CN108568279A - A kind of feather down protein nano microballoon and preparation method thereof - Google Patents
A kind of feather down protein nano microballoon and preparation method thereof Download PDFInfo
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- CN108568279A CN108568279A CN201810235626.9A CN201810235626A CN108568279A CN 108568279 A CN108568279 A CN 108568279A CN 201810235626 A CN201810235626 A CN 201810235626A CN 108568279 A CN108568279 A CN 108568279A
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J13/00—Colloid chemistry, e.g. the production of colloidal materials or their solutions, not otherwise provided for; Making microcapsules or microballoons
- B01J13/02—Making microcapsules or microballoons
- B01J13/06—Making microcapsules or microballoons by phase separation
- B01J13/14—Polymerisation; cross-linking
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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
- C08J3/24—Crosslinking, e.g. vulcanising, of macromolecules
- C08J3/246—Intercrosslinking of at least two polymers
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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
- C08J2389/00—Characterised by the use of proteins; Derivatives thereof
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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
- C08J2491/00—Characterised by the use of oils, fats or waxes; Derivatives thereof
- C08J2491/06—Waxes
Abstract
The present invention provides a kind of feather down protein nano microballoons and preparation method thereof, compared with prior art, the present invention has broken the traditional protein microspheres problem and limitation, first use compound lye system, the stirring and dissolving feather down under normal temperature condition, the dissolution rate of feather down is higher than 94%, the process advantages such as high, energy-saving with dissolution rate；Meanwhile it using emulsification and cross linked+ULTRASONIC COMPLEX effect technique, preparing the distribution of feather down molecular weight of albumen and concentrating, concentration is higher, can be directly used for microballoon preparation, has efficient process advantage when saving, it is controllable to realize microspherulite diameter, and balling-up is good, optimizes microspheres.
Description
Technical field
The invention belongs to protein microsphere preparation fields, and in particular to a kind of feather down protein nano microballoon and its preparation side
Method.
Background technology
Protein microsphere has the characteristics that good biocompatibility, biodegradable, large specific surface area, good dispersion,
By functions such as the infiltration of microglobulin cyst wall, selection filtering and controlled releases, using protein material, by core material, (such as drug contaminates
Material, function additive, mark substance etc.) processing be prepared into protein microsphere, be greatly improved the stability of core material, while assigning it can
The release function of control.Therefore protein microsphere technology will be in enzyme immobilizatio, biological antibody and vaccine development, new drug development and drug
The multiple fields such as sustained release have broad application prospects.
About the research hotspot of protein microsphere, mainly the technology of preparing including nanoparticle, microballoon wall material protein come at present
The expansion in source and performance study etc..Research shows that nanoprotein microballoon has higher dispersibility, excellent stable storing
Property, efficient drug release efficiency.Meanwhile feather down fibrous body is native protein, if feather down albumen is used,
Protein resource channel can be widened, while there is the social benefit to turn waste into wealth, is of great significance.
Traditional protein microspheres, including emulsion process, spray drying process, self-assembly method and laminar jet technology etc.,
But the above method has the following defects and problem：In emulsifying process, solvent removal is not thorough enough, or even will produce toxic
The problem of substance；The problem of drying process with atomizing easy tos produce accumulation, sticks together, and yield declines；Self assembly and spray drying process are micro-
Ball is at the problems such as spherical poor, grain size is difficult to control.
Invention content
In order to solve the above technical problems, the purpose of the present invention is to provide a kind of feather down protein nano microballoon and its preparations
Method, using emulsification and cross linked+ULTRASONIC COMPLEX effect technique, the extraction and feather down albumen that solve water-soluble feather down albumen are received
The preparation problem of meter Wei Qiu.The dissolution rate of feather down is high, is concentrated moreover, preparing the distribution of feather down molecular weight of albumen, and concentration is higher,
Microballoon preparation is can be directly used for, there is efficient process advantage when saving.
Specific technical solution of the present invention is as follows：
A kind of preparation method of feather down protein nano microballoon provided by the invention, includes the following steps：
1) compound lye dissolution system, is prepared：
Sodium carbonate, sodium hydroxide are dissolved in water, stirring and dissolving after being cooled to room temperature, adds moisture absorption cosolvent, and stirring is molten
Xie Hou adds stabilizer component carboxymethyl cellulose, stirs and evenly mixs to get compound lye dissolution system；
2), feather down is added in the compound lye dissolution system prepared, stirring at low speed dissolving is molten to get feather down albumen
Solve liquid；
3), under heating and stirring condition, 80 emulsifier of Span is added into atoleine, stops heating after adding,
Continual ultrasonic concussion is to get paraffin solution under the conditions of waste heat；
4), feather down protein dissolution liquid prepared by step 2) is added in the paraffin solution of step 3) preparation, ultrasound, until
It is formed and stablizes milky W/O lotions；
5), glutaraldehyde cross-linking agent is added in the system of step 4) preparation, continues to be ultrasonically treated, obtains microspheres solution；
6) isopropanol, is added into step 5) thus obtained microsphere solution, centrifuges, supernatant liquor is poured out, using petroleum ether to micro-
Ball is rinsed and is filtered repeatedly, and normal temperature and pressure is dried to get feather down protein nano microballoon.
Mass concentration 2-4% of the sodium carbonate in system in step 1)；The mass concentration 1-2% of sodium hydroxide；
Moisture absorption cosolvent described in step 1) is made of the raw material of following mass ratio：Urea：Thiocarbamide：Glycerine：Certain herbaceous plants with big flowers alcohol：It is different
Structure tridecanol=20：20：3：1：0.5.
Mass concentration of the moisture absorption cosolvent in system is 12-15% in step 1)；
The mass concentration in system of stabilizer component described in step 1) is 0.8-1.0%.
The lysate after moisture absorption cosolvent is added in step 1) under conditions of not dissolving feather down at once, it is steady without being added
Determine agent component, closing room temperature preserves, and stabilizer component is added thereto before dissolving feather down.
Step 2) mesoptile suede carries out under the conditions of being dissolved in 20-25 DEG C.
Step 2) mesoptile suede and the mass ratio of compound lye dissolution system are 2-5：100.The stirring at low speed is specially：
Under the conditions of 20-50r/min, stirring and dissolving 4-12h.
It is 5-10ml/min that the rate of 80 emulsifier of Span is added in step 3)；
It is specially under heating and stirring condition described in step 3)：In stir speed (S.S.) 20-30r/min and heating temperature
Under the conditions of 40-55 DEG C.
Ultrasonic vibration described in step 3) refers to：Ultrasonic power 80w, frequency 45KHz, time 5-10min.
Ultrasound described in step 4) refers to：Ultrasonic power 80w, frequency 45KHz, ultrasonic time 60min.
The mass concentration of the liquid of feather down protein dissolution described in step 4) is preferably 4%.
Feather down protein dissolution liquid prepared by step 2) is added to the paraffin solution middling speed of step 3) preparation in step 4)
Rate is：30-50ml/min.
It is ultrasonic described in step 5)：Power 80w, frequency 45KHz time 120min.
In above-mentioned preparation process, atoleine, 80 emulsifier of Span, feather down protein dissolution liquid and glutaraldehyde cross-linking agent
Volume ratio is 40-45：4：4-6：0.8-1.2.
A kind of feather down protein nano microballoon provided by the invention, is prepared using the above method.
The present invention first uses compound lye system, the dissolution rate of the stirring and dissolving feather down under normal temperature condition, feather down high
In 94%, the process advantages such as high, energy-saving with dissolution rate；Meanwhile using emulsification and cross linked+ULTRASONIC COMPLEX effect technique, system
Standby feather down molecular weight of albumen distribution is concentrated, and concentration is higher, can be directly used for microballoon preparation, efficient technique is excellent when having section
Gesture, it is controllable to realize microspherulite diameter, and balling-up is good, optimizes microspheres.The preparation method has broken traditional egg
The white microspheres problem and limitation.
Compared with prior art, the present invention is based on the unique shear action of ultrasonic wave and strong peptizaiton, pass through ultrasonic wave
The adjustment of the parameters such as power and frequency is completed simple to the control green high-efficient and method of feather down protein microsphere grain size.Breast
Change-crosslinking process selection ensures micro-sphere material stability and balling-up, can pass through the adjustment tune of the technological parameters such as dosage of crosslinking agent
Microballoon ultimate size and medicament slow release performance are saved, each link is easy to operate, and operability is strong.Same emulsification-the crosslinking of ultrasonic instrument
Technique is preferably agreed with, and the mechanical agitation process of traditional handicraft is reduced, and is conducive to homogeneous latex emulsion and is formed not cross-linking reaction offer
Good reaction condition, and shorten microballoon preparation time.Prepared microballoon possesses more uniform grain size compared with traditional handicraft
Distribution, microballoon pattern is more regular, and lamination and viscous glutinous phenomenon greatly reduce between microballoon, and process controllability further strengthens.
Description of the drawings
Figure 1A is before feather down dissolves；
Figure 1B is that feather down dissolves 6 hours；
Fig. 2 is that feather down dissolves process；
Fig. 3 A are high magnification numbe feather down protein microsphere surface sweeping Electronic Speculum；
Fig. 3 B are multiple feather down protein microsphere surface sweeping Electronic Speculum；
Fig. 4 feather down protein microsphere grain size distributions.
Specific implementation mode
Embodiment 1
A kind of preparation method of feather down protein nano microballoon, includes the following steps：
1) compound lye dissolution system is prepared：
At room temperature, sodium carbonate, sodium hydroxide are dissolved in water, sodium carbonate mass concentration is 2.5%, sodium hydroxide mass concentration
It is 1%；After stirring and dissolving, after being cooled to room temperature, moisture absorption cosolvent is added, after stirring and dissolving, moisture absorption cosolvent matter in system
Measure a concentration of 13%；Stabilizer component carboxymethyl cellulose is added, is stirred and evenly mixed, carboxymethyl cellulose quality in system is dense
Degree is for 0.8% to get compound lye dissolution system；The moisture absorption cosolvent is made of the raw material of following mass ratio：Urea：Sulphur
Urea：Glycerine：Certain herbaceous plants with big flowers alcohol：Isomerous tridecanol=20：20：3：1：0.5.
2) feather down is added in the compound lye dissolution system prepared, at 20 DEG C, under 30r/min mixing speeds, is stirred
Mix dissolving for 24 hours, the feather down protein dissolution liquid that dissolution rate 94.5% is 4% to get mass concentration；
Feather down is initially distributed in compound alkali systems, and is gradually dissolved；Pattern of the feather Down Fiber in dissolution system
As shown in FIG. 1A and 1B.Shown in Figure 1A and Figure 1B, compound alkali soluble enzymatic hydrolysis system is in water white transparency, submerges feather down under room temperature
Wherein, lysate is in rapidly yellow transparent shape, and as feather down further dissolves, solution is in light yellow muddy shape, dissolution system
Middle fiber morphology is as shown in Figure 2.As it can be seen that the compound alkali soluble system that uses of the present invention can at normal temperatures to feather down high-efficiency dissolution,
After dissolving for 24 hours, the solubility of feather down is 94.5%.
3), weighing 40mL goes atoleine solution to be placed in dry beaker, then in the consistent mechanical of rate 20r/min
It is heated to 40 DEG C under stirring condition, 80 emulsifier of 4mL Spans is added dropwise into atoleine according to 6ml/min rates, stops after adding
It only heats, continual ultrasonic shakes under the conditions of waste heat, and ultrasonic oscillation 8min is to get stone under the conditions of power 80w, frequency 45KHz
Wax solution；
4) power 80w, is kept, continues ultrasound under the conditions of frequency 45KHz, in ultrasound condition, takes the 4% of step 2) preparation
Feather down protein dissolution liquid 4ml is added in the paraffin solution of step 3) preparation, stablizes milky W/O lotions until being formed；It opens
Ultrasound, continual ultrasonic 60min under frequency 45kHz, 80w power stablize milky W/O lotions until being formed.(control frequency
45kHz, too low ultrasonic frequency can lead to prepare microspherulite diameter distribution and broaden, and excessively high frequency can then cause to be demulsified, drop
Humble ball yield, ultrasonic power, ultrasonic time affect microballoon ultimate size, and the present invention controls power 80w；High-power ultrasonic
Its shearing force is big when wave shakes, and microspherulite diameter reduces, and lotion reaches equilibration time reduction).Only rely on ultrasonic wave emulsification point by force
Scattered effect can not form stable feather down protein microsphere, need to continue to add crosslinking agent.
5) 1.2mL glutaraldehyde cross-linking agent, frequency are added in the feather down protein emulsion dispersion, prepared to step 4)
45kHz, 80w power lower duration 120min are made by the condensation reaction of amine aldehyde and aldol reaction of albumen and crosslinking agent
Feather down albumen is solidified into microballoon；
6) isopropanol of 3 times of volumes, is added into step 5) thus obtained microsphere solution, is centrifuged under 6000r/min rotating speeds
Supernatant liquor is poured out after 10min, microballoon is rinsed and filtered repeatedly using petroleum ether, and normal temperature and pressure is dried to get feather
Suede protein nano microballoon.
Microballoon is tested and characterization
It is as follows that the surveyed final performance of feather down protein microsphere is made using 1 the method for embodiment：
Microballoon form is observed using surface sweeping Electronic Speculum, finds albumen prepared by ultrasonic wave co-emulsifier-crosslinking process
Microballoon balling property is good, microsphere features smooth surface, and there is only a small amount of viscous glutinous.As shown in figs.3 a and 3b.
Microsphere Size is analyzed using Malvern particle size analyzer, the results showed that microsphere average grain diameter is
2072.5nm, is mainly distributed on two sections 164~295nm and 1990~5560nm, and grain size in 190nm, 3090nm and
Based on 5560nm distributions.As shown in Figure 4.
To sum up, this patent using ultrasonic wave co-emulsifier-crosslinking process prepare microballoon not only have good balling-up and
Controllability, and microspherulite diameter distribution is more concentrated, and the exploitation of the materials such as sustained-release micro-spheres is conducive to, before there is wide application
Scape.
Claims (10)
1. a kind of preparation method of feather down protein nano microballoon, which is characterized in that the preparation method comprises the following steps：
1) compound lye dissolution system, is prepared：
Sodium carbonate, sodium hydroxide are dissolved in water, stirring and dissolving after being cooled to room temperature, adds moisture absorption cosolvent, stirring and dissolving
Afterwards, stabilizer component carboxymethyl cellulose is added, is stirred and evenly mixed to get compound lye dissolution system；
2), feather down is added in the compound lye dissolution system prepared, stirring at low speed dissolves to get feather down protein dissolution
Liquid；
3), under heating and stirring condition, 80 emulsifier of Span is added into atoleine, stops heating after adding, in waste heat
Under the conditions of continual ultrasonic shake 5-10min to get paraffin solution；
4), feather down protein dissolution liquid prepared by step 2) is added in the paraffin solution of step 3) preparation, ultrasound, until being formed
Stablize milky W/O lotions；
5), glutaraldehyde cross-linking agent is added in the system of step 4) preparation, continues to be ultrasonically treated, obtains microspheres solution；
6) isopropanol, is added into step 5) thus obtained microsphere solution, centrifuge, pour out supernatant liquor, using petroleum ether to microballoon into
Row is rinsed and is filtered repeatedly, and normal temperature and pressure is dried to get feather down protein nano microballoon.
2. preparation method according to claim 1, which is characterized in that mass concentration of the sodium carbonate in system in step 1)
2-4%；The mass concentration 1-2% of sodium hydroxide.
3. preparation method according to claim 1 or 2, which is characterized in that moisture absorption cosolvent described in step 1) is by following
The raw material of mass ratio forms：Urea：Thiocarbamide：Glycerine：Certain herbaceous plants with big flowers alcohol：Isomerous tridecanol=20：20：3：1：0.5；Moisture absorption in step 1)
Mass concentration of the cosolvent in system is 12-15%.
4. preparation method according to claim 1 or 2, which is characterized in that stabilizer component is in system described in step 1)
Middle mass concentration is 0.8-1.0%.
5. preparation method according to claim 1 or 2, which is characterized in that step 2) mesoptile suede is dissolved with compound lye
The mass ratio of system is 2-5：100.
6. preparation method according to claim 1, which is characterized in that ultrasonic vibration described in step 3) refers to：Ultrasonic work(
Rate 80w, frequency 45KHz, time 40min；It is described to be specially under heating and stirring condition：In stir speed (S.S.) 20-30r/min and
Under the conditions of 40-55 DEG C of heating temperature.
7. preparation method according to claim 1, which is characterized in that ultrasound described in step 4) refers to：Ultrasonic power
80w, frequency 45KHz, ultrasonic time 60min；Feather down protein dissolution liquid prepared by step 2) is added to step in step 4)
3) the paraffin solution medium-rate prepared is：30-50ml/min.
8. preparation method according to claim 1, which is characterized in that ultrasonic described in step 5)：Power 80w, frequency
45KHz time 120min.
9. according to claim 1 be prepared, which is characterized in that atoleine, 80 emulsifier of Span, feather down albumen
Lysate and the volume ratio of glutaraldehyde cross-linking agent are 40-45：4：4-6：0.8-1.2.
10. a kind of feather down protein nano microballoon that claim 1-9 any one of them methods are prepared.
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