CN112023739B - Preparation method of micro-nano bubbles - Google Patents
Preparation method of micro-nano bubbles Download PDFInfo
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- CN112023739B CN112023739B CN202010912586.4A CN202010912586A CN112023739B CN 112023739 B CN112023739 B CN 112023739B CN 202010912586 A CN202010912586 A CN 202010912586A CN 112023739 B CN112023739 B CN 112023739B
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- 239000002101 nanobubble Substances 0.000 title claims abstract description 33
- 238000002360 preparation method Methods 0.000 title claims abstract description 14
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N Iron oxide Chemical compound [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 claims abstract description 84
- 239000002245 particle Substances 0.000 claims abstract description 53
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 49
- 238000000034 method Methods 0.000 claims abstract description 23
- 239000000243 solution Substances 0.000 claims abstract description 23
- 239000000725 suspension Substances 0.000 claims abstract description 14
- 238000001816 cooling Methods 0.000 claims abstract description 9
- 238000010438 heat treatment Methods 0.000 claims abstract description 7
- 230000009471 action Effects 0.000 claims abstract description 6
- 239000012047 saturated solution Substances 0.000 claims abstract description 6
- 230000001939 inductive effect Effects 0.000 claims abstract description 5
- 229920006395 saturated elastomer Polymers 0.000 claims abstract description 5
- 239000007789 gas Substances 0.000 claims description 20
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 claims description 16
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 claims description 15
- 239000001569 carbon dioxide Substances 0.000 claims description 8
- 229910002092 carbon dioxide Inorganic materials 0.000 claims description 8
- 230000003068 static effect Effects 0.000 claims description 6
- 230000010355 oscillation Effects 0.000 claims description 5
- 239000011259 mixed solution Substances 0.000 claims description 3
- WRIDQFICGBMAFQ-UHFFFAOYSA-N (E)-8-Octadecenoic acid Natural products CCCCCCCCCC=CCCCCCCC(O)=O WRIDQFICGBMAFQ-UHFFFAOYSA-N 0.000 claims description 2
- LQJBNNIYVWPHFW-UHFFFAOYSA-N 20:1omega9c fatty acid Natural products CCCCCCCCCCC=CCCCCCCCC(O)=O LQJBNNIYVWPHFW-UHFFFAOYSA-N 0.000 claims description 2
- QSBYPNXLFMSGKH-UHFFFAOYSA-N 9-Heptadecensaeure Natural products CCCCCCCC=CCCCCCCCC(O)=O QSBYPNXLFMSGKH-UHFFFAOYSA-N 0.000 claims description 2
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 2
- 239000005642 Oleic acid Substances 0.000 claims description 2
- ZQPPMHVWECSIRJ-UHFFFAOYSA-N Oleic acid Natural products CCCCCCCCC=CCCCCCCCC(O)=O ZQPPMHVWECSIRJ-UHFFFAOYSA-N 0.000 claims description 2
- 239000002202 Polyethylene glycol Substances 0.000 claims description 2
- 229920002873 Polyethylenimine Polymers 0.000 claims description 2
- 108010039918 Polylysine Proteins 0.000 claims description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 2
- 239000001257 hydrogen Substances 0.000 claims description 2
- 229910052739 hydrogen Inorganic materials 0.000 claims description 2
- QXJSBBXBKPUZAA-UHFFFAOYSA-N isooleic acid Natural products CCCCCCCC=CCCCCCCCCC(O)=O QXJSBBXBKPUZAA-UHFFFAOYSA-N 0.000 claims description 2
- ZQPPMHVWECSIRJ-KTKRTIGZSA-N oleic acid Chemical compound CCCCCCCC\C=C/CCCCCCCC(O)=O ZQPPMHVWECSIRJ-KTKRTIGZSA-N 0.000 claims description 2
- 239000001301 oxygen Substances 0.000 claims description 2
- 229910052760 oxygen Inorganic materials 0.000 claims description 2
- 229920001223 polyethylene glycol Polymers 0.000 claims description 2
- 229920000656 polylysine Polymers 0.000 claims description 2
- 238000011084 recovery Methods 0.000 claims description 2
- 229910052724 xenon Inorganic materials 0.000 claims description 2
- FHNFHKCVQCLJFQ-UHFFFAOYSA-N xenon atom Chemical compound [Xe] FHNFHKCVQCLJFQ-UHFFFAOYSA-N 0.000 claims description 2
- 238000001556 precipitation Methods 0.000 abstract description 3
- 229940031182 nanoparticles iron oxide Drugs 0.000 description 4
- 230000001276 controlling effect Effects 0.000 description 3
- 238000011161 development Methods 0.000 description 3
- 239000000463 material Substances 0.000 description 2
- NDLPOXTZKUMGOV-UHFFFAOYSA-N oxo(oxoferriooxy)iron hydrate Chemical compound O.O=[Fe]O[Fe]=O NDLPOXTZKUMGOV-UHFFFAOYSA-N 0.000 description 2
- 238000004064 recycling Methods 0.000 description 2
- 238000009360 aquaculture Methods 0.000 description 1
- 244000144974 aquaculture Species 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 239000002872 contrast media Substances 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 229940079593 drug Drugs 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 239000003937 drug carrier Substances 0.000 description 1
- 238000012377 drug delivery Methods 0.000 description 1
- 239000002961 echo contrast media Substances 0.000 description 1
- 238000004945 emulsification Methods 0.000 description 1
- 238000004108 freeze drying Methods 0.000 description 1
- 238000001415 gene therapy Methods 0.000 description 1
- 230000036571 hydration Effects 0.000 description 1
- 238000006703 hydration reaction Methods 0.000 description 1
- 238000003384 imaging method Methods 0.000 description 1
- 238000007641 inkjet printing Methods 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 230000001404 mediated effect Effects 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 238000012544 monitoring process Methods 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 230000000717 retained effect Effects 0.000 description 1
- 239000010865 sewage Substances 0.000 description 1
- 239000010409 thin film Substances 0.000 description 1
- 230000002537 thrombolytic effect Effects 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01F—MIXING, e.g. DISSOLVING, EMULSIFYING OR DISPERSING
- B01F23/00—Mixing according to the phases to be mixed, e.g. dispersing or emulsifying
- B01F23/20—Mixing gases with liquids
- B01F23/23—Mixing gases with liquids by introducing gases into liquid media, e.g. for producing aerated liquids
- B01F23/235—Mixing gases with liquids by introducing gases into liquid media, e.g. for producing aerated liquids for making foam
-
- 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
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01F—MIXING, e.g. DISSOLVING, EMULSIFYING OR DISPERSING
- B01F2101/00—Mixing characterised by the nature of the mixed materials or by the application field
- B01F2101/2202—Mixing compositions or mixers in the medical or veterinary field
Landscapes
- Health & Medical Sciences (AREA)
- Radiology & Medical Imaging (AREA)
- Physics & Mathematics (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Acoustics & Sound (AREA)
- Nuclear Medicine, Radiotherapy & Molecular Imaging (AREA)
- Chemical & Material Sciences (AREA)
- Epidemiology (AREA)
- Life Sciences & Earth Sciences (AREA)
- Animal Behavior & Ethology (AREA)
- General Health & Medical Sciences (AREA)
- Public Health (AREA)
- Veterinary Medicine (AREA)
- Compounds Of Iron (AREA)
Abstract
The invention discloses a preparation method of micro-nano bubbles, which specifically comprises the following steps: adding iron oxide particles into degassed water to form a suspension, placing the suspension in a constant-temperature water bath, and introducing gas of target bubbles to obtain a saturated gas solution; and (3) putting the gas saturated solution with the water bath into an alternating magnetic field, starting the magnetic field, forming a local hot point under the action of heating of iron oxide and cooling of an external water bath, reducing the local solubility of the solution to the gas, and inducing micro-nano bubbles to be separated out. According to the method, the alternating magnetic field acts on the uniform-size iron oxide particles in the solution to quickly generate hot spots, so that the solubility of gas dissolved in the solution is reduced under the action of the hot spots to form bubble precipitation.
Description
Technical Field
The invention relates to a preparation method of micro-nano bubbles.
Background
The micro-nano bubbles are bubbles with the diameter of about tens of nanometers to ten micrometers when the bubbles occur, the bubbles are between the micro-bubbles and the nano-bubbles, and compared with the conventional bubbles, the micro-nano bubbles have the characteristics of large specific surface area, high gas dissolution rate, capability of generating free radicals, high mass transfer efficiency and the like, and can be better applied to the fields of aquaculture, soilless culture, food and tableware cleaning, ecological restoration and sewage treatment. In recent years, the micro-nano bubbles are used as ultrasonic contrast agents and drug carriers, and show wide application prospects in the aspects of molecular imaging, drug delivery, mediated gene therapy, thrombolysis and the like.
At present, the known preparation methods of microbubble contrast agents include an alcohol-water replacement method, a thin film hydration method, a high shear emulsification method, a freeze drying method, an ultrasonic cavitation method and the like, but the methods are difficult to obtain micro-nano bubbles with uniform particle sizes. With the demand for bubble materials (gas contents) in the medical field and the development of material preparation techniques, new preparation methods including a microfluidic method and an inkjet printing method have emerged, which improve the particle size, stability and quality uniformity of microbubbles, but have low preparation efficiency.
Disclosure of Invention
The purpose of the invention is as follows: aiming at the problem of low bubble production efficiency in the prior art, the invention provides a micro-nano bubble preparation method.
The technical scheme is as follows: the preparation method of the micro-nano bubbles comprises the following steps:
(1) adding iron oxide particles into degassed water to form a suspension, placing the suspension in a constant-temperature water bath, and introducing gas of target bubbles to obtain a saturated gas solution;
(2) and (3) putting the gas saturated solution with the water bath into an alternating magnetic field, starting the magnetic field, forming a local hot point under the action of heating of iron oxide and cooling of an external water bath, reducing the local solubility of the solution to the gas, and inducing micro-nano bubbles to be separated out.
And the method also comprises an iron oxide particle recovery step, wherein after the alternating magnetic field is removed and the water bath is removed, a mixed solution of the iron oxide particles and the micro-nano bubbles is obtained, the mixed solution containing the iron oxide particles and the micro-nano bubbles is placed in a static magnetic field, and the iron oxide particles in the solution are recovered.
The invention can recycle the ferric oxide particles in the solution by adding the static magnetic field, so that the ferric oxide particles can be recycled; the magnetic iron oxide nanoparticles can be retained on the shell layer of the micro-nano bubbles to construct the magnetic micro-nano bubbles, and the magnetic micro-nano bubbles can realize the functions of magnetic resonance development and magnetic field regulation and control on one hand and can realize the monitoring of the target transported drugs at the focus part on the other hand through the ultrasonic development function of the micro-nano bubbles.
Wherein, in the step (1), the gas is one of carbon dioxide, oxygen, hydrogen or xenon.
In the step (1), the iron oxide particles are modified by oleic acid, citric acid, polyethylene glycol, polyethyleneimine or polylysine. The iron oxide particles can be effectively prevented from agglomerating through modification, so that the iron oxide particles are uniformly dispersed in the solution.
In the step (1), the particle size of the iron oxide particles is 10-1000 nm, and the addition amount of the iron oxide particles is 0.01-3% of the weight of the degassed water.
Wherein in the step (1), the temperature of the water bath is 0-40 ℃.
In the step (2), the oscillation frequency of the alternating magnetic field is 1 KHz-100 KHz, the power is 50-2000W, and the magnetic field opening time is 5-60 min.
The mechanism of the method of the invention is as follows: magnetic iron oxide particles are added into a saturated gas solution, external water cooling is utilized to keep the temperature of a main body solution, meanwhile, an alternating magnetic field is utilized to form local hot spots for heating, the local hot spots in the solution are maintained, and bubbles are separated out by utilizing the solubility difference of gas at different temperatures, so that micro-nano bubbles are prepared.
Has the advantages that: according to the method, the alternating magnetic field acts on the iron oxide particles with uniform size in the solution to quickly generate hot spots, so that the solubility of gas dissolved in the solution is reduced under the action of the hot spots, bubbles with uniform particle size are precipitated, the method can stably and efficiently prepare the micro-nano bubbles, and the particle size of the bubbles is controllable.
Detailed Description
The technical solution of the present invention is further described with reference to the following specific embodiments.
Example 1
The preparation method of the micro-nano bubbles specifically comprises the following steps:
adding citric acid modified magnetic iron oxide particles into degassed water, wherein the diameter of the particles is 100nm, the addition amount of the iron oxide nanoparticles is 0.1% of the weight of the degassed water, adding the iron oxide particles into the degassed water to form a suspension, cooling the suspension in the degassed water in a water bath at the temperature of 10 ℃, introducing carbon dioxide into the water after the suspension reaches the temperature, and enabling the solubility of carbon dioxide gas in the water to reach saturation; placing the gas saturated solution with water bath into an alternating magnetic field, maintaining the temperature of the water bath, controlling the oscillation frequency of the alternating magnetic field to be 7KHz and the power to be 300W, starting the magnetic field, and maintaining for 30 min. Forming local hot spots in the solution by the heating of the iron oxide and the cooling of an external water bath, inducing the precipitation of bubbles, recovering the iron oxide in the solution by using an external static magnetic field after the bubbles are formed, recycling the iron oxide, and respectively measuring the average particle diameter and PDI (dispersion index) of the prepared bubbles by a laser particle size analyzer to be 71.2nm and 0.327.
Example 2
The preparation method of the micro-nano bubbles specifically comprises the following steps:
adding citric acid modified magnetic iron oxide particles into degassed water, wherein the diameter of the particles is 1000nm, the addition amount of the iron oxide nanoparticles is 1% of the weight of the degassed water, forming a suspension of the iron oxide particles in the degassed water, adding a water bath to cool the liquid, wherein the temperature of the water bath is 40 ℃, introducing carbon dioxide into the water after the suspension reaches the temperature, and leading the solubility of the carbon dioxide in the water to be saturated; placing the gas saturated solution with water bath into an alternating magnetic field, maintaining the temperature of the water bath, controlling the oscillation frequency of the alternating magnetic field to be 1KHz and the power to be 50W, starting the magnetic field, and maintaining for 5 min. Forming local hot spots through the heating of iron oxide and the cooling of external water bath, inducing the precipitation of bubbles, recovering the iron oxide in the solution by using an external static magnetic field after the bubbles are formed, recycling, and measuring the average particle diameter and PDI of the prepared bubbles by a laser particle size analyzer to be 303.9nm and 0.429 respectively.
Example 3
The preparation method of the micro-nano bubbles specifically comprises the following steps:
adding citric acid modified magnetic iron oxide particles into degassed water, wherein the diameter of the particles is 10nm, the addition amount of the iron oxide nanoparticles is 0.01 percent of the weight of the degassed water, adding the iron oxide particles into the degassed water to form a suspension, cooling the suspension in the degassed water in a water bath at the temperature of 0 ℃, introducing carbon dioxide into the water after the suspension reaches the temperature, and enabling the solubility of carbon dioxide gas in the water to reach saturation; placing the gas saturated solution with water bath into an alternating magnetic field, maintaining the temperature of the water bath, controlling the oscillation frequency of the alternating magnetic field to be 50KHz and the power to be 2000W, and starting the magnetic field to maintain for 60 min. Local hot spots are formed under the action of iron oxide heating and external water bath cooling, air bubbles are induced to be precipitated, the iron oxide in the solution is recovered by using an external static magnetic field after the air bubbles are formed and recycled, and the average particle size and PDI (the smaller the PDI, the more uniform the particle size of the air bubbles is, the better the stability of the method of the invention) of the prepared air bubbles are respectively 31.2nm and 0.271.
The size of the bubbles can be regulated and controlled by adjusting the size and the adding amount of the iron oxide particles and the strength of the alternating magnetic field, when the iron oxide particles are larger, the strength of the alternating magnetic field is larger, more heat is generated, and the particle size of the generated bubbles is larger, when the strength of the alternating magnetic field is determined, and the particle size of the iron oxide particles in the solution is determined, the generated heat is determined, so the particle size of the bubbles is also determined, and the method can obtain the bubbles with uniform particle size under the determined magnetic field and the determined particle size of the iron oxide particles.
Claims (7)
1. A preparation method of micro-nano bubbles is characterized by comprising the following steps:
(1) adding iron oxide particles into degassed water to form a suspension, placing the suspension in a constant-temperature water bath, and introducing gas of target bubbles to obtain a saturated gas solution;
(2) and (3) putting the gas saturated solution with the water bath into an alternating magnetic field, starting the magnetic field, forming a local hot point under the action of heating of iron oxide and cooling of an external water bath, reducing the local solubility of the solution to the gas, and inducing micro-nano bubbles to be separated out.
2. The method for preparing the micro-nano bubbles according to claim 1, which is characterized by comprising the following steps: and the method also comprises an iron oxide particle recovery step, wherein the mixed solution containing the iron oxide particles and the micro-nano bubbles is placed in a static magnetic field, and the iron oxide particles in the solution are recovered.
3. The method for preparing the micro-nano bubbles according to claim 1, which is characterized by comprising the following steps: in the step (1), the gas is one of carbon dioxide, oxygen, hydrogen or xenon.
4. The method for preparing the micro-nano bubbles according to claim 1, which is characterized by comprising the following steps: in the step (1), the iron oxide particles are modified by oleic acid, citric acid, polyethylene glycol, polyethyleneimine or polylysine.
5. The method for preparing the micro-nano bubbles according to claim 1, which is characterized by comprising the following steps: in the step (1), the particle size of the iron oxide particles is 10-1000 nm, and the addition amount of the iron oxide particles is 0.01-3% of the weight of the degassed water.
6. The method for preparing the micro-nano bubbles according to claim 1, which is characterized by comprising the following steps: in the step (1), the temperature of the water bath is 0-40 ℃.
7. The method for preparing the micro-nano bubbles according to claim 1, which is characterized by comprising the following steps: in the step (2), the oscillation frequency of the alternating magnetic field is 1 KHz-100 KHz, the power is 50-2000W, and the magnetic field starting time is 1-60 min.
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| CN112023739A CN112023739A (en) | 2020-12-04 |
| CN112023739B true CN112023739B (en) | 2022-02-22 |
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| CN113363040A (en) * | 2021-05-28 | 2021-09-07 | 东南大学 | Method for preparing magnetic lipid bubbles by inducing interface self-assembly based on magnetocaloric effect |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104096491A (en) * | 2014-07-18 | 2014-10-15 | 中国科学院声学研究所 | Reverse bubble generator and preparation method |
| CN108261932A (en) * | 2018-02-01 | 2018-07-10 | 崔恩喜 | A kind of micro bubble generation device |
| CN109453902A (en) * | 2018-12-29 | 2019-03-12 | 江苏大丰新安德矿业有限公司 | A kind of floating magnetic separation column device and combined type bubble generator |
| CN109954143A (en) * | 2019-03-01 | 2019-07-02 | 雷建军 | A kind of preparation method of magnetic Nano iron oxide particles contrast agent |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| AU731099B2 (en) * | 1993-07-30 | 2001-03-22 | Imcor Pharmaceutical Company | Stablized microbubble compositions for ultrasound |
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Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104096491A (en) * | 2014-07-18 | 2014-10-15 | 中国科学院声学研究所 | Reverse bubble generator and preparation method |
| CN108261932A (en) * | 2018-02-01 | 2018-07-10 | 崔恩喜 | A kind of micro bubble generation device |
| CN109453902A (en) * | 2018-12-29 | 2019-03-12 | 江苏大丰新安德矿业有限公司 | A kind of floating magnetic separation column device and combined type bubble generator |
| CN109954143A (en) * | 2019-03-01 | 2019-07-02 | 雷建军 | A kind of preparation method of magnetic Nano iron oxide particles contrast agent |
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