temperature for 6000rpm centrifugation, and the solid obtained by centrifugal separation is washed and then dried in vacuum, so that the 800nm high-dispersion caramelized hollow nano-material with the particle size of 600 plus materials is obtained.
6. The use of caramelized hollow nanomaterial of claim 1 in the preparation of an ultrasound imaging agent or a photothermal therapeutic agent, the caramelized hollow nanomaterial being used at a concentration of 0.0625-1.0 mg/mL.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201911189810.5A CN111035770B (en) | 2019-11-28 | 2019-11-28 | Caramelized hollow nano material and preparation method and application thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201911189810.5A CN111035770B (en) | 2019-11-28 | 2019-11-28 | Caramelized hollow nano material and preparation method and application thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN111035770A CN111035770A (en) | 2020-04-21 |
| CN111035770B true CN111035770B (en) | 2021-10-22 |
Family
ID=70233926
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201911189810.5A Active CN111035770B (en) | 2019-11-28 | 2019-11-28 | Caramelized hollow nano material and preparation method and application thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN111035770B (en) |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107814374A (en) * | 2017-11-07 | 2018-03-20 | 北京化工大学 | A kind of method of regulation and control carbon material pattern |
| CN110279874A (en) * | 2019-07-10 | 2019-09-27 | 青岛科技大学 | A kind of Magnetic resonance imaging guidance tumor photo-thermal treats material and preparation method thereof |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20100129290A1 (en) * | 2008-11-26 | 2010-05-27 | I.S.T. Corporation | Smart contrast agent and detection method for detecting transition metal ions |
-
2019
- 2019-11-28 CN CN201911189810.5A patent/CN111035770B/en active Active
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107814374A (en) * | 2017-11-07 | 2018-03-20 | 北京化工大学 | A kind of method of regulation and control carbon material pattern |
| CN110279874A (en) * | 2019-07-10 | 2019-09-27 | 青岛科技大学 | A kind of Magnetic resonance imaging guidance tumor photo-thermal treats material and preparation method thereof |
Non-Patent Citations (2)
| Title |
|---|
| MemHsp70 Receptor-mediated Multifunctional Ordered Mesoporous Carbon Nanospheres for Photoacoustic Imaging-Guided Synergistic Targeting Trimodal Therapy;Shanshan Wang et al;《ACS Biomater. Sci. Eng.》;20170714;第3卷;第1702-1709页 * |
| 基于介孔碳纳米球的光声成像及光热/化学联合治疗肿瘤研究;周丽波;《中国博士学位论文全文数据库》;20190415(第04期);E072-17 * |
Also Published As
| Publication number | Publication date |
|---|---|
| CN111035770A (en) | 2020-04-21 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN106139144B (en) | A kind of hyaluronic acid decorated gold-Nano carbon balls and the preparation method and application thereof with synergistic antitumor characteristic | |
| CN108888767B (en) | Nano composite material, preparation method and application thereof | |
| CN108653754B (en) | Hyaluronic acid targeted polydopamine coated phase-change type liquid fluorocarbon nano ultrasonic contrast agent | |
| CN109453398B (en) | Mesoporous polydopamine-encapsulated liquid fluorocarbon ultrasonic contrast agent and preparation method thereof | |
| CN104548095B (en) | A kind of PLGA/MoS2Composite medicament stent material and its preparation method and application | |
| US11364312B2 (en) | Platinum sulfide protein nanoparticle having near-infrared photothermal effect and multimodal imaging function, preparation method therefor and application thereof | |
| Guo et al. | Emerging biocompatible nanoplatforms for the potential application in diagnosis and therapy of deep tumors | |
| Gao et al. | AuNRs@ MIL-101-based stimuli-responsive nanoplatform with supramolecular gates for image-guided chemo-photothermal therapy | |
| CN106692970A (en) | Bismuth selenide nanocomposite material and preparation method and application thereof | |
| CN114432265B (en) | Bionic nano delivery system loaded with bufalin and preparation method and application thereof | |
| CN104288093B (en) | Application of the nano drug transdermal preparation in tumour | |
| CN109125723A (en) | Compound sound sensitiser, preparation method, application, application method, purposes and pharmaceutical composition | |
| Ostovar et al. | Nanocomposite of chitosan/gelatin/carbon quantum dots as a biocompatible and efficient nanocarrier for improving the Curcumin delivery restrictions to treat brain cancer | |
| CN111035770B (en) | Caramelized hollow nano material and preparation method and application thereof | |
| Yang et al. | Boosting immunotherapy of triple negative breast cancer through the synergy of mild PTT and Fe-loaded organosilica nanoparticles | |
| CN109550050B (en) | Melanin-loaded molybdenum dioxide drug-loaded compound and preparation and application thereof | |
| Wang et al. | Progress in cancer therapy with functionalized Fe3O4 nanomaterials | |
| CN108771760B (en) | Platinum sulfide protein nanoparticle with near infrared photothermal effect and multi-mode imaging function, and preparation method and application thereof | |
| CN113274499B (en) | Bionic bismuth nanoflower and preparation method and application thereof | |
| CN107890566A (en) | A kind of diagnosing tumor treatment preparation and its preparation method and application | |
| CN110917172B (en) | Molybdenum oxide nanosheet plugging hollow mesoporous silicon nanomaterial and preparation and application thereof | |
| CN111388671A (en) | Nano-drug carrier, drug-carrying system containing nano-drug carrier and preparation method of drug-carrying system | |
| CN111701030A (en) | Preparation method of active targeting zirconium dioxide nanoparticles with defect of acoustic power effect | |
| CN110938423B (en) | Degradable antimony-coated rare earth upconversion nanocomposite structure, preparation method and application | |
| US20220402763A1 (en) | Graphene oxide (go)-based composite nanoparticle drug delivery system and preparation method thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |