CN110229368A - Janus particle with biocompatibility and preparation method thereof - Google Patents
Janus particle with biocompatibility and preparation method thereof Download PDFInfo
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- CN110229368A CN110229368A CN201910621443.5A CN201910621443A CN110229368A CN 110229368 A CN110229368 A CN 110229368A CN 201910621443 A CN201910621443 A CN 201910621443A CN 110229368 A CN110229368 A CN 110229368A
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J3/00—Processes of treating or compounding macromolecular substances
- C08J3/12—Powdering or granulating
- C08J3/14—Powdering or granulating by precipitation from solutions
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J7/00—Chemical treatment or coating of shaped articles made of macromolecular substances
- C08J7/04—Coating
- C08J7/0427—Coating with only one layer of a composition containing a polymer binder
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- 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
- C09K23/00—Use of substances as emulsifying, wetting, dispersing, or foam-producing agents
- C09K23/017—Mixtures of compounds
- C09K23/018—Mixtures of two or more different organic oxygen-containing compounds
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- 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
- C09K23/00—Use of substances as emulsifying, wetting, dispersing, or foam-producing agents
- C09K23/16—Amines or polyamines
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2367/00—Characterised by the use of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Derivatives of such polymers
- C08J2367/04—Polyesters derived from hydroxy carboxylic acids, e.g. lactones
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2393/00—Characterised by the use of natural resins; Derivatives thereof
- C08J2393/02—Shellac
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2477/00—Characterised by the use of polyamides obtained by reactions forming a carboxylic amide link in the main chain; Derivatives of such polymers
- C08J2477/04—Polyamides derived from alpha-amino carboxylic acids
Abstract
The invention discloses a kind of Janus particle and preparation method thereof with biocompatibility.The present invention uses biocompatible materials, lac and poly-lactic acid material are dissolved in common good solvent, then mixed solution is rapidly injected in the aqueous solution containing surfactant at a certain temperature, based on co-precipitation and phase separating mechanism, obtaining one end is lac-polylactic acid Janus nano particle that the lac other end is polylactic acid.By adjusting the concentration of lac and polylactic acid in good solvent, the size of Janus nano particle can be regulated and controled；By adjusting the proportion of lac and polylactic acid in good solvent, the ratio of lac hemisphere and polylactic acid hemisphere in Janus nano particle can be regulated and controled.Then it is interacted by positive and negative charge, there is the polylysine of biocompatibility in the modification of lac hemisphere surface, improve the hydrophily of lac hemisphere.Janus nano particle with biocompatibility of the invention have it is amphipathic, can the lotion of stable oil in water well as granule surface activity agent.
Description
Technical field
The present invention relates to granular materials fields, and in particular to a kind of Janus particle and its preparation with biocompatibility
Method.
Background technique
Lotion has broad application prospects in fields such as food, cosmetics.Lotion includes Aqueous dispersions in oily phase
Water-in-oil emulsion is mutually dispersed in the oil-in-water emulsion in water phase with oil.The stabilization of lotion usually requires addition surfactant.It passes
The surfactant of system is the amphipathic molecule that a kind of existing hydrophilic radical has hydrophobic grouping again, and water/oil interface can be effectively reduced
Tension.But traditional molecular surface active agent at interface is the dynamic equilibrium of an adsorption and desorption, drop because of warm-up movement
It is easy to happen fusion.On the other hand, under the influence of Ostwald ripening, droplet will be gradually become smaller, and big drop will be by
Gradual change is big, eventually leads to and mutually separates.Amphipathic solid particle can effectively replace molecular surface active agent.Solid particle will not be because
Desorption occurs in water/oil interface for warm-up movement, stable Pickering lotion can be with long-time stable.However, at present still
There is not biocompatible Janus particle, significantly limits it in the application in the fields such as food, cosmetics.
The present invention uses biocompatible materials, and by being co-precipitated and mutually separating, the adjustable lac-polylactic acid of property is made
Janus nano particle.Polylysine further is modified by positive and negative charge interactive surfaces, improves the hydrophilic of lac hemisphere
Property.The obtained Janus nano particle with biocompatibility have it is amphipathic, can be very as granule surface activity agent
Stablize the lotion of oil in water well.
Summary of the invention
For the deficiency in the prior art, the present invention provides a kind of lac-polylactic acid Janus with biocompatibility
Particle and preparation method thereof.The preparation method uses biocompatible materials, such as lac, polylactic acid and polylysine material,
Such material has good biocompatibility and biodegradability, and green non-pollution has edibility.This method is easy
Easy, size, composition and the pattern for the Janus particle being prepared can carry out accuracy controlling, be based on its amphipathic structure, this
The Janus nano particle with biocompatibility of invention can be used as the granule surface activity agent of food-grade, well stable oil
Lotion in water.
To achieve the above object, the present invention provides following solution, includes the following steps:
(1) lac is dissolved in tetrahydrofuran, stirring is completely dissolved to obtain shellac solution to lac；Polylactic acid is added,
Obtain the mixed solution of lac and polylactic acid；Tween 80 is add to deionized water, it is water-soluble to obtain Tween 80 for ultrasonic disperse
Liquid；
(2) mixed solution obtained in step (1) and Tween 80 aqueous solution are heated, mixed solution is injected into Tween 80
In aqueous solution, rock uniformly mixed, the lac-polylactic acid Janus particle for obtaining having biocompatibility is in Tween 80 solution
Uniform dispersion；
(3) by the lac-polylactic acid Janus particle with biocompatibility being prepared in step (2) in tween
The uniform dispersion of 80 solution is stood at room temperature, is then taken above-mentioned solution, is centrifuged in supercentrifuge, is removed after centrifugation
Layer clear liquid, is then added deionized water, particle is uniformly dispersed again in water；Centrifugal dispersion process is repeated, surface is removed
Active agent tween 80 completes washing to Janus particle, obtains having the Janus particle of biocompatibility in deionized water
Uniform dispersion.
(4) polylysine is dissolved in deionized water, be added in step (3) the Janus particle that is prepared go from
Uniform dispersion in sub- water is stood, and positively charged polylysine passes through the mutual of positive and negative charge with electronegative lac hemisphere
Effect, obtains the uniform dispersion of the amphipathic Janus particle of Mercapto-group modification lac hemisphere in water.
As a preference of the present invention, in step (1),
The mass range that the lac is added in 1mL tetrahydrofuran is 2-100mg；It is further preferred that the lac
The mass range being added in 1mL tetrahydrofuran is 2-50mg, and the lac is a kind of natural lapping, is soluble in ethyl alcohol etc.
Organic solvent and alkaline solution but it is insoluble in neutral or acid solution.
The mass range that the polylactic acid is added in 1mL water is 2-100mg；It is further preferred that the polylactic acid exists
The mass range being added in 1mL tetrahydrofuran is 2-50mg, and the polylactic acid is a kind of high molecular material of synthesis, is soluble in four
Hydrogen furans but it is insoluble in ethyl alcohol.
The molecular weight ranges of the polylactic acid are 2000-5000；It is further preferred that the molecular weight of polylactic acid is 3000.
The volume fraction range that the Tween 80 is added in 1mL water is 0.5%-5%；It is further preferred that described spit
The volume fraction range that temperature 80 is added in 1mL water is 0.8%-2%.
As a preference of the present invention, in step (2),
The preparation process need to carry out in 65 DEG C -90 DEG C of water-bath, and the particle of generation can be in room temperature long-time stable.
It is further preferred that bath temperature is 70 DEG C.
It is 5ml/h-30ml/h that the mixed solution, which is injected into the injection rate in Tween 80 aqueous solution,；Further preferably
, injection rate 15ml/h-20ml/h.
The mixed solution and the volume percent range of Tween 80 aqueous solution are 1.67%-6.67%；Further preferably
, the volume fraction range of mixed solution and Tween 80 aqueous solution is 1.67%-3.33%.
As a preference of the present invention, in step (3),
The time range stood at room temperature is 4h-12h；It is further preferred that standing the time model of preservation at room temperature
It encloses for 6h.
The range of the Centrifugal dispersion number is 3 times -10 times；It is further preferred that centrifugal washing times are 5 times.
As a preference of the present invention, in step (4),
The quality of the polylysine and Janus particle is 2:1-5:1 than range；It is further preferred that polylysine with
The quality of Janus particle is 3:1-4:1 than range.
Another aspect of the present invention discloses the method and the Janus particle with biocompatibility is prepared, described
Janus particle size morphology controllable, the ratio of lac hemisphere and polylactic acid hemisphere is controllable in Janus particle.
The invention also discloses a kind of particle stabilized oil-in-water types of the amphipathic Janus of Mercapto-group modification lac hemisphere
The preparation method of lotion, includes the following steps:
Take the amphipathic Janus particle of the Mercapto-group modification lac hemisphere being prepared in claim 1 in water
Uniform dispersion adds silk oil, and oil is mutually 1:5 with the volume ratio of uniform dispersion, mixes water-oil phase 1-8min, obtains
The amphipathic Janus of Mercapto-group modification lac hemisphere particle stabilized emulsion oil-in-water.
The beneficial effects of the present invention are:
(1) using biocompatible materials as raw material, the Janus particle being prepared has good biocompatibility and life
Biodegradable, it is nontoxic to the human body non-stimulated, have edibility.At the same time, two hemisphere of Janus particle are by difference
Material composition, therefore Janus particle has the property there are two types of material simultaneously, the advantages of having taken into account lac and polylactic acid.
(2) size, the accuracy controlling of composition and pattern that Janus particle can be achieved, such as by adjusting lac and polylactic acid
Concentration in good solvent can regulate and control the size of Janus nano particle；By adjusting matching for lac and polylactic acid in good solvent
Than the ratio of lac hemisphere and polylactic acid hemisphere in Janus nano particle can be regulated and controled.
(3) the amphipathic Janus particle that the present invention prepares obtained Mercapto-group modification lac hemisphere can be used as particle
Surfactant improves the emulsion intercalation method of oil in water.
Detailed description of the invention
The present invention is further described with reference to the accompanying drawings and examples.
Fig. 1 (a) is the schematic diagram for the Janus particle that preparation has biocompatibility；
Fig. 1 (b) is the illustraton of model for the Janus particle that embodiment 1 is prepared；
Fig. 1 (c) is the scanning electron microscope (SEM) photograph for the Janus particle that embodiment 1 is prepared；
Fig. 2 is the optical imagery of embodiment 2Janus particle granule-morphology change procedure in alkaline solution；
Fig. 3 is the scanning electron microscope image of the Janus particle for the different-grain diameter size that embodiment 3 is prepared；
Fig. 4 is the scanning electron microscope image of the Janus particle for the different-shape that embodiment 4 is prepared；
Fig. 5 (a) is the model of the amphipathic Janus particle for the Mercapto-group modification lac hemisphere that embodiment 5 is prepared
Figure；
Fig. 5 (b) be the amphipathic Janus of Mercapto-group modification lac hemisphere that embodiment 5 is prepared it is particle stabilized
The schematic diagram of oil droplet in water；
Fig. 5 (c) is that the amphipathic Janus for the Mercapto-group modification lac hemisphere that embodiment 5 is prepared is particle stabilized
The optical imagery of oil droplet in emulsion oil-in-water；
Fig. 6 is the particle stabilized water packet of the amphipathic Janus for the Mercapto-group modification lac hemisphere that embodiment 5 is prepared
The image of the Janus that the image and embodiment 1 of water emulsion are prepared particle stabilized emulsion oil-in-water；
The amphipathic Janus particle of the Mercapto-group modification lac hemisphere that Fig. 7 (a) embodiment 5 is prepared is in water
The potential measurement of uniform dispersion；
The amphipathic Janus particle of the Mercapto-group modification lac hemisphere that Fig. 7 (b) embodiment 5 is prepared is in water
The measurement of the interfacial tension of uniform dispersion and oil.
Fig. 8 is the scanning electron microscope image for the particle that comparative example 1 is prepared；
Fig. 9 is the scanning electron microscope image for the particle that comparative example 2 is prepared；
Figure 10 is the scanning electron microscope image for the particle that comparative example 3 is prepared.
Specific embodiment
Embodiment 1: preparing has biocompatibility, the Janus particle that partial size is about 400nm
Referring to attached drawing 1 (a), there is the Janus particle of biocompatibility using method preparation of the invention, specific steps are such as
Under:
(1) 120mg lac is dissolved in 5ml tetrahydrofuran, is put into rotor and is stirred on magnetic agitation platform, until lac is complete
Dissolution obtains the shellac solution that concentration is 24mg/ml；120mg polylactic acid is dissolved in shellac solution again, ultrasonic disperse obtains
The mixed solution that lac concentration be 24mg/ml and PLA concentration is 24mg/ml.By 1ml Tween 80 be added to 100ml go from
In sub- water, the ultrasonic disperse in ultrasonic washing instrument, then filtered with disposable aspiration needle formula filter (specification: Φ 25mm*0.45 μm),
Obtain Tween 80 aqueous solution.
(2) Tween 80 aqueous solution of mixed solution and 3ml obtained in step (1) is taken to heat in thermostat water bath, if
Mixed solution obtained in the step of setting bath temperature is 70 DEG C, heats 15min, takes 100 μ l (1), by mixed solution with 20ml/
It in the step of flow velocity of h is injected into 3ml (1) in Tween 80 aqueous solution obtained, rocks uniformly mixed, obtains with bio-compatible
Uniform dispersion of the lac-polylactic acid Janus particle of property in Tween 80 solution.
(3) by the lac-polylactic acid Janus particle with biocompatibility being prepared in step (2) in tween
The uniform dispersion of 80 solution stands 6h at room temperature, then takes above-mentioned solution, is centrifuged in supercentrifuge, and setting revolving speed is
10000rpm, centrifugation time 8min remove supernatant liquor, deionized water are then added after centrifugation, in water again by particle
It is uniformly dispersed；It repeats Centrifugal dispersion process 5 times, removes surface active agent tween 80, complete the washing to Janus particle, obtain
To the uniform dispersion (such as shown in attached drawing 1 (b)) of the Janus particle with biocompatibility in deionized water, Janus particle
Scanning electron microscope (SEM) photograph such as attached drawing 1 (c) shown in, average grain diameter is about 400nm.
Embodiment 2:Janus particle granule-morphology change procedure in alkaline solution
(1) 150mg lac is dissolved in 5ml tetrahydrofuran, is put into rotor and is stirred on magnetic agitation platform, until lac is complete
Dissolution obtains the shellac solution that concentration is 30mg/ml；150mg polylactic acid is dissolved in shellac solution again, ultrasonic disperse obtains
The mixed solution that lac concentration be 30mg/ml and PLA concentration is 30mg/ml.By 1ml Tween 80 be added to 100ml go from
In sub- water, the ultrasonic disperse in ultrasonic washing instrument, then filtered with disposable aspiration needle formula filter (specification: Φ 25mm*0.45 μm),
Obtain Tween 80 aqueous solution.
(2) Tween 80 aqueous solution of mixed solution and 3ml obtained in step (1) is taken to heat in thermostat water bath, if
Mixed solution obtained in the step of setting bath temperature is 70 DEG C, heats 15min, takes 100 μ l (1), by mixed solution with 20ml/
It in the step of flow velocity of h is injected into 3ml (1) in Tween 80 aqueous solution obtained, rocks uniformly mixed, obtains with bio-compatible
Uniform dispersion of the lac-polylactic acid Janus particle of property in Tween 80 solution.
(3) by the lac-polylactic acid Janus particle with biocompatibility being prepared in step (2) in tween
The uniform dispersion of 80 solution stands 6h at room temperature, then takes above-mentioned solution, is centrifuged in supercentrifuge, and setting revolving speed is
10000rpm, centrifugation time 8min remove supernatant liquor, deionized water are then added after centrifugation, in water again by particle
It is uniformly dispersed；It repeats Centrifugal dispersion process 5 times, removes surface active agent tween 80, complete the washing to Janus particle, obtain
To the uniform dispersion of Janus particle in deionized water with biocompatibility.
(4) 4g sodium hydroxide is taken, with the deionized water dissolving of 50ml, the sodium hydroxide solution of dissolution is cooled to room temperature,
Adding deionized water to liquor capacity again is 100ml, obtains the pH=13 sodium hydroxide solution that concentration is 0.1mol/L.
(5) take the Janus particle with biocompatibility being prepared in step (3) in deionized water uniformly point
Deionized water dilution is added in dispersion liquid, obtains the uniform dispersion that Janus granule density is 2mg/mL, takes the 100 above-mentioned solution of μ L,
It is added drop-wise on glass slide, and is covered with coverslip, the 20 μ l of sodium hydroxide solution being prepared in step (4) is taken, in coverslip
Edge is slowly added to, and the pattern for observing some Janus particle under an optical microscope changes with time, as shown in Fig. 2,
The process that first swelling is gradually dissolved after becoming larger occurs for one of hemisphere of Janus particle, and another hemisphere is neither swollen nor
Dissolution, finally only exists a hemisphere in alkaline solution, this is because lac can gradually dissolve in alkaline environment, and poly- cream
Acid is not influenced by alkaline environment, and thus demonstrating the Janus particle half is lac material, and half is poly-lactic acid material.
Embodiment 3: the initial concentration by changing material regulates and controls the size of Janus particle
(1) according to embodiment 1 the step of, changes the concentration of lac and polylactic acid in tetrahydrofuran, but keeps lac dense
Spend identical as PLA concentration, several groups of following concentration be set: 2mg/ml, 6mg/ml, 12mg/ml, 18mg/ml, 24mg/ml,
30mg/ml, is prepared that lac hemisphere is identical with polylactic acid hemisphere volume respectively, but the overall dimensions of particle are in several hundred nanometers
In the range of the Janus particle that changes, as shown in Fig. 3.
(2) the various sizes of Janus particle DLS method being prepared in step (1) is measured into particle diameter distribution, result
It is as follows:
When lac and PLA concentration are 2mg/ml, the average grain diameter of Janus particle is about 230nm；
When lac and PLA concentration are 6mg/ml, the average grain diameter of Janus particle is about 270nm；
When lac and PLA concentration are 12mg/ml, the average grain diameter of Janus particle is about 300nm；
When lac and PLA concentration are 18mg/ml, the average grain diameter of Janus particle is about 350nm；
When lac and PLA concentration are 24mg/ml, the average grain diameter of Janus particle is about 400nm；
When lac and PLA concentration are 30mg/ml, the average grain diameter of Janus particle is about 700nm.
Embodiment 4: the initial concentration ratio by changing material regulates and controls the volume ratio of two hemisphere of Janus particle
(1) according to embodiment 1 the step of, keeping concentration of the PLA in tetrahydrofuran is that 12mg/ml is constant, changes lac
Concentration, is arranged several groups of following lac concentration: 4mg/ml, 8mg/ml, 12mg/ml, 16mg/ml, 20mg/ml, 24mg/ml,
The Janus particle that the volume ratio of two hemisphere in particle gradually changes is prepared in 28mg/ml, 32mg/ml respectively, such as attached
Shown in Fig. 4.
(2) the Janus particle DLS method being prepared in step (1) is measured into particle diameter distribution, result is as follows:
When it is 12mg/ml that lac, which is 4mg/ml, PLA concentration, the average grain diameter of Janus particle is about 300nm；
When it is 12mg/ml that lac, which is 8mg/ml, PLA concentration, the average grain diameter of Janus particle is about 330nm；
When it is 12mg/ml that lac, which is 12mg/ml, PLA concentration, the average grain diameter of Janus particle is about 340nm；
When it is 12mg/ml that lac, which is 16mg/ml, PLA concentration, the average grain diameter of Janus particle is about 380nm；
When it is 12mg/ml that lac, which is 20mg/ml, PLA concentration, the average grain diameter of Janus particle is about 390nm；
When it is 12mg/ml that lac, which is 24mg/ml, PLA concentration, the average grain diameter of Janus particle is about 400nm；
When it is 12mg/ml that lac, which is 28mg/ml, PLA concentration, the average grain diameter of Janus particle is about 450nm；
When it is 12mg/ml that lac, which is 32mg/ml, PLA concentration, the average grain diameter of Janus particle is about 5000nm.
Embodiment 5: the amphipathic Janus of Mercapto-group modification lac hemisphere particle stabilized emulsion oil-in-water
(1) 170mg polylysine is dissolved in 4ml deionized water, is added in 1ml embodiment 1 and is prepared into step (3)
The uniform dispersion of the Janus particle arrived in deionized water, Janus granule density are 48mg/mL, stand 4h, positively charged
Polylysine and electronegative lac hemisphere are interacted by positive and negative charge, obtain the amphiphilic of Mercapto-group modification lac hemisphere
Property Janus particle uniform dispersion in water (such as shown in attached drawing 5 (a)).
(2) the Sudan's II dyestuff for taking 50mg is added in the silk oil of 10ml, is sufficiently mixed, then with disposable aspiration needle formula
Filter (specification: Φ 25mm*0.45 μm) filtering obtains the silk oil of the Sudan's II dyeing.
(3) the amphipathic Janus particle of the Mercapto-group modification lac hemisphere being prepared in step (1) is taken in water
The silk oil of the Sudan's II dyeing obtained in 1ml step (2) is added, with whirlpool blending instrument Vortex in uniform dispersion 5ml
Mixer mixing water-oil phase 1min obtains the particle stabilized oil-in-water type of the amphipathic Janus of Mercapto-group modification lac hemisphere
Lotion, amphipathic Janus granular absorption is in oil droplets, as shown in attached drawing 5 (b).Observation is dispersed in water under the microscope
Oil droplet, as shown in attached drawing 5 (c).
(4) uniform dispersion of the Janus particle being prepared in step (3) in Example 1 in deionized water, obtains
The uniform dispersion that Janus granule density to 1mL is 48mg/mL, in the step of deionized water and 1ml of 4ml is added (1)
To the silk oil of the Sudan's II dyeing, with whirlpool blending instrument Vortex Mixer mixing water-oil phase 1min, Janus is obtained
The stable emulsion oil-in-water of grain is observed and is prepared into oil droplet and step (3) in the particle stabilized emulsion oil-in-water of Janus
To Mercapto-group modification lac hemisphere the particle stabilized emulsion oil-in-water of amphipathic Janus in oil droplet variation comparison
Figure, such as attached drawing 6.
Since the carboxy moiety of the lac hemisphere in Janus particle ionizes, cause lac surface negatively charged, and polylysine
Middle there are positively charged amino, and by the electrostatic interaction of positive and negative charge, lac hemisphere surface is adsorbed with positively charged gathering and relies
Propylhomoserin.Because polylysine has hydrophily, the lac hemisphere of Mercapto-group modification is also provided with hydrophily, while polylactic acid half
Ball has a hydrophobicity, therefore the Janus particle has amphipathic, and lac hemisphere is hydrophilic, and polylactic acid hemisphere is hydrophobic, according to the amphiphilic
Property can by Janus particle be used as surfactant, stablize water-oil phase.It is in attached drawing 7 (a) the experimental results showed that, gather rely
The current potential of amphipathic Janus particle of propylhomoserin modification lac hemisphere is decreased obviously, i.e., the negative electrical charge in Janus particle with gather
Positive charge in lysine neutralizes, and Electrostatic Absorption reaction has occurred in the two.It is in attached drawing 7 (b) the experimental results showed that, it is unmodified
Janus particle uniform dispersion in water and silk oil between interfacial tension it is larger, and Mercapto-group modification lac half
The amphipathic Janus particle of ball can significantly reduce the interfacial tension between grease, to realize the function of stable water-oil phase.
Comparative example 1: the influence that organic solvent forms Janus particle
Using the preparation process of embodiment 1, difference is step (1), wherein 120mg lac is dissolved in 5ml acetone.
Attached drawing 8 is the scanning electron microscope image for the particle that comparative example 1 is prepared.That comparative example 1 is prepared is of irregular shape
Grain, does not form the Janus particle of dumbbell shaped, and be prepared in embodiment 1 be one end be lac material, one end is poly- cream
The dumbbell shaped Janus particle of sour material, the comparative example illustrate have to the formation of Janus particle using different organic solvents
Important influence.
Comparative example 2: the influence that temperature forms Janus particle
Using the preparation process of embodiment 1, difference is step (2), wherein obtained mixed in the step of taking 100 μ l (1)
Solution is closed, in the step of mixed solution is injected into 3ml with the flow velocity of 20ml/h (1) in Tween 80 aqueous solution obtained, is rocked
It is uniformly mixed, obtains the Tween 80 solution of the particle containing Janus.Attached drawing 9 is the scanning electron microscope (SEM) photograph for the particle that comparative example 2 is prepared
As can be seen from the figure there is the particle of part dumbbell shape in picture, but most of particle is elliposoidal, compared with Example 1, right
The particle that ratio 2 is prepared only is partially the Janus particle of dumbbell shaped, which illustrates temperature to Janus particle
Formation have important influence.
Comparative example 3: the influence that surfactant forms Janus particle
Using the preparation process of embodiment 1, difference is to be added without Tween 80 surfactant, is spat with deionized water replacement
Warm 80 aqueous solutions.Attached drawing 10 is the scanning electron microscope image for the particle that comparative example 3 is prepared.The particle that comparative example 3 is prepared
Be elliposoidal, dumbbell shaped Janus particle be not prepared, and be prepared in embodiment 1 be one end be lac material, one
End is the dumbbell shaped Janus particle of poly-lactic acid material, which illustrates shape of the presence to Janus particle of surfactant
At with important influence.
Claims (7)
1. a kind of preparation method of the Janus particle with biocompatibility, which comprises the steps of:
(1) lac is dissolved in tetrahydrofuran, concentration range of the lac in tetrahydrofuran is 2-100mg/ml, stirring to lac
It is completely dissolved to obtain shellac solution；Polylactic acid is added, concentration range of the polylactic acid in tetrahydrofuran is 2-100mg/ml, is obtained
To the mixed solution of lac and polylactic acid；Tween 80 is add to deionized water, the volume of Tween 80 in deionized water point
Number range is 0.5%-5%, and ultrasonic disperse obtains Tween 80 aqueous solution；
(2) mixed solution obtained in step (1) and Tween 80 aqueous solution are heated separately to 65 DEG C -90 DEG C, at this temperature
Mixed solution is injected into Tween 80 aqueous solution with the speed of 5ml/h-30ml/h, the body of mixed solution and Tween 80 aqueous solution
Product percentage range is 1.67%-6.67%, rocks uniformly mixed, obtains the lac-polylactic acid with biocompatibility
Uniform dispersion of the Janus particle in Tween 80 solution；
(3) lac-polylactic acid Janus particle with biocompatibility being prepared in step (2) is molten in Tween 80
The uniform dispersion of liquid is stood at room temperature, is then taken above-mentioned solution, is centrifuged in supercentrifuge, and it is clear that upper layer is removed after centrifugation
Then deionized water is added in liquid, particle is uniformly dispersed again in water；Centrifugal dispersion process is repeated, surface-active is removed
Agent Tween 80 completes washing to Janus particle, obtains having the Janus particle of biocompatibility in deionized water equal
Even dispersion liquid.
(4) polylysine is dissolved in deionized water, the Janus particle being prepared in step (3) is added in deionized water
In uniform dispersion, the concentration range of polylysine in water is 24-400mg/mL, and Janus particle is dispersed in water dense
Degree range is 12-100mg/mL, and the quality of polylysine and Janus particle is 2:1-5:1 than range, stands 1-8h, positively charged
Polylysine and electronegative lac hemisphere by the interaction of positive and negative charge, obtain Mercapto-group modification lac hemisphere
The uniform dispersion of amphipathic Janus particle in water.
2. the preparation method of the Janus particle according to claim 1 with biocompatibility, which is characterized in that in step
Suddenly in (1),
The mass range that the lac is added in 1mL tetrahydrofuran is 2-100mg；
The mass range that the polylactic acid is added in 1mL water is 2-100mg；
The molecular weight ranges of the polylactic acid are 1000-5000；
The volume fraction range that the Tween 80 is added in 1mL water is 0.5%-5%.
3. the preparation method of the Janus particle according to claim 1 with biocompatibility, which is characterized in that in step
Suddenly in (2),
The preparation process need to carry out in 65 DEG C -90 DEG C of water-bath, and the particle of generation can be in room temperature long-time stable；
It is 5ml/h-30ml/h that the mixed solution, which is injected into the injection rate in Tween 80 aqueous solution,；
The mixed solution and the volume percent range of Tween 80 aqueous solution are 1.67%-6.67%.
4. the preparation method of the Janus particle according to claim 1 with biocompatibility, which is characterized in that in step
Suddenly in (3),
The time range stood at room temperature is 4h-12h；
The range of the Centrifugal dispersion number is 3 times -10 times.
5. the preparation method of the Janus particle according to claim 1 with biocompatibility, which is characterized in that in step
Suddenly in (4),
The quality of the polylysine and Janus particle is 2:1-5:1 than range.
6. the Janus particle with biocompatibility is prepared in method according to claim 1-5.
7. a kind of preparation method for the emulsion oil-in-water that the amphipathic Janus of Mercapto-group modification lac hemisphere is particle stabilized,
It is characterized by comprising following steps:
Take the amphipathic Janus particle for the Mercapto-group modification lac hemisphere being prepared in claim 1 in water uniform
Dispersion liquid adds silk oil, and oil is mutually 1:5 with the volume ratio of uniform dispersion, mixes water-oil phase 1-8min, obtains poly- rely
The amphipathic Janus of propylhomoserin modification lac hemisphere particle stabilized emulsion oil-in-water.
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111763292A (en) * | 2020-07-13 | 2020-10-13 | 中国科学院化学研究所 | Snowman-shaped Janus particle and preparation method thereof |
| CN112569879A (en) * | 2020-12-11 | 2021-03-30 | 苏州大学 | Template Janus microsphere, preparation method thereof and functionalized Janus microsphere |
| CN116102892A (en) * | 2022-12-23 | 2023-05-12 | 中国农业科学院农产品加工研究所 | Janus particle based on natural biological macromolecules and controllable preparation method and application thereof |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105513741A (en) * | 2016-01-11 | 2016-04-20 | 中国科学院化学研究所 | Magnetic nanoparticle/macromolecular Janus microparticle and preparation method and application thereof |
| US20170326073A1 (en) * | 2014-11-25 | 2017-11-16 | Cbc Co., Ltd. | Janus nanoparticle and method for producing the same |
| CN108912265A (en) * | 2018-06-26 | 2018-11-30 | 安徽大学 | A kind of Janus structural inorganic polymer hybrid microballoon and preparation method thereof |
| CN109364833A (en) * | 2018-09-25 | 2019-02-22 | 西北大学 | A method of preparing dual character nano particle |
-
2019
- 2019-07-10 CN CN201910621443.5A patent/CN110229368B/en active Active
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20170326073A1 (en) * | 2014-11-25 | 2017-11-16 | Cbc Co., Ltd. | Janus nanoparticle and method for producing the same |
| CN105513741A (en) * | 2016-01-11 | 2016-04-20 | 中国科学院化学研究所 | Magnetic nanoparticle/macromolecular Janus microparticle and preparation method and application thereof |
| CN108912265A (en) * | 2018-06-26 | 2018-11-30 | 安徽大学 | A kind of Janus structural inorganic polymer hybrid microballoon and preparation method thereof |
| CN109364833A (en) * | 2018-09-25 | 2019-02-22 | 西北大学 | A method of preparing dual character nano particle |
Non-Patent Citations (1)
| Title |
|---|
| KIETZKE T, ET AL.: ""Phase Separation of Bianry Blends in Polymer Nanoparticles"", 《SMALL》 * |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111763292A (en) * | 2020-07-13 | 2020-10-13 | 中国科学院化学研究所 | Snowman-shaped Janus particle and preparation method thereof |
| CN112569879A (en) * | 2020-12-11 | 2021-03-30 | 苏州大学 | Template Janus microsphere, preparation method thereof and functionalized Janus microsphere |
| CN112569879B (en) * | 2020-12-11 | 2022-04-22 | 苏州大学 | Template Janus microsphere, preparation method thereof and functionalized Janus microsphere |
| CN116102892A (en) * | 2022-12-23 | 2023-05-12 | 中国农业科学院农产品加工研究所 | Janus particle based on natural biological macromolecules and controllable preparation method and application thereof |
| CN116102892B (en) * | 2022-12-23 | 2024-04-09 | 中国农业科学院农产品加工研究所 | Janus particle based on natural biological macromolecules and controllable preparation method and application thereof |
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