CN106883463A - A kind of preparation method of pattern and size tunable type starch nanometer granule - Google Patents
A kind of preparation method of pattern and size tunable type starch nanometer granule Download PDFInfo
- Publication number
- CN106883463A CN106883463A CN201710099143.6A CN201710099143A CN106883463A CN 106883463 A CN106883463 A CN 106883463A CN 201710099143 A CN201710099143 A CN 201710099143A CN 106883463 A CN106883463 A CN 106883463A
- Authority
- CN
- China
- Prior art keywords
- starch
- nanometer granule
- prepared
- preparation
- starch nanometer
- 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.)
- Granted
Links
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L3/00—Compositions of starch, amylose or amylopectin or of their derivatives or degradation products
- C08L3/12—Amylose; Amylopectin; Degradation products thereof
-
- 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
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08B—POLYSACCHARIDES; DERIVATIVES THEREOF
- C08B30/00—Preparation of starch, degraded or non-chemically modified starch, amylose, or amylopectin
- C08B30/20—Amylose or amylopectin
-
- C—CHEMISTRY; METALLURGY
- C12—BIOCHEMISTRY; BEER; SPIRITS; WINE; VINEGAR; MICROBIOLOGY; ENZYMOLOGY; MUTATION OR GENETIC ENGINEERING
- C12P—FERMENTATION OR ENZYME-USING PROCESSES TO SYNTHESISE A DESIRED CHEMICAL COMPOUND OR COMPOSITION OR TO SEPARATE OPTICAL ISOMERS FROM A RACEMIC MIXTURE
- C12P19/00—Preparation of compounds containing saccharide radicals
- C12P19/04—Polysaccharides, i.e. compounds containing more than five saccharide radicals attached to each other by glycosidic bonds
-
- C—CHEMISTRY; METALLURGY
- C12—BIOCHEMISTRY; BEER; SPIRITS; WINE; VINEGAR; MICROBIOLOGY; ENZYMOLOGY; MUTATION OR GENETIC ENGINEERING
- C12P—FERMENTATION OR ENZYME-USING PROCESSES TO SYNTHESISE A DESIRED CHEMICAL COMPOUND OR COMPOSITION OR TO SEPARATE OPTICAL ISOMERS FROM A RACEMIC MIXTURE
- C12P19/00—Preparation of compounds containing saccharide radicals
- C12P19/16—Preparation of compounds containing saccharide radicals produced by the action of an alpha-1, 6-glucosidase, e.g. amylose, debranched amylopectin
Abstract
The invention discloses a kind of method for preparing pattern and size tunable type starch nanometer granule as template with natural polysaccharide, the short straight chain of starch prepared using biological enzyme, during short straight chain self assembly prepares nano particle, original position addition natural polysaccharide template, screen the polysaccharide template of different molecular structures, the pattern and particle diameter of starch nanometer granule are controlled, suitable different demands, pattern (hollow, spindle, spheroid) and the controllable nano particle of particle diameter (20 120nm) are prepared.Present device low, the process is simple of requirement, easy to operate, reaction is gentle, and the reaction time is short, efficiency high, is adapted to large-scale production.Preparation cost of the present invention is low, and energy resource consumption is few, does not have bazardous waste to produce, and meets the modern production requirement of " green production, environmental protection and energy saving ".
Description
Technical field
The invention belongs to field of nanometer technology, the system of specifically a kind of pattern and size tunable type starch nanometer granule
Preparation Method.
Background technology
Starch nanometer granule is a kind of starch granules of particle diameter less than 300nm, and preparing for current starch nanometer granule is main
It is most commonly seen with acid hydrolyzation using chemical method and Physical, mainly use H2SO4Or HCl/water solution starch granules is amorphous
Area, obtains nanometer starch crystal.Starch nanometer granule can also be prepared by the method such as anti-solvent, high-pressure homogeneous, crosslinking microemulsified,
But above method low yield, power consumption is big, relatively costly.Processed by the de- branch of biology enzyme and obtain short amylose, through self assembly system
Standby starch nanometer granule, yield is high, energy consumption is small, and green safety.But nano particle diameter prepared by the method is distributed more widely, because
The amount of the active material loaded between this nano particle differs greatly, and is unfavorable for the accurate quantification to active material；And pattern is more
More single for spherical, the application in some fields is limited, and limits the bioavailability of the active material of its delivery.According to text
Offer report, hollow nano particle will be significantly higher than solid nano particle to the embedding rate of active material, and bar-shaped nanometer
Particle can flow with vessel directions, improve the bioavailability of its active material delivered as wall material.
The content of the invention
Wide, particle diameter and the uncontrollable problem of pattern, purport of the present invention are distributed for nano particle diameter prepared by existing method
The preparation method of a kind of pattern and size tunable type starch nanometer granule is being provided.
The preparation method of a kind of pattern and size tunable type starch nanometer granule, its preparation process is：
(1) cushioning liquid is prepared：Prepare the sodium dihydrogen phosphate-citrate buffer solution of pH=4-6；
(2) general Shandong indigo plant enzyme pretreatment：General Shandong indigo plant enzyme is diluted to 120-150NPUN/mL with distilled water, general Shandong indigo plant enzyme is reduced
Denseness, it is dispersed in gelatinized starch beneficial to it；
(3) starch milk is prepared：The starch of mass-volume concentration 10-20% is prepared with sodium dihydrogen phosphate-citrate buffer solution
Emulsion；
(4) it is gelatinized：The starch milk that will be prepared makes starch be gelatinized completely in 100 DEG C of water-bath 20-60min, is then cooled to
55-65℃；
(5) digest：The general Shandong indigo plant enzyme liquid pre-processed to addition in the colloid starch solution after gelatinization, enzyme liquid is done with starch
The ratio of base is 0.1mL/g, 55-65 DEG C of enzymolysis 6-8h；
(6) low-speed centrifugal：The enzymolysis liquid that will be obtained is centrifuged 3-5min with the rotating speed of 2500-3500r/min while hot, to remove
Long linear starch；
(7) go out enzyme：Continue to heat, elevate the temperature to more than 90 DEG C, and keep 10-15min, enzyme is thoroughly inactivated,
2-5min is centrifuged under 2500-3500r/min, the enzyme of denaturation is sloughed, short amylose is obtained, washing, vacuum freeze drying are obtained
Short amylose dry powder；
(8) addition polysaccharide template in situ：Short amylose sodium dihydrogen phosphate-citrate buffer solution is prepared into mass body
Solution of the product than 5-15%, and to natural polysaccharide is added in solution, short amylose is 4-10 with the mass ratio of natural polysaccharide:1；
(9) self assembly prepares starch nanometer granule：The short amylose solution for adding natural polysaccharide is placed in 0-8 DEG C next time
Raw treatment 10-15h obtains starch nanometer granule suspension, and washing, vacuum freeze drying obtain starch nanometer granule.
Further, the natural polysaccharide is any in shitosan, guar gum, Arabic gum, sodium alginate, gum rosin
Kind.
Further, retrogradation processing procedure is stirred in step (9), and the rotating speed of stirring is 200-300r/min.
Further, it is amylopectin content starch high to be prepared in step (3) used by starch milk, including waxy corn forms sediment
One or more in powder, taro starch, rice starch, glutinous millet starch.
Further, the concrete operations of washing are in step (7), (9)：5000-7000r/min is centrifuged 5-15min, washing
4-5
Further, the temperature of vacuum freeze drying is -90--80 DEG C in step (7), (9), and pressure is 0-1Pa, time
It is 48-72h.
The inventive method has the advantage that：
Natural polysaccharide green, safety that the present invention is used, good biocompatibility, and with the difference point such as linear, dendroid
Minor structure, is added to natural polysaccharide as template original position in short amylose solution, and short amylose is by different structure
Polysaccharide molecule chain surface stacks, and forms specific nanostructured, then by further aggregation, assembling, can effectively control
The pattern (hollow, spindle, spheroid) and particle diameter (20-120nm) of starch nanometer granule.Hollow nano particle, it is internal empty
Chamber can be filled up completely with active material, and the charging ratio to active material is high.The nano particle of spheroid, its specific surface area is maximum,
Grain is smaller, is more conducive to adsorbing some small molecules, can fix enzyme molecule, improves the action activity of enzyme.The nano particle of spindle,
It has elongated nanostructured, is conducive to it in Optical Electro-Chemistry field and as the application in terms of reinforcer.
The method of addition in situ of the invention is different from the method wrapped up afterwards in the prior art, and parcel is to be prepared into nanometer afterwards
After particle, then in one layer of polysaccharide of outer finishing coat.The natural polysaccharide added in the present invention plays a part of emulsifying agent, by original position
Addition, can be as template before nano particle formation, that is, polysaccharide molecule chain is used as template, so as to form pattern not
Same, the less nanoparticle structure of particle diameter.Formed after nano particle, unnecessary polysaccharide can be coated with forming painting outside
Layer.
Present device low, the process is simple of requirement, easy to operate, reaction is gentle, and the reaction time is short, efficiency high, is adapted to big
Large-scale production.
Preparation cost of the present invention is low, and energy resource consumption is few, does not have bazardous waste to produce, and meets " green production, environmental protection section
The modern production requirement of energy ".
Brief description of the drawings
Fig. 1 is not added with polysaccharide (A), addition shitosan (B) in situ, guar gum (C), Arabic gum (D), sodium alginate (E)
The starch nanometer granule transmission electron microscope picture prepared with gum rosin (F)；
Fig. 2 is not added with polysaccharide (A), addition shitosan (B) in situ, guar gum (C), Arabic gum (D), sodium alginate (E)
The starch nanometer granule grain size distribution prepared with gum rosin (F)；
Fig. 3 is not added with the shallow lake of polysaccharide, addition shitosan in situ, guar gum, Arabic gum, sodium alginate and gum rosin preparation
The X- diffraction patterns of powder nano particle.
Fig. 4 is not added with polysaccharide (◇), addition shitosan () in situ, guar gum (△), Arabic gum (×), sodium alginate
The particle diameter of starch nanometer granule prepared by (*) and gum rosin (zero) under different pH treatment；
Fig. 5 is not added with polysaccharide (◇), addition shitosan () in situ, guar gum (△), Arabic gum (×), sodium alginate
The particle diameter of starch nanometer granule prepared by (*) and gum rosin (zero) under treatment of different temperature；
Fig. 6 is not added with polysaccharide (◇), addition shitosan () in situ, guar gum (△), Arabic gum (×), sodium alginate
The particle diameter of starch nanometer granule prepared by (*) and gum rosin (zero) under the treatment of different salt ionic concentrations；
Specific embodiment
In order to make the purpose , technical scheme and advantage of the present invention be clearer, it is right below in conjunction with drawings and Examples
The present invention is further elaborated.It should be appreciated that specific embodiment described herein is only used to explain the present invention, not
For limiting the present invention.
Material therefor, reagent and instrument, equipment are as follows in the embodiment of the present invention：
Embodiment 1
Prepare the starch nanometer granule of different-shape and particle diameter respectively according to following steps：
(1) cushioning liquid is prepared：Accurately weigh 3.27g disodium hydrogen phosphates and 2.24g citric acids are dissolved in 200mL distilled water
In, stirring makes it fully dissolve, stand-by；
(2) general Shandong indigo plant enzyme pretreatment：It is accurate to measure the general Shandong indigo plant enzyme instillation 10mL distillations that 1mL concentration is 1350NPUN/mL
In water, stirring is allowed to be sufficiently mixed, stand-by；
(3) starch milk is prepared：Weigh in 15g waxy corn starch addition 100mL cushioning liquid, mass volume ratio is obtained
15% starch emulsion；
(4) it is gelatinized：The starch milk that will be prepared makes starch be gelatinized completely in 100 DEG C of water-bath 20min, is then cooled to 58 DEG C；
(5) digest：To adding the general Shandong indigo plant enzyme 1.5mL, 58 DEG C of enzymolysis 6h that handle well in the colloid starch solution after gelatinization；
(6) low-speed centrifugal：The solution that will be obtained is centrifuged 3min with the rotating speed of 3000r/min while hot, to remove long linear shallow lake
Powder；
(7) go out enzyme：Continue to heat, elevate the temperature to 100 DEG C, keep 10min, enzyme is thoroughly lost activity, 3000r/
3min is centrifuged under min, the enzyme of denaturation is sloughed, short amylose is obtained, 6000r/min centrifugation 4 times (10min/ times) of washing will be heavy
Form sediment and partly obtain short amylose dry powder in -86 DEG C of vacuum freeze dryings；
(8) addition polysaccharide template in situ：Short amylose sodium dihydrogen phosphate-citrate buffer solution is prepared into mass body
Solution of the product than 10%, is divided into 6 parts, respectively to addition shitosan, guar gum, Arabic gum, sea in 5 parts of short amylose solutions
Mosanom and gum rosin, short amylose and shitosan, guar gum, Arabic gum, sodium alginate and gum rosin and Arabic gum
Mass ratio be 10:1, polysaccharide is not added with remaining 1 part of short amylose solution, as control.
(9) self assembly prepares starch nanometer granule：Stirred at the short amylose solution for adding natural polysaccharide is placed in into 4 DEG C
Retrogradation treatment 12h obtains starch nanometer granule suspension.6000r/min centrifugation washing 5 times (10min/ times), by sediment fraction-
86 DEG C of vacuum freeze drying 48h obtain starch nanometer granule.
Following performance detection is carried out to the above-mentioned 6 kinds of starch nanometer granules for preparing：
1. nano particle pattern and droplet measurement
Nano particle transmissioning electric mirror determining：Nano particle is dissolved in ultra-pure water, make its it is fully dispersed it is uniform after, drip in band
There is carbon to support on the copper mesh of film, and unnecessary solution is siphoned away with filter paper, then to the common drying of copper mesh, dried sample is put
Enter in transmission electron microscope system, vacuumize 5min, observed under 2kv accelerating potentials, take pictures.
Dynamic light scattering determines the size of nano particle diameter：Nano particle is dissolved in ultra-pure water, makes its fully dispersed
After uniform, 1mL suspensions are taken with liquid-transfering gun, after slowly being injected along one jiao of cuvette edge, be put into testboard and test, each sample
Test three times respectively, average.
As shown in Figure 1A, 2A, the starch nanometer granule for being not added with polysaccharide preparation is spherical in shape, and particle diameter is mainly distributed on 70-
Between 90nm.
As shown in Figure 1B, 2B, starch nanometer granule prepared by original position addition shitosan is spherical in shape, and very small, particle diameter is in 20-
Between 50nm, and most of chitosan nano particle is in uniform core shell structure, and inside has certain cavity, is conducive to living
The embedding of property material.
As shown in Fig. 1 C, 2C, starch nanometer granule prepared by original position addition guar gum is in irregular spherical particle, aggregation
Substantially, particle diameter is between 90-150nm for phenomenon.
As shown in Fig. 1 D, 2D, starch nanometer granule prepared by original position addition Arabic gum is in uniform core shell structure, wherein
Part is hollow, and particle diameter is mainly distributed between 40-70nm.
As shown in Fig. 1 E, 2E, starch nanometer granule prepared by original position addition sodium alginate is in dispersed spindle, long
Degree is mainly distributed between 120-170nm, and diameter is mainly distributed between 40-70nm.
As shown in Fig. 1 F, 2F, starch nanometer granule prepared by original position addition gum rosin is in irregular spherical, and nanometer
Particle surface has many little particles to assemble.Particle diameter very little, between 30-50nm.
2. thermal characteristics is determined
9 ± 1mg starch nanometer granule samples are weighed, it is 1 to pass through mass ratio with distilled water：2 ratio is well mixed, will be mixed
Close uniform sample and be placed on and 30min is balanced in aluminium crucible, then heated up with the speed of 10 DEG C/min, temperature range is 25
~120 DEG C, its T is determined respectivelyo(initial gelatinization temperature), Tp(peak value gelatinization point), Tc(end is worth gelatinization point) and enthalpy (△
H situation of change).
As shown in table 1, addition natural polysaccharide in situ significantly improves the peak value gelatinization point of starch nanometer granule, and it is last
The difference of value gelatinization point and initial gelatinization temperature reduces, and starch nanometer granule crystallization prepared by this explanation addition natural polysaccharide is more
Perfect, crystallite size is more uniform.Nano particle prepared by original position addition sodium alginate has highest peak value gelatinization point, heat
Stability is best.
The natural polysaccharide of table 1 is the thermal characteristics of starch nanometer granule prepared by template
3. X-ray diffraction is determined
After starch nanometer granule sample drying is ground, equilibrium water conten to 20%, using the special window film-making of X- diffraction.X-
Ray tube is put for copper-cobalt, and wave-length coverage is 1.54nm；Pipe presses 40kV, pipe stream 40mA, and scanning area is that the angle of diffraction is 3 °~60 °；
Diffraction speed is the 0.02 ° of angle of diffraction/3s.Crystallinity is calculated by software MDI Jade 5.0.
The X- diffracting spectrums of starch nanometer granule as shown in Figure 3, all of nanoparticle sample 2 θ be 5.6 °,
15.3 °, 17.1 °, 22.5 ° and 24.3 ° have diffraction maximum, and the crystalline form for illustrating starch nanometer granule is Type B.Original position addition natural polysaccharide
The starch nanometer granule of preparation 2 θ be 5.6 °, 15.3 °, the diffraction peak intensity at 17.1 ° significantly increases.Original position addition is natural more
The crystallinity of starch nanometer granule prepared by sugar is raised, and is increased mainly due to the interaction force between short amylose molecule
By force, and when natural polysaccharide is used as template, short amylose molecule is aligned in template surface, caused by order enhancing.
And apparently higher than other several nanoparticle samples, this says the crystallinity of starch nanometer granule prepared by original position addition gum rosin
Bright gum rosin is a kind of good template, can control aligning for nucleus and starch molecule, increases it and is arranged with sequence.Have
The increase of sequence advantageously forms the nanostructured outer shell of more consolidation, as nano-carrier application after, can be more effectively
Ground protection activity material damage, while slowing down the release of active material, reaches sustained release, improves the effect of utilization ratio of drug.
4. nano particle ph stability analysis
Distilled water is modulated into the water of different pH (pH=3,4,5,6,7,8,9,10) with the HCl and NaOH of 0.05M respectively
Solution, then adds the suspension that starch nanometer granule is made mass volume ratio 0.1%, and ultrasonic disperse stands half an hour, shakes up
After measure particle size.
As shown in figure 4, the ph stability of the starch nanometer granule prepared as template with natural polysaccharide is improved significantly,
Especially gum rosin and shitosan are that starch nanometer granule prepared by template is that can be kept more in the range of 3-10 in pH value
The particle diameter of stabilization.
5. nano particle thermal stability analysis
Starch nanometer granule is made the suspension of mass volume ratio 0.1% with the distilled water that pH is 7, ultrasonic disperse is placed in
Particle size is measured after standing half an hour in the water-bath of different temperatures (30 DEG C, 40 DEG C, 50 DEG C, 60 DEG C, 70 DEG C, 80 DEG C, 90 DEG C).
As shown in figure 5, the thermal characteristics of the starch nanometer granule prepared as template with natural polysaccharide is improved significantly so that
Nano particle still is able to keep stability higher at 80 DEG C.
6. nano particle salt ion stability analysis
Respectively mass volume ratio is prepared with the NaCl solution of various concentrations (100mM, 200mM, 300mM, 400mM, 500mM)
0.1% starch nanometer granule suspension, ultrasonic disperse stands half an hour, and particle size is measured after shaking up.
As shown in fig. 6, the starch nanometer granule prepared as template with natural polysaccharide is obtained substantially to the stability of salt ion
Improve, especially gum rosin remains to keep stability higher when salt ionic concentration is up to 500mM.
Embodiment 2
(1) cushioning liquid is prepared：Accurately weigh 1.635g disodium hydrogen phosphates and 1.12g citric acids are dissolved in 100mL distilled water
In, stirring makes it fully dissolve, stand-by；
(2) general Shandong indigo plant enzyme pretreatment：It is accurate to measure the general Shandong indigo plant enzyme instillation 9mL distilled water that 1mL concentration is 1350NPUN/mL
In, stirring is allowed to be sufficiently mixed, stand-by；
(3) starch milk is prepared：Weigh in 10g waxy corn starch addition 100mL cushioning liquid, mass volume ratio is obtained
15% starch emulsion；
(4) it is gelatinized：The starch milk that will be prepared makes starch be gelatinized completely in 100 DEG C of water-bath 40min, is then cooled to 55 DEG C；
(5) digest：To adding the general Shandong indigo plant enzyme 1mL, 55 DEG C of enzymolysis 6h that handle well in the colloid starch solution after gelatinization；
(6) low-speed centrifugal：The solution that will be obtained is centrifuged 5min with the rotating speed of 2500r/min while hot, to remove long linear shallow lake
Powder；
(7) go out enzyme：Continue to heat, elevate the temperature to 95 DEG C, keep 15min, enzyme is thoroughly lost activity, 2500r/
5min is centrifuged under min, the enzyme of denaturation is sloughed, short amylose is obtained, 5000r/min centrifugation 4 times (15min/ times) of washing will be heavy
Form sediment and partly obtain short amylose dry powder in -80 DEG C of vacuum freeze dryings；
(8) addition polysaccharide template in situ：Short amylose sodium dihydrogen phosphate-citrate buffer solution is prepared into mass body
Solution of the product than 10%, and to gum rosin is added in short amylose solution, short amylose is 6 with the mass ratio of gum rosin:
1。
(9) self assembly prepares starch nanometer granule：The short amylose solution for adding gum rosin is placed at 0 DEG C and is stirred back
Raw treatment 10h obtains starch nanometer granule suspension.5000r/min centrifugation 4 times (15min/ times) of washing, by sediment fraction -80
DEG C vacuum freeze drying 60h obtains starch nanometer granule.
The detection of pattern and particle diameter is carried out to above-mentioned starch nanometer granule, as a result shows that its is spherical in shape, particle size is 20-
40nm。
Embodiment 3
(1) cushioning liquid is prepared：Accurately weigh 6.54g disodium hydrogen phosphates and 4.48g citric acids are dissolved in 400mL distilled water
In, stirring makes it fully dissolve, stand-by；
(2) general Shandong indigo plant enzyme pretreatment：It is accurate to measure the general Shandong indigo plant enzyme instillation 8mL distilled water that 1mL concentration is 1350NPUN/mL
In, stirring is allowed to be sufficiently mixed, stand-by；
(3) starch milk is prepared：Weigh in 20g waxy corn starch addition 100mL cushioning liquid, mass volume ratio is obtained
20% starch emulsion；
(4) it is gelatinized：The starch milk that will be prepared makes starch be gelatinized completely in 100 DEG C of water-bath 50min, is then cooled to 60 DEG C；
(5) digest：To adding the general Shandong indigo plant enzyme 2mL, 60 DEG C of enzymolysis 6h that handle well in the colloid starch solution after gelatinization；
(6) low-speed centrifugal：The solution that will be obtained is centrifuged 3min with the rotating speed of 3500r/min while hot, to remove long linear shallow lake
Powder；
(7) go out enzyme：Continue to heat, elevate the temperature to 100 DEG C, keep 10min, enzyme is thoroughly lost activity, 3500r/
3min is centrifuged under min, the enzyme of denaturation is sloughed, short amylose is obtained, 7000r/min centrifugation 5 times (5min/ times) of washing will be heavy
Form sediment and partly obtain short amylose dry powder in -90 DEG C of vacuum freeze dryings；
(8) addition polysaccharide template in situ：Short amylose sodium dihydrogen phosphate-citrate buffer solution is prepared into mass body
Solution of the product than 5%, and to adding sodium alginate in short amylose solution, short amylose is with the mass ratio of sodium alginate
9:1。
(9) self assembly prepares starch nanometer granule：Stirred at the short amylose solution for adding sodium alginate is placed in into 8 DEG C
Retrogradation treatment 15h obtains starch nanometer granule suspension.7000r/min centrifugation 5 times (5min/ times) of washing, by sediment fraction -90
DEG C vacuum freeze drying 72h obtains starch nanometer granule.
The detection of pattern and particle diameter is carried out to above-mentioned starch nanometer granule, as a result shows that it is in spindle, length is mainly divided
Between 90-120nm, diameter is mainly distributed between 30-50nm cloth.
It should be appreciated that for those of ordinary skills, can according to the above description be improved or converted,
And all these modifications and variations should all belong to the protection domain of appended claims of the present invention.
Claims (6)
1. the preparation method of a kind of pattern and size tunable type starch nanometer granule, it is characterised in that its preparation process is：
(1) cushioning liquid is prepared：Prepare the sodium dihydrogen phosphate-citrate buffer solution of pH=4-6；
(2) general Shandong indigo plant enzyme pretreatment：General Shandong indigo plant enzyme is diluted to 120-150NPUN/mL with distilled water；
(3) starch milk is prepared：The starch emulsion of mass-volume concentration 10-20% is prepared with sodium dihydrogen phosphate-citrate buffer solution；
(4) it is gelatinized：The starch milk that will be prepared makes starch be gelatinized completely in 100 DEG C of water-bath 20-60min, is then cooled to 55-65
℃；
(5) digest：The general Shandong indigo plant enzyme liquid pre-processed to addition in the colloid starch solution after gelatinization, enzyme liquid and starch on dry basis
Ratio is 0.1mL/g, 55-65 DEG C of enzymolysis 6-8h；
(6) low-speed centrifugal：The enzymolysis liquid that will be obtained is centrifuged 3-5min with the rotating speed of 2500-3500r/min while hot, long straight to remove
Chain starch；
(7) go out enzyme：Continue to heat, elevate the temperature to more than 90 DEG C, and keep 10-15min, enzyme is thoroughly inactivated, 2500-
2-5min is centrifuged under 3500r/min, the enzyme of denaturation is sloughed, short amylose is obtained, washing, vacuum freeze drying obtain short straight chain
Starch dry powder；
(8) addition polysaccharide template in situ：Short amylose sodium dihydrogen phosphate-citrate buffer solution is prepared into mass volume ratio
The solution of 5-15%, and to natural polysaccharide is added in solution, short amylose is 4-10 with the mass ratio of natural polysaccharide:1；
(9) self assembly prepares starch nanometer granule：At the short amylose solution for adding natural polysaccharide is placed in into 0-8 DEG C at retrogradation
Reason 10-15h obtains starch nanometer granule suspension, and washing, vacuum freeze drying obtain starch nanometer granule.
2. the preparation method of pattern according to claim 1 and size tunable type starch nanometer granule, it is characterised in that step
Suddenly it is amylopectin content starch high to be prepared in (3) used by starch milk, including waxy corn starch, taro starch, rice form sediment
One or more in powder, glutinous millet starch.
3. the preparation method of pattern according to claim 1 and size tunable type starch nanometer granule, it is characterised in that step
Suddenly natural polysaccharide is any one in shitosan, guar gum, Arabic gum, sodium alginate, gum rosin in (8).
4. the preparation method of pattern according to claim 1 and size tunable type starch nanometer granule, it is characterised in that step
Suddenly retrogradation processing procedure is stirred in (9), and the rotating speed of stirring is 200-300r/min.
5. the preparation method of pattern according to claim 1 and size tunable type starch nanometer granule, it is characterised in that step
Suddenly the concrete operations of washing are in (7), (9)：5000-7000r/min is centrifuged 5-15min, washes 4-5 times.
6. the preparation method of pattern according to claim 1 and size tunable type starch nanometer granule, it is characterised in that step
Suddenly the temperature of vacuum freeze drying is -90--80 DEG C in (7), (9), and pressure is 0-1Pa, and the time is 48-72h.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201710099143.6A CN106883463B (en) | 2017-02-23 | 2017-02-23 | A kind of preparation method of pattern and size tunable type starch nanometer granule |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201710099143.6A CN106883463B (en) | 2017-02-23 | 2017-02-23 | A kind of preparation method of pattern and size tunable type starch nanometer granule |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN106883463A true CN106883463A (en) | 2017-06-23 |
| CN106883463B CN106883463B (en) | 2019-05-07 |
Family
ID=59179917
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201710099143.6A Active CN106883463B (en) | 2017-02-23 | 2017-02-23 | A kind of preparation method of pattern and size tunable type starch nanometer granule |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN106883463B (en) |
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107602715A (en) * | 2017-09-06 | 2018-01-19 | 青岛农业大学 | A kind of preparation method and application of modified starch nano particle |
| CN107674247A (en) * | 2017-09-12 | 2018-02-09 | 青岛农业大学 | A kind of short amylose protein nano particle and its preparation method and application |
| CN109942842A (en) * | 2019-01-30 | 2019-06-28 | 青岛农业大学 | A kind of preparation method of edible glue nano particle |
| CN110714040A (en) * | 2019-10-28 | 2020-01-21 | 江南大学 | Biosynthesis method of dendritic glucosyl nanoparticles |
| CN113003593A (en) * | 2021-04-19 | 2021-06-22 | 陕西科技大学 | Method for preparing micron-sized granular aluminum oxide by taking guar gum as template |
| CN113072086A (en) * | 2021-04-19 | 2021-07-06 | 陕西科技大学 | Method for preparing micron-sized spherical alumina by taking Arabic gum as template |
| CN114197088A (en) * | 2021-11-09 | 2022-03-18 | 华南理工大学 | Method for preparing nano-fiber or nano-microsphere by ultrasonic induction and film formed by nano-material |
Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101721965A (en) * | 2009-12-10 | 2010-06-09 | 中国科学院长春应用化学研究所 | Method for preparing starch-based nanospheres |
| US20110183380A1 (en) * | 2010-01-26 | 2011-07-28 | North Carolina State University | Porous, carbohydrate-based foam structures and associated methods |
| KR20140107792A (en) * | 2013-02-28 | 2014-09-05 | 고려대학교 산학협력단 | Crystalline starch nanoparticle and its preparation process using hydrolysis and ultrasonic treatment |
| CN104099317A (en) * | 2014-07-18 | 2014-10-15 | 江南大学 | Method for fixing pullulanase with chitosan magnetic nanoparticles |
| CN104189914A (en) * | 2014-07-10 | 2014-12-10 | 华南理工大学 | Self-assembly starch nanoparticle and preparation method thereof |
| CN104804200A (en) * | 2015-04-09 | 2015-07-29 | 青岛农业大学 | Process for moderate-temperature self-assembly preparation of nano starch from enzymolysis short amylose |
| CN105218836A (en) * | 2015-07-31 | 2016-01-06 | 青岛农业大学 | A kind of emulsifying agent assists biological enzyme to prepare the method for size tunable type starch nanometer granule |
-
2017
- 2017-02-23 CN CN201710099143.6A patent/CN106883463B/en active Active
Patent Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101721965A (en) * | 2009-12-10 | 2010-06-09 | 中国科学院长春应用化学研究所 | Method for preparing starch-based nanospheres |
| US20110183380A1 (en) * | 2010-01-26 | 2011-07-28 | North Carolina State University | Porous, carbohydrate-based foam structures and associated methods |
| KR20140107792A (en) * | 2013-02-28 | 2014-09-05 | 고려대학교 산학협력단 | Crystalline starch nanoparticle and its preparation process using hydrolysis and ultrasonic treatment |
| CN104189914A (en) * | 2014-07-10 | 2014-12-10 | 华南理工大学 | Self-assembly starch nanoparticle and preparation method thereof |
| CN104099317A (en) * | 2014-07-18 | 2014-10-15 | 江南大学 | Method for fixing pullulanase with chitosan magnetic nanoparticles |
| CN104804200A (en) * | 2015-04-09 | 2015-07-29 | 青岛农业大学 | Process for moderate-temperature self-assembly preparation of nano starch from enzymolysis short amylose |
| CN105218836A (en) * | 2015-07-31 | 2016-01-06 | 青岛农业大学 | A kind of emulsifying agent assists biological enzyme to prepare the method for size tunable type starch nanometer granule |
Non-Patent Citations (1)
| Title |
|---|
| 黄志宇 等: "《表面及胶体化学(第二版)》", 31 August 2012, 石油工业出版社 * |
Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107602715A (en) * | 2017-09-06 | 2018-01-19 | 青岛农业大学 | A kind of preparation method and application of modified starch nano particle |
| CN107674247A (en) * | 2017-09-12 | 2018-02-09 | 青岛农业大学 | A kind of short amylose protein nano particle and its preparation method and application |
| CN109942842A (en) * | 2019-01-30 | 2019-06-28 | 青岛农业大学 | A kind of preparation method of edible glue nano particle |
| CN110714040A (en) * | 2019-10-28 | 2020-01-21 | 江南大学 | Biosynthesis method of dendritic glucosyl nanoparticles |
| CN113003593A (en) * | 2021-04-19 | 2021-06-22 | 陕西科技大学 | Method for preparing micron-sized granular aluminum oxide by taking guar gum as template |
| CN113072086A (en) * | 2021-04-19 | 2021-07-06 | 陕西科技大学 | Method for preparing micron-sized spherical alumina by taking Arabic gum as template |
| CN113003593B (en) * | 2021-04-19 | 2023-09-01 | 陕西科技大学 | Method for preparing micron-sized granular alumina by taking guar gum as template |
| CN114197088A (en) * | 2021-11-09 | 2022-03-18 | 华南理工大学 | Method for preparing nano-fiber or nano-microsphere by ultrasonic induction and film formed by nano-material |
| CN114197088B (en) * | 2021-11-09 | 2023-04-21 | 华南理工大学 | Method for preparing nanofiber or nanoparticle by ultrasonic induction and film formed by nanomaterial |
Also Published As
| Publication number | Publication date |
|---|---|
| CN106883463B (en) | 2019-05-07 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN106883463B (en) | A kind of preparation method of pattern and size tunable type starch nanometer granule | |
| CN106750388B (en) | A kind of preparation method of Arabic gum hollow nano-sphere | |
| CN107384326B (en) | Preparation method of gelatin chitosan-nano silicon dioxide multi-core phase change energy storage microcapsule | |
| WO2021253727A1 (en) | Method for preparing low dielectric hollow silica microsphere | |
| CN103588886B (en) | A kind of Easily-water dispersible nanocrystalline cellulose and preparation method thereof | |
| CN108761581B (en) | SiO with adjustable refractive index2Preparation method of antireflection film | |
| CN103553023B (en) | Preparation method of nitrogen hybridized spherical mesoporous carbon | |
| CN106867019A (en) | One kettle way prepares SiO2The method of cellulose composite aerogel material | |
| CN105672014B (en) | The preparation method of super-hydrophobic magnetic Nano cellulose paper | |
| CN105502342A (en) | Method for preparing nanometer hollow carbon spheres with dopamine serving as carbon source | |
| CN106905437B (en) | Redispersible powder Cellulose nanocrystal of high heat resistance and preparation method thereof | |
| CN110205809A (en) | A kind of method for sizing of carbon fiber and its application | |
| CN107121714A (en) | A kind of colour generation has free from flaw photonic crystal of low angle dependence and preparation method thereof | |
| Napso et al. | Cellulose gel dispersion: From pure hydrogel suspensions to encapsulated oil-in-water emulsions | |
| CN105070522B (en) | Graphene/titania nanotube prepares flexible bending folding thin-film electrode | |
| CN105541119B (en) | A kind of method that sol-gal process prepares transparent hydrophobic coating | |
| Ji et al. | Controlling the length of self-assembled nanotubes by sonication followed by polymer wrapping | |
| CN104741605B (en) | Nanometer silver parcel silicon dioxide receives micron ball conductive powder and its preparation method and application | |
| CN107674247A (en) | A kind of short amylose protein nano particle and its preparation method and application | |
| CN109929126A (en) | A kind of preparation method of the redisperse of water after drying type Nanowire cellulose | |
| CN106276843A (en) | A kind of method preparing monodisperse hollow carbon microspheres | |
| CN110548878B (en) | Preparation method of uniform and ordered platinum cubic or polyhedral nanoparticle array | |
| Zhou et al. | Highly Water‐Dispersible, Highly Conductive, and Biocompatible Polypyrrole‐Coated Silica Particles Stabilized and Doped by Chondroitin Sulfate | |
| CN105255199A (en) | Silk protein glue/silicon dioxide composite material of hollow structure and preparation method thereof | |
| CN102352082A (en) | Preparation method of micron / submicron gold nanoparticle ring and gold ring |
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 |