CN110713734B - Preparation method of nano fluorescent dye - Google Patents
Preparation method of nano fluorescent dye Download PDFInfo
- Publication number
- CN110713734B CN110713734B CN201810770070.3A CN201810770070A CN110713734B CN 110713734 B CN110713734 B CN 110713734B CN 201810770070 A CN201810770070 A CN 201810770070A CN 110713734 B CN110713734 B CN 110713734B
- Authority
- CN
- China
- Prior art keywords
- fluorescent dye
- feed liquid
- nano fluorescent
- nano
- prepare
- 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
Images
Classifications
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09B—ORGANIC DYES OR CLOSELY-RELATED COMPOUNDS FOR PRODUCING DYES, e.g. PIGMENTS; MORDANTS; LAKES
- C09B67/00—Influencing the physical, e.g. the dyeing or printing properties of dyestuffs without chemical reactions, e.g. by treating with solvents grinding or grinding assistants, coating of pigments or dyes; Process features in the making of dyestuff preparations; Dyestuff preparations of a special physical nature, e.g. tablets, films
- C09B67/0001—Post-treatment of organic pigments or dyes
- C09B67/0014—Influencing the physical properties by treatment with a liquid, e.g. solvents
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y20/00—Nanooptics, e.g. quantum optics or photonic crystals
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y40/00—Manufacture or treatment of nanostructures
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09B—ORGANIC DYES OR CLOSELY-RELATED COMPOUNDS FOR PRODUCING DYES, e.g. PIGMENTS; MORDANTS; LAKES
- C09B19/00—Oxazine dyes
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09B—ORGANIC DYES OR CLOSELY-RELATED COMPOUNDS FOR PRODUCING DYES, e.g. PIGMENTS; MORDANTS; LAKES
- C09B57/00—Other synthetic dyes of known constitution
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09B—ORGANIC DYES OR CLOSELY-RELATED COMPOUNDS FOR PRODUCING DYES, e.g. PIGMENTS; MORDANTS; LAKES
- C09B57/00—Other synthetic dyes of known constitution
- C09B57/001—Pyrene dyes
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09B—ORGANIC DYES OR CLOSELY-RELATED COMPOUNDS FOR PRODUCING DYES, e.g. PIGMENTS; MORDANTS; LAKES
- C09B57/00—Other synthetic dyes of known constitution
- C09B57/02—Coumarine dyes
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K11/00—Luminescent, e.g. electroluminescent, chemiluminescent materials
- C09K11/06—Luminescent, e.g. electroluminescent, chemiluminescent materials containing organic luminescent materials
Abstract
The invention discloses a preparation method of a nano fluorescent dye, which comprises the following steps: dissolving a fluorescent dye in an organic solvent to prepare a fluorescent dye organic solution, and marking as feed liquid A; dissolving a surfactant in water to prepare a surfactant aqueous solution, and marking as feed liquid B; simultaneously injecting the feed liquid A and the feed liquid B into a supergravity rotating packed bed through a feed inlet, fully mixing and precipitating the feed liquid A and the feed liquid B in a supergravity environment, discharging the mixture from a discharge outlet, and collecting to obtain nano fluorescent dye slurry; and removing the organic solvent from the nano fluorescent dye slurry in a reduced pressure distillation mode to prepare the nano fluorescent dye. The method adopts a supergravity rotating packed bed, and the particle size of the prepared nano fluorescent dye particles is less than or equal to 100 nanometers; the particle size distribution is uniform, the dispersibility is good, and the PDI value is less than or equal to 0.3; the preparation process is simple and the reaction time is short; the method solves the problems of complex dye nanocrystallization process, large product particle size, uneven particle size distribution and the like.
Description
Technical Field
The invention relates to the technical field of fluorescent dye preparation, and in particular relates to a preparation method of a nano fluorescent dye.
Background
Fluorescent dyes are a class of novel dyes developed in recent years, and are more and more concerned by the industry as functional materials, and researchers continue to search and research fluorescent dyes, especially organic fluorescent dyes. The organic fluorescent dye is based on a single photon excitation process, is usually excited by light with higher energy and shorter wavelength, and emitted light has the characteristics of lower energy and longer wavelength. The organic fluorescent dye has the advantages of good selectivity, high sensitivity, high light stability, high fluorescence quantum yield, simple and quick operation and the like. Therefore, the method is widely applied to various fields such as biology, chemical engineering, medicine, electrochemistry, military industry and the like.
Compared with the traditional fluorescent dye, the water-based fluorescent dye can emit strong fluorescence without using an organic solvent, has the advantages of no toxicity, low cost, accordance with the health and environmental protection concept and the like, and is the development trend of the existing fluorescent dye. However, the existing organic fluorescent dyes have some problems of hydrophobicity, easy aggregation and the like, and the hydrophobic organic fluorescent dyes are easy to aggregate in aqueous solution and can undergo fluorescence quenching, so that the application of the organic fluorescent dyes is limited, and therefore, the organic fluorescent dyes have important scientific research and market values for solving the water solubility problem of the organic fluorescent dyes.
As is well known, nanotechnology is increasingly becoming the leading technology for the advance of science and technology, and it is one of the scientific revolution marks at the beginning of the new century. The field of nanotechnology is quite extensive, and relates to knowledge in multiple fields such as polymer chemistry, colloid chemistry, physical chemistry, biochemistry, material science, condensed state physics, quantum mechanics, microelectronic technology and the like, so that the interdisciplinary of multiple disciplines has great significance for promoting the development of nanotechnology. The fluorescent dye is combined with the nanotechnology, nanoparticles are formed by self-aggregation of fluorescent dye-loaded nanoparticles or dye small molecules, the particle size is reduced, and the specific surface area is improved to solve the problems of water solubility and the like. Furthermore, it is an important direction for the development of fluorescent dyes to control, influence and improve the relevant properties of the materials by using the formed nano-structures, so that the materials can be better applied.
At present, a great deal of work is done by technicians to prepare nanoscale fluorescent dyes to solve the problem of hydrophobicity of some fluorescent dyes. For example, chinese patent application publication No. CN103012812A discloses a method for preparing water-soluble fluorescent nano-microspheres, wherein the method comprises coating fluorescent dye with amphiphilic block copolymer under heating condition, and modifying to obtain nano-fluorescent dye with small particle size and narrow particle size distribution. But it has the disadvantages that: the preparation process is complex, the reaction time is long, and high-temperature treatment is required. The invention discloses a preparation method of nano fluorescent microspheres in Chinese patent application with publication number CN106632834A, which comprises the steps of adding a comonomer, an initiator, a cross-linking agent, a dispersing agent, a dispersion medium and a fluorescent dye solution into a reaction vessel, stirring to ensure that the mixture is uniformly dispersed and reacts for a period of time to prepare the nano fluorescent dye with good water solubility. But the disadvantages are that: the reaction time is long in the preparation process, the process is complex, the preparation process is difficult to control, and mass production is difficult to realize. Coriias et al used a media milling process to prepare nano fluorescent dyes (coriias F, Schlich M, Silico C, et al, nile red nanosuspensions as invasive model to study the fluorescent targets of drug nanocrystals [ J ]. Int J Pharm,2017,524(1): 1-8.). The media milling method is to convert mechanical energy into crushing energy for materials by using the action of external machinery through grinding media, and disperse and crush material particles by means of friction, shear and collision among the grinding media. The preparation method has the advantage of simple process, but has some defects: the prepared nano fluorescent dye has large and uneven particle size, wider particle size distribution, long grinding time in the preparation process and high energy consumption.
Therefore, in order to overcome the existing defects, a preparation method of the nano fluorescent dye with simple preparation process, low energy consumption, short reaction time, good dispersibility in aqueous solution and small particle size is needed.
Disclosure of Invention
The invention aims to provide a preparation method of a nano fluorescent dye. The method adopts a supergravity rotating packed bed, so that the mixing process of the fluorescent dye organic solution and the surfactant aqueous solution can be greatly enhanced, the particle size distribution of the prepared nano fluorescent dye particles is uniform, and the PDI value is less than or equal to 0.3; the grain diameter is less than or equal to 100 nanometers; the dispersibility in aqueous solution is good, and the fluorescence intensity is high; the preparation process is simple and the reaction time is short; the method well solves the problems of hydrophobicity of the fluorescent dye, complex nanocrystallization process, large product particle size, uneven particle size distribution and the like, and is easy for large-scale production.
In order to solve the technical problems, the invention adopts the following technical scheme:
a preparation method of nano fluorescent dye comprises the following steps:
s1, dissolving the fluorescent dye in an organic solvent to prepare a fluorescent dye organic solution, and marking as feed liquid A;
s2, dissolving a surfactant in water to prepare a surfactant aqueous solution, and marking as feed liquid B;
s3, simultaneously injecting the feed liquid A and the feed liquid B into a supergravity rotary packed bed through a feed inlet, premixing the feed liquid A and the feed liquid B through a liquid distributor, then entering a packing layer, providing a strong supergravity environment for a molecular mixing process through high-speed rotation of an inner rotor in the packing layer, fully mixing and precipitating the feed liquid A and the feed liquid B, then flowing into cavities of the inner wall and the rotor, then discharging from a discharge outlet, and collecting to obtain nano fluorescent dye slurry;
s4, removing the organic solvent from the nano fluorescent dye slurry obtained in the step S3 in a reduced pressure distillation mode to prepare the nano fluorescent dye.
As a further improvement of the technical solution, in step S1, the fluorescent dye is a hydrophobic fluorescent dye; the hydrophobic fluorescent dye comprises one or more of nile red, curcumin, fluorescein, pyrene and coumarin.
Preferably, in step S1, the concentration of the fluorescent dye organic solution is 5-600 μ g/mL; more preferably, the concentration of the organic solution of the fluorescent dye is 10-500. mu.g/mL.
Preferably, in step S1, the organic solvent is selected from one or more of methanol, ethanol, propanol, acetone, acetonitrile, tetrahydrofuran; more preferably, the organic solvent is selected from one or more of methanol, ethanol, acetone and tetrahydrofuran.
Preferably, in the steps S1 and S2, the volume ratio of the feed liquid A to the feed liquid B is 1:1-1: 30; more preferably, the volume ratio of the feed liquid A to the feed liquid B is 1:1-1: 20.
As a further improvement of the technical solution, in step S2, the surfactant is selected from one or more of tween 20, tween 80, sodium dodecyl sulfate, sodium dodecyl benzene sulfonate, polyethylene glycol 400, polyethylene glycol 600, polyethylene glycol 1000, polyethylene glycol 2000, polyvinyl alcohol, hydroxypropyl methyl cellulose, polyoxyethylene castor oil, and polyvinylpyrrolidone.
Preferably, in step S2, the concentration of the surfactant aqueous solution is 0.2-10 mg/mL; more preferably, the concentration of the aqueous surfactant solution is 0.4-10 mg/mL.
As a further improvement of the technical scheme, in step S3, the rotating speed of the rotor of the high-gravity rotating packed bed is 300-2500 rpm.
Preferably, in step S3, the temperature of the mixture of feed liquid A and feed liquid B in the high-gravity rotating packed bed is 5-50 ℃.
As a further improvement of the technical solution, in step S4, the vacuum distillation parameters: the temperature is 30-70 ℃, and the vacuum degree is 0.02-0.1 MPa.
Any range recited herein is intended to include the endpoints and any number between the endpoints and any subrange subsumed therein or defined therein.
The starting materials of the present invention are commercially available, unless otherwise specified, and the equipment used in the present invention may be any equipment conventionally used in the art or may be any equipment known in the art.
Compared with the prior art, the invention has the following beneficial effects:
1. the method utilizes the excellent molecular mixing capability of the supergravity rotating packed bed to match with corresponding reaction parameters to obtain the particle size of less than or equal to 100 nanometers; the particle size distribution is narrow, and the PDI value is less than or equal to 0.3; and the nano fluorescent dye particles with good water dispersibility;
2. the preparation process of the invention does not need a method which is easy to damage the components of the fluorescent dye, such as high temperature, high pressure, chemical reaction and the like, and has mild process conditions;
3. the method adopts a reduced pressure distillation treatment method to remove the organic solvent, is simple to operate and has good organic solvent removal effect;
4. the invention has simple process, short reaction time, low energy consumption and high production efficiency, and is suitable for mass production.
Drawings
The following detailed description of embodiments of the invention is provided in connection with the accompanying drawings
FIG. 1 shows a transmission electron microscope image of the nano fluorescent dye prepared in example 1 of the present invention.
FIG. 2 shows a photograph of the fluorescent dye prepared in example 1 of the present invention.
FIG. 3 shows the fluorescence spectrum of the nano fluorescent dye prepared in example 1 of the present invention.
FIG. 4 shows a scanning electron micrograph and a real micrograph of the nano fluorescent dye prepared in comparative example 1 of the present invention.
FIG. 5 shows a transmission electron microscope image of the nano fluorescent dye prepared in comparative example 2 of the present invention.
FIG. 6 is a graph showing the comparison of fluorescence spectra of the nano fluorescent dye prepared by the supergravity rotating packed bed and the conventional stirred tank in comparative example 2 of the present invention.
FIG. 7 shows a transmission electron microscope image of the nano fluorescent dye prepared in comparative example 3 of the present invention.
Detailed Description
In order to more clearly illustrate the invention, the invention is further described below in connection with preferred embodiments. It is to be understood by persons skilled in the art that the following detailed description is illustrative and not restrictive, and is not to be taken as limiting the scope of the invention.
The invention relates to a preparation method of a nano fluorescent dye, which comprises the following steps:
s1, dissolving the fluorescent dye in an organic solvent to prepare a fluorescent dye organic solution, and marking as feed liquid A;
s2, dissolving a surfactant in water to prepare a surfactant aqueous solution, and marking as feed liquid B;
s3, simultaneously injecting the feed liquid A and the feed liquid B into a supergravity rotary packed bed through a feed inlet, premixing the feed liquid A and the feed liquid B through a liquid distributor, then entering a packing layer, providing a strong supergravity environment for a molecular mixing process through high-speed rotation of an inner rotor in the packing layer, fully mixing and precipitating the feed liquid A and the feed liquid B, then flowing into cavities of the inner wall and the rotor, then discharging from a discharge outlet, and collecting to obtain nano fluorescent dye slurry;
s4, removing the organic solvent from the nano fluorescent dye slurry obtained in the step S3 in a reduced pressure distillation mode to prepare the nano fluorescent dye.
According to some embodiments of the invention, in step S1, the fluorescent dye is a hydrophobic fluorescent dye; the hydrophobic fluorescent dye comprises one or more of nile red, curcumin, fluorescein, pyrene and coumarin.
According to some embodiments of the invention, in step S1, the concentration of the organic solution of the fluorescent dye is 5-600. mu.g/mL, or 5-550. mu.g/mL, or 5-500. mu.g/mL, or 5-450. mu.g/mL, or 5-400. mu.g/mL, or 5-350. mu.g/mL, or 5-300. mu.g/mL, or 5-250. mu.g/mL, or 5-200. mu.g/mL, or 5-150. mu.g/mL, or 5-100. mu.g/mL, or 5-50. mu.g/mL, or 5-550. mu.g/mL, or 10-500. mu.g/mL, or 10-450. mu.g/mL, or 10-400. mu.g/mL, or 10-350. mu.g/mL, or, Or 10-300. mu.g/mL, or 10-250. mu.g/mL, or 10-200. mu.g/mL, or 10-150. mu.g/mL, or 10-100. mu.g/mL, or 10-50. mu.g/mL, or 50-550. mu.g/mL, or 50-500. mu.g/mL, or 50-450. mu.g/mL, or 50-400. mu.g/mL, or 50-350. mu.g/mL, or 50-300. mu.g/mL, or 50-250. mu.g/mL, or 50-200. mu.g/mL, or 50-150. mu.g/mL, or 50-100. mu.g/mL, or 100-550. mu.g/mL, or 100-500. mu.g/mL, or 100-450. mu.g/mL, or 100-400. mu.g/mL, Or 350 μ g/mL of 100-, Or 250-550 μ g/mL, or 250-500 μ g/mL, or 250-450 μ g/mL, or 250-400 μ g/mL, or 250-350 μ g/mL, or 250-300 μ g/mL, or 300-550 μ g/mL, or 300-500 μ g/mL, or 300-450 μ g/mL, or 300-400 μ g/mL, or 300-350 μ g/mL, or 350-550 μ g/mL, or 350-500 μ g/mL, or 350-450 μ g/mL, or 350-400 μ g/mL, or 400-550 μ g/mL, or 400-400 μ g/mL, or 400-450 μ g/mL, or 450-550 μ g/mL, or 450-500 μ g/mL, or 450-450 μ g/mL, Or 500-550 μ g/mL; the concentration of the fluorescent dye organic solution is too low, the production efficiency of the nano dye is reduced, and when the concentration is too high, the collision degree of the nano dye particles in the obtained fluorescent dye slurry is increased, so that the nano particles are agglomerated.
According to certain preferred embodiments of the present invention, the concentration of the organic solution of the fluorescent dye is 10 to 500. mu.g/mL.
According to certain embodiments of the invention, in step S1, the organic solvent is selected from one or more of methanol, ethanol, propanol, acetone, acetonitrile, tetrahydrofuran. The boiling point of the selected organic solvent is too high, so that the organic solvent cannot be removed; the solubility of the fluorescent dye in the solvent is too low, which reduces the efficiency of removing the organic solvent in the vacuum distillation process.
According to certain preferred embodiments of the present invention, the organic solvent is selected from one or more of methanol, ethanol, acetone, and tetrahydrofuran.
According to certain embodiments of the invention, the volume ratio of feed liquid a to feed liquid B in steps S1 and S2 is 1:1-1:30, or 1:2.5-1:30, or 1:5-1:25, or 1:5-1:20, or 1:5-1:15, or 1:5-1:10, or 1:10-1:30, or 1:10-1:25, or 1:10-1:20, or 1:10-1:15, or 1:15-1:30, or 1:15-1:20, or 1:20-1:30, or 1:20-1:25, or 1:25-1: 30; when the volume ratio of the feed liquid A to the feed liquid B is too small, the prepared nano fluorescent dye particles are seriously agglomerated and cannot be stably dispersed; when the volume ratio of the feed liquid A to the feed liquid B is too large, the solid content in the fluorescent dye slurry is low, the reduced pressure distillation time is prolonged, and the production efficiency is reduced.
According to certain preferred embodiments of the present invention, the volume ratio of the feed liquid A to the feed liquid B is 1:1 to 1: 20.
According to certain embodiments of the invention, in step S2, the surfactant is selected from one or more of tween 20, tween 80, sodium lauryl sulfate, sodium dodecyl benzene sulfonate, polyethylene glycol 400, polyethylene glycol 600, polyethylene glycol 1000, polyethylene glycol 2000, polyvinyl alcohol, hydroxypropyl methylcellulose, polyoxyethylene castor oil, and polyvinylpyrrolidone. If the selected surfactant is not suitable, the agglomeration is serious and the nano fluorescent dye cannot be stably dispersed in the aqueous solution.
According to certain embodiments of the invention, in step S2, the concentration of the aqueous surfactant solution is 0.2-10mg/mL, or 0.2-8mg/mL, or 0.2-6mg/mL, or 0.2-4mg/mL, or 0.2-2mg/mL, or 0.5-10mg/mL, or 0.5-8mg/mL, or 0.5-6mg/mL, or 0.5-4mg/mL, or 0.5-2mg/mL, or 2-10mg/mL, or 2-8mg/mL, or 2-6mg/mL, or 2-4mg/mL, or 4-10mg/mL, or 4-8mg/mL, or 4-6mg/mL, or 6-10mg/mL, or 6-8mg/mL, or, Or 8-10 mg/mL; more preferably, the concentration of the aqueous surfactant solution is 0.4-10 mg/mL. When the surfactant aqueous solution is too high or too low, the nano fluorescent dye particles are increased in size and seriously agglomerated.
According to some embodiments of the present invention, in step S3, the rotor speed of the hypergravity rotation packed bed is 300-.
According to some embodiments of the invention, the temperature at which the feed liquid A and the feed liquid B are mixed in the high-gravity rotating packed bed in step S3 is 5 to 50 ℃, or 10 to 40 ℃, or 10 to 30 ℃, or 10 to 20 ℃, or 20 to 50 ℃, or 20 to 40 ℃, or 20 to 30 ℃, or 30 to 50 ℃, or 30 to 40 ℃, or 40 to 50 ℃.
According to some embodiments of the invention, in step S4, the vacuum distillation parameters are: the temperature is 30-70 ℃, and the vacuum degree is 0.02-0.1 MPa.
The preparation method comprises the selection of the supergravity rotating packed bed equipment, and the selection of all parameters form an integral technical scheme, and the nanometer fluorescent dye can be obtained only by matching. The overstepping of any condition will cause the object of the present invention to be impossible.
Example 1
A preparation method of nano fluorescent dye comprises the following steps:
1) dissolving fluorescent dye nile red in acetone to prepare 100mL of fluorescent dye acetone solution with the concentration of 10 mg/L;
2) preparing 700mL of surfactant aqueous solution with 0.8g/L of Tween 80 and deionized water;
3) starting the super-gravity rotating packed bed, and adjusting the rotating speed to 500 rpm; starting a feeding pump, and controlling the feeding rate of the fluorescent dye acetone solution to be 85mL/min and the feeding rate of the surfactant aqueous solution to be 600 mL/min; simultaneously conveying the fluorescent dye acetone solution and the surfactant aqueous solution to a supergravity rotary packed bed for mixed precipitation reaction at the reaction temperature of 25 ℃, and closing the supergravity rotary packed bed after the fluorescent dye acetone solution is fed to obtain nano fluorescent dye slurry;
4) and removing the organic solvent from the obtained nano fluorescent dye slurry in a reduced pressure distillation mode to prepare the nano fluorescent dye.
FIG. 1 shows a transmission electron microscope image of the nano fluorescent dye prepared in example 1 of the present invention. As can be seen from the figure, the average particle diameter of the nano fluorescent dye particles is 35 nm; the particle size distribution PDI was 0.12.
Fig. 2 shows a photograph of a sample and a fluorescent photograph of the nano fluorescent dye prepared in example 1 of the present invention, and it can be seen from the photograph that the prepared nano fluorescent dye can emit bright red fluorescence.
FIG. 3 shows the fluorescence spectrum of the nano-fluorescent dye prepared in example 1 of the present invention, from which it can be seen that the fluorescent dye is not fluorescent when it is directly dissolved in water, and after the nano-fluorescent dye is formed, the dispersion stability of the nano-fluorescent dye in water is improved, so that it can emit strong fluorescence, and the maximum emission wavelength is about 640 nm.
Example 2
A preparation method of nano fluorescent dye comprises the following steps:
1) dissolving curcumin in ethanol to prepare 100mL of ethanol solution of the fluorescent dye with the concentration of 50 mg/L;
2) preparing 500mL of surfactant aqueous solution of 2g/L by using polyethylene glycol 600 and deionized water;
3) starting the super-gravity rotating packed bed, and adjusting the rotating speed to 1000 rpm; starting a feeding pump, and controlling the feeding rate of the fluorescent dye ethanol solution to be 120mL/min and the feeding rate of the surfactant aqueous solution to be 600 mL/min; simultaneously conveying the fluorescent dye ethanol solution and the surfactant aqueous solution to a supergravity rotary packed bed for mixing and precipitation reaction at the reaction temperature of 30 ℃, and closing the supergravity rotary packed bed after the fluorescent dye ethanol solution is fed to obtain nano fluorescent dye slurry;
4) and removing the organic solvent from the obtained nano fluorescent dye slurry in a reduced pressure distillation mode to prepare the nano fluorescent dye. Through detection, the average particle diameter of the nano fluorescent dye particles is 60nm, and the particle size distribution PDI value is 0.19.
Example 3
A preparation method of nano fluorescent dye comprises the following steps:
1) dissolving fluorescent dye coumarin 6 in methanol to prepare 100mL of fluorescent dye methanol solution with the concentration of 200 mg/L;
2) preparing 4g/L of surfactant aqueous solution 1500mL by polyvinylpyrrolidone and deionized water;
3) starting the super-gravity rotating packed bed, and adjusting the rotating speed to 1500 rpm; starting a feeding pump, and controlling the feeding rate of the fluorescent dye methanol solution to be 40mL/min and the feeding rate of the surfactant aqueous solution to be 600 mL/min; simultaneously conveying the fluorescent dye methanol solution and the surfactant aqueous solution to a supergravity rotary packed bed for mixing and precipitation reaction at the reaction temperature of 40 ℃, and closing the supergravity rotary packed bed after the fluorescent dye methanol solution is fed to obtain nano fluorescent dye slurry;
4) and removing the organic solvent from the obtained nano fluorescent dye slurry in a reduced pressure distillation mode to prepare the nano fluorescent dye. The nano fluorescent dye particles have the average particle diameter of 75nm and the particle size distribution PDI value of 0.12.
Example 4
A preparation method of nano fluorescent dye comprises the following steps:
1) dissolving the fluorescent dye pyrene in tetrahydrofuran to prepare 100mL of the fluorescent dye tetrahydrofuran solution with the concentration of 300 mg/L;
2) preparing 1000mL of surfactant aqueous solution with the concentration of 6g/L by using lauryl sodium sulfate and deionized water;
3) starting the super-gravity rotating packed bed, and adjusting the rotating speed to 2000 rpm; starting a feeding pump, and controlling the feeding rate of the fluorescent dye tetrahydrofuran solution to be 60mL/min and the feeding rate of the surfactant aqueous solution to be 600 mL/min; simultaneously conveying the fluorescent dye tetrahydrofuran solution and the surfactant aqueous solution to a supergravity rotary packed bed for mixed precipitation reaction at the reaction temperature of 35 ℃, and closing the supergravity rotary packed bed after the fluorescent dye tetrahydrofuran solution is fed, so as to obtain nano fluorescent dye slurry;
4) and removing the organic solvent from the obtained nano fluorescent dye slurry in a reduced pressure distillation mode to prepare the nano fluorescent dye. Through detection, the average particle diameter of the nano fluorescent dye particles is 85nm, and the particle size distribution PDI value is 0.27.
Example 5
A preparation method of nano fluorescent dye comprises the following steps:
1) dissolving fluorescent dye nile red in acetone to prepare 100mL of fluorescent dye acetone solution with the concentration of 500 mg/L;
2) preparing 2000mL of surfactant aqueous solution of 10g/L from Tween 80 and deionized water;
3) starting the super-gravity rotating packed bed, and adjusting the rotating speed to 800 rpm; starting a feeding pump, and controlling the feeding rate of the fluorescent dye acetone solution to be 30mL/min and the feeding rate of the surfactant aqueous solution to be 600 mL/min; simultaneously conveying the fluorescent dye acetone solution and the surfactant aqueous solution to a supergravity rotary packed bed for mixed precipitation reaction at the reaction temperature of 5 ℃, and closing the supergravity rotary packed bed after the fluorescent dye acetone solution is fed to obtain nano fluorescent dye slurry;
4) and removing the organic solvent from the obtained nano fluorescent dye slurry in a reduced pressure distillation mode to prepare the nano fluorescent dye. The nano fluorescent dye particles have the average particle diameter of 100nm and the particle size distribution PDI value of 0.30.
Example 6
A preparation method of nano fluorescent dye comprises the following steps:
1) dissolving fluorescent dye coumarin 6 in acetone to prepare 100mL of fluorescent dye acetone solution with the concentration of 100 mg/L;
2) preparing sodium dodecyl benzene sulfonate and deionized water into 1000mL of surfactant aqueous solution of 3 g/L;
3) starting the super-gravity rotating packed bed, and adjusting the rotating speed to 2500 rpm; starting a feeding pump, and controlling the feeding rate of the fluorescent dye acetone solution to be 60mL/min and the feeding rate of the surfactant aqueous solution to be 600 mL/min; simultaneously conveying the fluorescent dye acetone solution and the surfactant aqueous solution to a supergravity rotary packed bed for mixed precipitation reaction at the reaction temperature of 50 ℃, and closing the supergravity rotary packed bed after the fluorescent dye acetone solution is fed to obtain nano fluorescent dye slurry;
4) and removing the organic solvent from the obtained nano fluorescent dye slurry in a reduced pressure distillation mode to prepare the nano fluorescent dye. Through detection, the average particle diameter of the nano fluorescent dye particles is 65nm, and the particle size distribution PDI value is 0.16.
Example 7
A preparation method of nano fluorescent dye comprises the following steps:
1) dissolving the fluorescent dye pyrene in ethanol to prepare 200mL of fluorescent dye ethanol solution with the concentration of 20 mg/L;
2) preparing 400mL of surfactant aqueous solution of 3g/L from hydroxypropyl methylcellulose and deionized water;
3) starting the super-gravity rotating packed bed, and adjusting the rotating speed to 1800 rpm; starting a feeding pump, and controlling the feeding rate of the fluorescent dye ethanol solution to be 300mL/min and the feeding rate of the surfactant aqueous solution to be 600 mL/min; simultaneously conveying the fluorescent dye ethanol solution and the surfactant aqueous solution to a supergravity rotary packed bed for mixing and precipitation reaction at the reaction temperature of 45 ℃, and closing the supergravity rotary packed bed after the fluorescent dye ethanol solution is fed to obtain nano fluorescent dye slurry;
4) and removing the organic solvent from the obtained nano fluorescent dye slurry in a reduced pressure distillation mode to prepare the nano fluorescent dye. The nano fluorescent dye particles have the average particle diameter of 95nm and the particle size distribution PDI value of 0.22.
Example 8
A preparation method of nano fluorescent dye comprises the following steps:
1) dissolving fluorescent dye nile red in methanol to prepare 100mL of fluorescent dye methanol solution with the concentration of 150 mg/L;
2) preparing 4g/L of surfactant aqueous solution 1500mL by using Tween 20 and deionized water;
3) starting the super-gravity rotating packed bed, and adjusting the rotating speed to 1000 rpm; starting a feeding pump, and controlling the feeding rate of the fluorescent dye methanol solution to be 40mL/min and the feeding rate of the surfactant aqueous solution to be 600 mL/min; simultaneously conveying the fluorescent dye methanol solution and the surfactant aqueous solution to a supergravity rotary packed bed for mixing and precipitation reaction at the reaction temperature of 15 ℃, and closing the supergravity rotary packed bed after the fluorescent dye methanol solution is fed to obtain nano fluorescent dye slurry;
4) and removing the organic solvent from the obtained nano fluorescent dye slurry in a reduced pressure distillation mode to prepare the nano fluorescent dye. Through detection, the average particle diameter of the nano fluorescent dye particles is 70nm, and the particle size distribution PDI value is 0.24.
Example 9
A preparation method of nano fluorescent dye comprises the following steps:
1) dissolving fluorescent dye coumarin 6 in ethanol to prepare 100mL of fluorescent dye ethanol solution with the concentration of 20 mg/L;
2) preparing 2000mL of surfactant aqueous solution of 400mg/L by using polyvinyl alcohol and deionized water;
3) starting the super-gravity rotating packed bed, and adjusting the rotating speed to 1500 rpm; starting a feeding pump, and controlling the feeding rate of the fluorescent dye ethanol solution to be 30mL/min and the feeding rate of the surfactant aqueous solution to be 600 mL/min; simultaneously conveying the fluorescent dye ethanol solution and the surfactant aqueous solution to a supergravity rotary packed bed for mixing and precipitation reaction at the reaction temperature of 35 ℃, and closing the supergravity rotary packed bed after the fluorescent dye ethanol solution is fed to obtain nano fluorescent dye slurry;
4) and removing the organic solvent from the obtained nano fluorescent dye slurry in a reduced pressure distillation mode to prepare the nano fluorescent dye. The nano fluorescent dye particles have the average particle diameter of 55nm and the particle size distribution PDI value of 0.18.
Example 10
A preparation method of nano fluorescent dye comprises the following steps:
1) dissolving fluorescent dye nile red in ethanol to prepare 100mL of fluorescent dye ethanol solution with the concentration of 30 mg/L;
2) preparing 800mL of surfactant aqueous solution with the concentration of 1.5g/L by polyvinylpyrrolidone and deionized water;
3) starting the super-gravity rotating packed bed, and adjusting the rotating speed to 800 rpm; starting a feeding pump, and controlling the feeding rate of the fluorescent dye ethanol solution to be 75mL/min and the feeding rate of the surfactant aqueous solution to be 600 mL/min; simultaneously conveying the fluorescent dye ethanol solution and the surfactant aqueous solution to a supergravity rotary packed bed for mixing and precipitation reaction at the reaction temperature of 10 ℃, and closing the supergravity rotary packed bed after the fluorescent dye ethanol solution is fed to obtain nano fluorescent dye slurry;
4) and removing the organic solvent from the obtained nano fluorescent dye slurry in a reduced pressure distillation mode to prepare the nano fluorescent dye. Through detection, the average particle diameter of the nano fluorescent dye particles is 80nm, and the particle size distribution PDI value is 0.26.
Comparative example 1
Example 1 was repeated with the only difference that: no surfactant was added to the aqueous solution. Fig. 4 shows a scanning electron micrograph and a real micrograph of the nano fluorescent dye prepared in comparative example 1. As can be seen from the figure, the obtained nano fluorescent dye has micron-sized particles, is seriously agglomerated and cannot be stably dispersed in water to directly generate precipitate.
Comparative example 2
Example 1 was repeated with the only difference that: the reaction device adopts a traditional stirring kettle. FIG. 5 shows a transmission electron micrograph of the nano fluorescent dye prepared in comparative example 2, from which it can be seen that the average particle diameter of the nano fluorescent dye particles prepared in the conventional stirred tank is 55nm, which is larger than the size of the nano particles prepared in the super-gravity rotating bed. FIG. 6 shows fluorescence spectra of the nano fluorescent dyes prepared in comparative example 2 and example 1, from which it can be seen that the nano fluorescent dye prepared in the conventional stirred tank has lower fluorescence intensity than that prepared in the super-gravity rotating bed.
Comparative example 3
Example 1 was repeated with the only difference that: dissolving fluorescent dye nile red in acetone to prepare a fluorescent dye acetone solution with the concentration of 800 mg/L. Fig. 7 shows a transmission electron micrograph of the nano fluorescent dye prepared in comparative example 3. As can be seen from the figure, the nano fluorescent dye has the advantages of obviously increased particle size, serious particle agglomeration and poor stability.
Comparative example 4
Example 1 was repeated with the only difference that: tween 80 and deionized water are prepared into 0.1g/L surfactant aqueous solution. The results show that the prepared nano fluorescent dye particles can not be stably dispersed in aqueous solution, the size is 800nm, and the PDI value is 0.76.
Comparative example 5
Example 1 was repeated with the only difference that: the volume ratio of the acetone solution of the fluorescent dye to the aqueous solution of the surfactant is 2: 1. The result shows that the prepared nano fluorescent dye particles are seriously agglomerated and have obviously increased size, and the nano fluorescent dye particles cannot be obtained.
Comparative example 6
Example 1 was repeated with the only difference that: the speed of the super-gravity rotating packed bed is 200 rpm. The results showed that the prepared nano fluorescent dye particles were enlarged, the size was 600nm, and the PDI value was 0.62.
Comparative example 7
Example 1 was repeated with the only difference that: the mixing temperature of the supergravity rotating packed bed is 60 ℃. The result shows that the prepared nano fluorescent dye has larger particle size of 500 nm; the particle size distribution was not uniform, and the PDI value was 0.83.
It should be understood that the above-described embodiments of the present invention are merely examples for clearly illustrating the present invention, and are not intended to limit the embodiments of the present invention. Other variations and modifications will be apparent to persons skilled in the art in light of the above description. Not all embodiments are exhaustive. All obvious changes and modifications which are obvious to the technical scheme of the invention are covered by the protection scope of the invention.
Claims (8)
1. A preparation method of a nano fluorescent dye is characterized by comprising the following steps:
s1, dissolving the fluorescent dye in an organic solvent to prepare a fluorescent dye organic solution, and marking as feed liquid A;
s2, dissolving a surfactant in water to prepare a surfactant aqueous solution, and marking as feed liquid B;
s3, simultaneously injecting the feed liquid A and the feed liquid B into a supergravity rotary packed bed through a feed inlet, premixing the feed liquid A and the feed liquid B through a liquid distributor, then entering a packing layer, providing a strong supergravity environment for a molecular mixing process through high-speed rotation of an inner rotor in the packing layer, fully mixing and precipitating the feed liquid A and the feed liquid B, then flowing into cavities of the inner wall and the rotor, then discharging from a discharge outlet, and collecting to obtain nano fluorescent dye slurry;
s4, removing the organic solvent from the nano fluorescent dye slurry obtained in the step S3 in a reduced pressure distillation mode to prepare nano fluorescent dye;
in step S1, the fluorescent dye is a hydrophobic fluorescent dye; the hydrophobic fluorescent dye comprises one or more of nile red, curcumin, fluorescein, pyrene and coumarin;
in step S1, the concentration of the fluorescent dye organic solution is 5-600 mug/mL;
in the steps S1 and S2, the volume ratio of the feed liquid A to the feed liquid B is 1:1-1: 30;
in step S2, the concentration of the surfactant aqueous solution is 0.2-10 mg/mL;
in step S3, the rotating speed of the rotor of the super-gravity rotating packed bed is 300-;
in step S3, the temperature of the mixture of feed liquid A and feed liquid B in the high gravity rotating packed bed is 5-50 ℃.
2. The method for preparing nano fluorescent dye according to claim 1, wherein: the concentration of the fluorescent dye organic solution is 10-500 mu g/mL.
3. The method for preparing nano fluorescent dye according to claim 1, wherein: in step S1, the organic solvent is selected from one or more of methanol, ethanol, propanol, acetone, acetonitrile, and tetrahydrofuran.
4. The method for preparing nano fluorescent dye according to claim 3, wherein: in step S1, the organic solvent is one or more selected from methanol, ethanol, acetone, and tetrahydrofuran.
5. The method for preparing nano fluorescent dye according to claim 1, wherein: the volume ratio of the feed liquid A to the feed liquid B is 1:1-1: 20.
6. The method for preparing nano fluorescent dye according to claim 1, wherein: in step S2, the surfactant is selected from one or more of tween 20, tween 80, sodium dodecyl sulfate, sodium dodecyl benzene sulfonate, polyethylene glycol 400, polyethylene glycol 600, polyethylene glycol 1000, polyethylene glycol 2000, polyvinyl alcohol, hydroxypropyl methyl cellulose, polyoxyethylene castor oil, and polyvinylpyrrolidone.
7. The method for preparing nano fluorescent dye according to claim 1, wherein: the concentration of the surfactant aqueous solution is 0.4-10 mg/mL.
8. The method for preparing nano fluorescent dye according to claim 1, wherein: in step S4, the vacuum distillation parameters: the temperature is 30-70 ℃, and the vacuum degree is 0.02-0.1 MPa.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201810770070.3A CN110713734B (en) | 2018-07-13 | 2018-07-13 | Preparation method of nano fluorescent dye |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201810770070.3A CN110713734B (en) | 2018-07-13 | 2018-07-13 | Preparation method of nano fluorescent dye |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN110713734A CN110713734A (en) | 2020-01-21 |
| CN110713734B true CN110713734B (en) | 2020-12-25 |
Family
ID=69208541
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201810770070.3A Active CN110713734B (en) | 2018-07-13 | 2018-07-13 | Preparation method of nano fluorescent dye |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN110713734B (en) |
Families Citing this family (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111234809B (en) * | 2020-03-17 | 2023-08-08 | 哈尔滨工业大学(深圳)(哈尔滨工业大学深圳科技创新研究院) | Universal preparation method of water-soluble organic long-afterglow nano aqueous solution |
| WO2022239852A1 (en) * | 2021-05-13 | 2022-11-17 | 国立大学法人東京海洋大学 | Staining solution, plastic detecting method, processing device, and program |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO1999007876A2 (en) * | 1997-08-12 | 1999-02-18 | Byk Gulden Lomberg Chemische Fabrik Gmbh | Method for assaying cellular protein |
| CN101803741A (en) * | 2010-04-20 | 2010-08-18 | 浙江新和成股份有限公司 | Method for preparing nano vitamin E water dispersing powder preparation by using supergravity method |
| CN104262522A (en) * | 2014-09-04 | 2015-01-07 | 江南大学 | Method for preparing nano fluorescent pigment dispersion |
| CN108017771A (en) * | 2017-12-30 | 2018-05-11 | 北京化工大学 | A kind of method that aqueous polyurethane nano lotion is prepared by supergravity reactor |
-
2018
- 2018-07-13 CN CN201810770070.3A patent/CN110713734B/en active Active
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO1999007876A2 (en) * | 1997-08-12 | 1999-02-18 | Byk Gulden Lomberg Chemische Fabrik Gmbh | Method for assaying cellular protein |
| CN101803741A (en) * | 2010-04-20 | 2010-08-18 | 浙江新和成股份有限公司 | Method for preparing nano vitamin E water dispersing powder preparation by using supergravity method |
| CN104262522A (en) * | 2014-09-04 | 2015-01-07 | 江南大学 | Method for preparing nano fluorescent pigment dispersion |
| CN108017771A (en) * | 2017-12-30 | 2018-05-11 | 北京化工大学 | A kind of method that aqueous polyurethane nano lotion is prepared by supergravity reactor |
Also Published As
| Publication number | Publication date |
|---|---|
| CN110713734A (en) | 2020-01-21 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| Nidhin et al. | Synthesis of iron oxide nanoparticles of narrow size distribution on polysaccharide templates | |
| CN110713734B (en) | Preparation method of nano fluorescent dye | |
| CN103937478B (en) | Preparation method of nanofluid for improving oil recovery | |
| CN108192602B (en) | Metal-free polymer carbon dot with room-temperature phosphorescence property, and preparation method and application thereof | |
| EP2143776B1 (en) | Dispersions of luminescent rare earth oxide particles, varnish comprising these particles, method for preparing them and method for marking substrates | |
| US11407941B2 (en) | Fluorescent nanomaterial and preparation method and applications thereof | |
| CN103857385B (en) | Self-assembled nano structures granule and preparation method | |
| Yin et al. | High‐gravity‐assisted synthesis of aqueous nanodispersions of organic fluorescent dyes for counterfeit labeling | |
| TW552250B (en) | Barium titanate dispersions | |
| CN111426659B (en) | Magnetic fluorescent coding microsphere and preparation method thereof | |
| CN111334296A (en) | Ultrathin SiO2Encapsulated NaYF4Method for synthesizing Yb, Er composite nano particle | |
| Nguyen et al. | Encapsulation by Directed PISA: RAFT‐Based Polymer‐Vesiculated Pigment for Opacity Enhancement in Paint Films | |
| CN109199873B (en) | Inorganic nanoparticle cluster for dental repair resin and preparation method thereof | |
| CN110499043B (en) | Preparation method of nano disperse dye | |
| FR2862631A1 (en) | Producing rare earth metal oxide powders, e.g. useful as luminescent or colored pigments or catalyst supports, comprises heating nitrate precursors in a polar organic solvent | |
| CN107603347B (en) | Water-based nano color paste dispersing agent and preparation method thereof | |
| CN108822302B (en) | Janus nano-particle and preparation method and application thereof | |
| Liu et al. | Recovery of TiO2 nanoparticles synthesized in reverse micelles by antisolvent CO2 | |
| CN114672307B (en) | Carbon dot-based room-temperature phosphorescent composite material and preparation method thereof | |
| Cao et al. | Dispersing hydrophilic nanoparticles in nonaqueous solvents with superior long-term stability | |
| JP4870383B2 (en) | Method for concentrating nanoparticles | |
| Lu et al. | Ru (bpy) 2 (phen-5-NH 2) 2+ doped ultrabright and photostable fluorescent silica nanoparticles | |
| CN113460995A (en) | Method for simultaneously preparing carbon dots and nano zinc oxide | |
| CN105776306A (en) | Surface modification method of sub-10 nanometer NaGdF4 nanocrystalline and application of method to nuclear magnetic resonance | |
| CN112299467A (en) | Preparation method of monodisperse oil phase nano barium sulfate dispersoid |
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 |