CN112023739B - Preparation method of micro-nano bubbles - Google Patents

Preparation method of micro-nano bubbles Download PDF

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Publication number
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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iron oxide
micro
nano bubbles
magnetic field
solution
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CN112023739A (en
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焦真
王甲妲
顾宁
孙剑飞
陈怡�
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Southeast University
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Southeast University
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    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01FMIXING, e.g. DISSOLVING, EMULSIFYING OR DISPERSING
    • B01F23/00Mixing according to the phases to be mixed, e.g. dispersing or emulsifying
    • B01F23/20Mixing gases with liquids
    • B01F23/23Mixing gases with liquids by introducing gases into liquid media, e.g. for producing aerated liquids
    • B01F23/235Mixing gases with liquids by introducing gases into liquid media, e.g. for producing aerated liquids for making foam
    • AHUMAN NECESSITIES
    • A61MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61KPREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K49/00Preparations for testing in vivo
    • A61K49/22Echographic preparations; Ultrasound imaging preparations ; Optoacoustic imaging preparations
    • A61K49/222Echographic preparations; Ultrasound imaging preparations ; Optoacoustic imaging preparations characterised by a special physical form, e.g. emulsions, liposomes
    • A61K49/223Microbubbles, hollow microspheres, free gas bubbles, gas microspheres
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01FMIXING, e.g. DISSOLVING, EMULSIFYING OR DISPERSING
    • B01F2101/00Mixing characterised by the nature of the mixed materials or by the application field
    • B01F2101/2202Mixing compositions or mixers in the medical or veterinary field

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  • 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

Preparation method of micro-nano bubbles
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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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)

* Cited by examiner, † Cited by third party
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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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
AU731099B2 (en) * 1993-07-30 2001-03-22 Imcor Pharmaceutical Company Stablized microbubble compositions for ultrasound

Patent Citations (4)

* Cited by examiner, † Cited by third party
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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