CN107602715A - A kind of preparation method and application of modified starch nano particle - Google Patents
A kind of preparation method and application of modified starch nano particle Download PDFInfo
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- CN107602715A CN107602715A CN201710795962.4A CN201710795962A CN107602715A CN 107602715 A CN107602715 A CN 107602715A CN 201710795962 A CN201710795962 A CN 201710795962A CN 107602715 A CN107602715 A CN 107602715A
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- starch
- nanometer granule
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Abstract
The invention provides a kind of method of modifying of starch nanometer granule, utilize sodium hypochlorite modified starch nano particle, hydroxyl in starch nanometer granule is oxidized to carboxyl, makes the negative electrical charge of starch nanometer granule increase, improves dispersiveness and stability of the starch nanometer granule in moisture phase.Obtained starch nanometer granule can be used as Pb2+Or Cu2+Etc. the adsorbent of heavy metal ion.The preparation process of the modified starch nano particle of the present invention is green, and preparation method is simple, efficient.
Description
Technical field
The present invention relates to starch nanometer granule technical field of modification, more particularly to a kind of starch for improving dispersion stabilization
The method of modifying of nano particle.
Background technology
Starch enriches reproducible natural polymer as a kind of, and starch nanometer granule can be from by various preparation methods
It is made in native starch.Micron-sized starch bulky grain is degraded to nanoscale, can by the advantages of starch and nano particle spy
Property is combined.Because size is small, specific surface area is big, and compact structure etc., starch nanometer granule, which shows many ative starch, not to be had
Physicochemical characteristics, be a kind of multi-functional material of biology, can assign the special light of formed composite nano materials,
The special natures such as electricity, magnetic, power and bioactivity.Good biocompatibility simultaneously, is easy to degrade, is particularly suitable for use in security and drop
Solution property requires higher field, has potential application value in fields such as packaging material, food, biological medicines.
Starch nanometer granule prepared by enzymolysis recrystallization has preferable prospects for commercial application, but in moisture dephasing easily
Aggregation, forms micron-sized aggregation.When nano particle is dispersed in polymer composites, in order to strengthen the machinery of compound
Property, it is also desirable to which nano particle has preferable dispersiveness.
The content of the invention
It is an object of the invention to provide a kind of method of modifying of starch nanometer granule, overcome starch nanometer granule electrically charged
The defects of few, increase the dispersiveness of nano granule suspension and stability by producing functional group carboxyl, promote it more
Further apply in field.
In order to solve the above-mentioned technical problem, technical scheme is as follows：
The invention provides a kind of method of modifying of starch nanometer granule, comprise the following steps：
Starch nanometer granule and water are configured to the starch slurry that concentration is 3~5wt%；
The starch slurry is mixed with sodium hypochlorite, is 30~40 DEG C in temperature, pH value aoxidizes anti-under conditions of being 9~11
After answering 2~4h, the pH value of solution is adjusted to 6.0~7.0 terminating reactions；The dosage of the sodium hypochlorite accounts for institute based on effective chlorine
State the 0.5~10% of starch nanometer granule butt quality；
The solution centrifugal that the oxidation reaction is obtained, the obtained precipitation that centrifuges obtain through washing and being freeze-dried
Modified starch nano particle.
Preferably, the starch nanometer granule is that starch is prepared through digesting de- branch.
In the present invention, the preparation method of the starch nanometer granule preferably includes following steps：
(1) starch is mixed with the phosphate buffer that pH value is 4.0~5.5, boiling water bath gelatinization, the shallow lake after being gelatinized
Powder breast；
(2) according to 10~30ASPU/g of enzyme dosage, the starch milk after the gelatinization is mixed with Pullulanase, 50~65
6~12h is digested at DEG C, obtains enzymolysis liquid；
(3) enzymolysis liquid is centrifuged, obtained supernatant is placed at 4 DEG C to bring back to life through 6~12h and recrystallized, will be described heavy
Starch nanometer granule is obtained after crystallized product is lyophilized.
Wherein, in step (1), the mass-volume concentration before the starch milk gelatinization is 5~15%.
In step (3), the step of enzymolysis liquid also includes enzyme deactivation before centrifugation.
The starch slurry before sodium hypochlorite reaction with also including：By starch slurry ultrasound, the ultrasonic time is 1~5min.
In the present invention, preferably during starch slurry and sodium hypochlorite reaction, adjusted with NaOH solution or HCl solution anti-
The pH value for answering liquid is 9~11.
It is furthermore preferred that the NaOH or described HCl molar concentration independently is 0.2~0.4mol/L.
In the present invention, the condition of preferably described freeze-drying includes：5~10Pa of vacuum, temperature -80~-60 DEG C, time
48~72 hours.
Present invention additionally comprises the modified starch nano particle that the above method is prepared answering in heavy metal ion is adsorbed
With.
Compared with prior art, the present invention has advantages below：
A kind of method of modifying of starch nanometer granule disclosed by the invention, using sodium hypochlorite modified starch nano particle,
Hydroxyl in starch nanometer granule is oxidized to carboxyl, makes the negative electrical charge of starch nanometer granule increase, improves starch nano
Dispersiveness and stability of the grain in moisture phase.The functional modification of starch nanometer granule can promote it to enter one in multiple fields
Step application.Obtained starch nanometer granule can be by electrostatic interaction and positively charged matter interaction, it is possible thereby to conduct
Pb2+Or Cu2+Etc. the adsorbent of heavy metal ion.The preparation process of the modified starch nano particle of the present invention is green, prepares
Method is simple, efficient.
Brief description of the drawings
The potential diagram of starch nanometer granule when Fig. 1 is embodiment 1-6 differences available chlorine content (0~10%)；
The grain size distribution of starch nanometer granule when Fig. 2 is embodiment 1-5 differences available chlorine content (0~5%)；
The transmission electron microscope picture of starch nanometer granule when Fig. 3 is embodiment 1-5 differences available chlorine content (0~5%)；
The dispersion stabilization observation figure of starch nanometer granule when Fig. 4 is embodiment 1-5 differences available chlorine content (0~5%)；
Fig. 5 is the ative starch nano particle of embodiment 7 and effective chlorine is the starch nanometer granule of 5% oxidation to various concentrations
Pb2+With Cu2+Energy of adsorption try hard to.
Embodiment
The invention provides a kind of method of modifying of starch nanometer granule, overcomes starch nanometer granule is electrically charged few to lack
Fall into, increase the dispersiveness of starch nanometer granule suspension and stability by producing functional group carboxyl, expand it and apply model
Enclose.Specific method of modifying comprises the following steps：
Starch nanometer granule and water are configured to starch slurry；Oxidation reaction is occurred into for starch slurry and sodium hypochlorite, makes starch
Nano particle hydroxyl is oxidized to carboxyl, and the precipitation obtained after solution centrifugal obtains modified starch after washing, being freeze-dried and received
Rice grain.
The present invention is not particularly limited to the source of starch nanometer granule, using the normal starch nano particle in this area
.In the specific embodiment of the invention, it is preferred to use the starch nanometer granule that enzyme solution is prepared.
The method that the present invention prepares starch nanometer granule to amylorrhexis is not particularly limited, using those skilled in the art
Well known enzyme solution.In the present invention, the enzymolysis preparation of the starch nanometer granule preferably includes following steps：
Certain density starch milk is prepared first.In the present invention, the mass-volume concentration of preferred starch breast is 5~15%,
More preferably 8~12%.The starch milk of this concentration is advantageous to the enzymolysis of Pullulanase, makes enzymolysis more abundant.In the present invention, preferably
Starch and phosphate buffer are prepared into starch milk, to maintain the pH stable of solution in enzymolysis process.The present invention is to starch
Species is not particularly limited, in the specific embodiment of the invention, it is preferred to use waxy corn starch is that raw material prepares starch nano
Particle.Starch milk will be prepared after waxy corn starch degreasing.The present invention is not particularly limited to degreasing method, it is preferred to use methanol
Degreasing.In the present invention, the pH value of the phosphate buffer is 4.0~5.5, more preferably 4.2~4.6, makes the pH of starch milk
Value adapts to the optimal enzymolysis environment of Pullulanase, and hydrolysis result is preferable.In the present invention, preferably answered with disodium hydrogen phosphate and citric acid
With the cushioning liquid for preparing above-mentioned pH scopes.The above-mentioned starch being prepared is mixed with phosphate buffer solution, is prepared
Starch milk.
Obtained starch milk is gelatinized.The present invention is not particularly limited to the mode of gelatinization, it is preferred to use boiling water bath
Gelatinization.The time of gelatinization is preferably 30~60min, more preferably 40~50min, to ensure the abundant gelatinization of starch milk.
Starch milk after gelatinization with Pullulanase digest and takes off branch.In the present invention, in terms of starch on dry basis, the general Shandong
The dosage of blue enzyme is preferably 10~30ASPU/g, more preferably 18~26ASPU/g.By the starch milk and Pullulanase after gelatinization
Mixed, be 50~65 DEG C in temperature, more preferably 53~62 DEG C are digested.Enzymolysis time is 6~12h, more preferably 8
~10h.Enzymolysis liquid is obtained after enzymolysis.Contain the amylose that side chain is sloughed after Pullulanase digests in enzymolysis liquid.
Obtained enzymolysis liquid is centrifuged, retrogradation recrystallization, starch nanometer granule is obtained after freezing.
In the present invention, preferably before centrifugation, obtained enzymolysis liquid is first subjected to enzyme deactivation.The present invention does not have to the mode of enzyme deactivation
Particular determination, the mode that can inactivate the Pullulanase in enzymolysis liquid is all within protection scope of the present invention.In the present invention
In specific embodiment, it is preferred to use boiling water bath enzyme deactivation.Preferably, enzymolysis liquid is centrifuged, obtained supernatant is gone out
Enzyme.In the present invention, the rotating speed of enzymolysis liquid centrifugation is not particularly limited, it is preferred to use 3500~10000r/min rotating speed, more
Preferably 5000~8000r/min.The time of centrifugation is preferably 1~3min, more preferably 2min.Supernatant is subjected to boiling water bath
The time of enzyme deactivation, preferably enzyme deactivation is 10~20min.
Enzymolysis solution after enzyme deactivation is centrifuged, discards cotton-shaped fermentoid.Obtained supernatant is placed under low temperature to bring back to life and tied again
It is brilliant.Supernatant preferably is placed in bring back to life in 2~6 DEG C of environment and recrystallized by the present invention.It is preferred that supernatant handle at low temperature when
Between be 6~12h, more preferably 8~10h.
Recrystallized after retrogradation.In the present invention, preferred pair recrystallized product is washed, and washes the impurity such as buffer salt off.
In the present invention, the number preferably washed is 3~4 times.
Recrystallized product after washing is freezed.The present invention is not particularly limited to lyophilized mode, using ability
Routine in domain freezes mode.In the specific embodiment of the invention, it is preferred to use vacuum freeze drying.Vacuum freeze drying
Vacuum be preferably 5~10Pa, more preferably 6~9Pa；Temperature is preferably -80~-60 DEG C, more preferably -75~-65 DEG C；
Time is preferably 48~72 hours.Starch nanometer granule is obtained after lyophilized, for being modified.
Starch nanometer granule is mixed with water, is configured to starch slurry.In the present invention, the concentration of preferred starch slurry for 3~
5%, more preferably 4%.The starch slurry of this concentration range is advantageous to the abundant reaction with sodium hypochlorite.It is prepared to improve
Starch slurry, is preferably ultrasonically treated by the dispersiveness of starch slurry, makes starch slurry using the cavitation of ultrasonic wave in a liquid
It is more uniform.In the present invention, preferably ultrasonic frequency is 20~40KHZ, more preferably 25~30KHZ；The time of ultrasonic disperse
Preferably 1~5min, more preferably 2~4min.Finely dispersed starch slurry is obtained after ultrasound.
Sodium hypochlorite is added in starch slurry, is 30~40 DEG C in temperature, pH under conditions of being 9~11 aoxidize instead
Should.
The present invention is not particularly limited to the reaction unit of starch slurry and sodium hypochlorite, is able to maintain that the device of reaction temperature
It can be applied in the present invention.In order to ensure the abundant progress of oxidation reaction, oxidation effectiveness is improved, the present invention is preferably in reaction
During be stirred.The oxidation reaction of preferred starch slurry and sodium hypochlorite is entered in constant-temperature heating magnetic stirring apparatus in the present invention
OK.Because of oxidation reaction heat release, during need between or close heating power supply, make reaction temperature control at 30~40 DEG C, more preferably
For 33~38 DEG C.
In the present invention, sodium hypochlorite is added in starch slurry, the addition of sodium hypochlorite accounts for the starch based on effective chlorine
The 0.5~10% of nano particle butt quality, more preferably 1~5%.
In the present invention, the oxidation reaction of starch slurry and sodium hypochlorite is carried out under the conditions of pH value is 9~11, and preferable ph is
10.Before sodium hypochlorite is added, first by reaction condition needed for the pH value adjustment of starch slurry.In the present invention, preferably by starch slurry
Mixed with sodium hydroxide, starch slurry pH value is adjusted to 9~11.Hypochlorous acid is added dropwise in the starch slurry after adjusting pH value
Sodium.During sodium hypochlorite is added, the pH of solution rises, be now preferably added to appropriate acid keep solution ph 9~
11.Hydrochloric acid is preferably used in the present invention.After sodium hypochlorite adds, the hydroxyl of starch nanometer granule is oxidized to carboxyl, the pH of solution
Value declines.Alkali is added in the solution adjusts its pH value 9~11.In the present invention, alkali is preferably sodium hydroxide.
In the present invention, sodium hydroxide is preferably added in the form of solution, and preferably sodium hydroxide solution is mole dense
Spend for 0.2~0.4mol/L, more preferably 0.3mol/L.
In the present invention, hydrochloric acid is preferably added with the form of aqueous hydrochloric acid solution, and the molar concentration of preferably hydrochloric acid solution is
0.2~0.4mol/L, more preferably 0.3mol/L.
Starch slurry carries out oxidation reaction under these conditions with sodium hypochlorite, terminates after reacting 2~4h.In the present invention, adjust
The pH value of whole solution is to 6.0~7.0 terminating reactions.It is preferred that adding hydrochloric acid in the solution adjusts pH value to 6.0~7.0.React
Cheng Hou, the hydroxyl in starch nanometer granule are oxidized to carboxyl, add the surface negative charge of starch nanometer granule.
Reacted solution is centrifuged, obtained precipitation washed, be freeze-dried after, obtain modified starch and receive
Rice grain.
The present invention is not particularly limited to the rotating speed of centrifugation, it is preferred to use 7000~10000r/min rotating speed, more preferably
For 8000~9000r/min.The time of centrifugation is preferably 5~10min, more preferably 6~9min.
The precipitation obtained after centrifugation is washed, removes unreacted sodium hypochlorite.The present invention does not have to the number of washing
There is particular determination, preferably wash 2~4 times.
Precipitation after washing is freeze-dried.The present invention is not particularly limited to the mode of freeze-drying, is preferably adopted
Use vacuum freeze drying.In the present invention, the vacuum of preferably vacuum freeze drying is preferably 5~10Pa, more preferably 6~9Pa；
Temperature is preferably -80~-60 DEG C, more preferably -75~-65 DEG C；Time is preferably 48~72 hours.
The starch nanometer granule of the present invention after modified, the increase of its surface negative charge, improves nano particle in moisture phase
In dispersiveness and stability.Because modified starch nanometer granule surface carries negative electrical charge, modified starch nano can be with
Can be by electrostatic interaction and positively charged matter interaction, therefore, modified starch nano particle of the invention can be used as weight
Metal ion such as Pb2+And Cu2+Adsorbent, the improvement for heavy metal water pollution.In the present invention, metal ion solution
Concentration be 20~200mg/L, more preferably 50~100mg/L.In the present invention, the matter used in the modified starch nano particle
Amount amount is the 0.1%~0.5% of metal ion solution volume, more preferably 0.2%~0.4%.
For the object, technical solutions and advantages of the present invention are more clearly understood, the present invention is entered with reference to embodiment
Row detailed description, but they can not be interpreted as limiting the scope of the present invention.
Embodiment 1
The oxidized starch nano particle that effective chlorine is 1% is prepared in accordance with the following steps
(1) preparation of waxy corn starch nano particle：Waxy corn starch is after methanol degreasing, enzymolysis recrystallization legal system
Obtain starch nanometer granule.
PH=4 phosphate buffer is made into ADSP (28.4g/L) and citric acid (19.2g/L), it is accurate
A certain amount of degreasing waxy corn starch is really weighed, adds buffer solution to be tuned into 5% starch milk (m/v), boiling water bath 30min makes its gelatinization
Completely, stirred in boiling, can occasional agitation after sticky.50 DEG C are cooled to after the completion of gelatinization, adds Pullulanase (10ASPU/
G) de- branch, water-bath 6h are carried out.3500r/min centrifugations 2min, discards lower sediment and obtains supernatant, 20min boiling water baths after de- branch
Enzyme deactivation, again centrifugation discard cotton-shaped fermentoid.Be cooled to room temperature, then be placed in 4 DEG C of refrigerator 6h retrogradation recrystallization, after through washing 3
It is secondary, 8Pa, freeze 50 hours at -80 DEG C and obtain starch nanometer granule (SNPs).
The preparation of (2) 1% effective chlorine oxidized starch nano particles：5g SNPs are weighed in 250ml beakers, add deionization
Water is made into 3% starch slurry, ultrasonic 1min, is placed in constant-temperature heating magnetic stirring apparatus to gross weight 167g, and temperature is set to 30 DEG C,
Because of oxidation reaction heat release, during need between or close heating power supply.Starch slurry pH to 9 is adjusted with 0.2mol/l NaOH first,
Sodium hypochlorite 0.5g (0.05g effective chlorine/5g starch, effective chlorine 1%), is added slowly in starch slurry, adds 0.2mol/L HCl
It is 9 to keep pH, and after sodium hypochlorite adds, with the progress of oxidation reaction, hydroxyl is oxidized to carbonyl and carboxyl, and pH declines, then adds
NaOH adjusts pH to 9.The timing from being added sodium hypochlorite, aoxidize 2h, then with HCl adjust pH6.0 terminating reactions, 7000r/min from
Heart 5min must be precipitated, and be washed 3 times, 8Pa, the oxidized starch nano particle for obtaining that effective chlorine is 1% for 50 hours be freezed at -80 DEG C.
Embodiment 2
The oxidized starch nano particle that effective chlorine is 2% is prepared in accordance with the following steps
(1) preparation of starch nanometer granule：It is made into ADSP (28.4g/L) and citric acid (19.2g/L)
PH=4.5 phosphate buffer, a certain amount of degreasing waxy corn starch is accurately weighed, adds buffer solution to be tuned into 10% starch milk
(m/v), boiling water bath 40min makes its gelatinization complete, is stirred in boiling, can occasional agitation after sticky.It is cooled to after the completion of gelatinization
55 DEG C, add Pullulanase (20ASPU/g) and carry out de- branch, water-bath 8h.5000r/min centrifugations 2min, discards lower floor and sinks after de- branch
Shallow lake obtains supernatant, 20min boiling water bath enzyme deactivations, and centrifugation again discards cotton-shaped fermentoid.Room temperature is cooled to, then is placed in 4 DEG C of refrigerators
8h retrogradation recrystallization, after through washing 3 times, 10Pa, -70 DEG C freeze-drying 60h obtain starch nanometer granule (SNPs).
The preparation of (2) 2% effective chlorine oxidized starch nano particles：5g SNPs are weighed in 200ml beakers, add deionization
Water is made into 4% starch slurry, ultrasonic 2min, is placed in constant-temperature heating magnetic stirring apparatus to gross weight 125g, and temperature is set to 35 DEG C,
Because of oxidation reaction heat release, during need between or close heating power supply.First starch slurry pH is adjusted with 0.3mol/l NaOH extremely
9.5, sodium hypochlorite 1g (0.1g effective chlorine/5g starch, effective chlorine 2%), are added slowly in starch slurry, add 0.3mol/L HCl
It is 9.5 to keep pH, and after sodium hypochlorite adds, with the progress of oxidation reaction, hydroxyl is oxidized to carbonyl and carboxyl, and pH declines, then
NaOH is added to adjust pH to 9.5.The timing from being added sodium hypochlorite, 3h is aoxidized, then adjust pH6.5 terminating reactions, 8000r/ with HCl
Min centrifugations 5min must be precipitated, and be washed 3 times, 10Pa, -70 DEG C of freeze-drying 60h.
Embodiment 3
The oxidized starch nano particle that effective chlorine is 3% is prepared in accordance with the following steps
(1) preparation of starch nanometer granule：It is made into ADSP (28.4g/L) and citric acid (19.2g/L)
PH=5 phosphate buffer, a certain amount of degreasing waxy corn starch is accurately weighed, adds buffer solution to be tuned into 15% starch milk
(m/v), boiling water bath 50min makes its gelatinization complete, is stirred in boiling, can occasional agitation after sticky.It is cooled to after the completion of gelatinization
60 DEG C, add Pullulanase (30ASPU/g) and carry out de- branch, water-bath 10h.6000r/min centrifugations 2min, discards lower floor after de- branch
Precipitation obtains supernatant, 20min boiling water bath enzyme deactivations, and centrifugation again discards cotton-shaped fermentoid.Room temperature is cooled to, then is placed in 4 DEG C of ice
Case 10h retrogradation recrystallizations, after through washing 3 times, 5Pa will be deposited in, freeze 72 hours at -60 DEG C and obtain starch nano
Grain (SNPs).
The preparation of (2) 3% effective chlorine oxidized starch nano particles：5g SNPs are weighed in 200ml beakers, add deionization
Water is made into 5% starch slurry, ultrasonic 3min, is placed in constant-temperature heating magnetic stirring apparatus to gross weight 100g, and temperature is set to 40 DEG C,
Because of oxidation reaction heat release, during need between or close heating power supply.Starch slurry pH to 10 is adjusted with 0.4mol/l NaOH first,
Sodium hypochlorite 1.5g (0.15g effective chlorine/5g starch, effective chlorine 3%), is added slowly in starch slurry, adds 0.4mol/L HCl
It is 10 to keep pH, and after sodium hypochlorite adds, with the progress of oxidation reaction, hydroxyl is oxidized to carbonyl and carboxyl, and pH declines, then adds
NaOH adjusts pH to 10.The timing from being added sodium hypochlorite, aoxidize 4h, then with HCl adjust pH7.0 terminating reactions, 9000r/min from
Heart 5min must be precipitated, and be washed 3 times, 5Pa, be freeze-dried 72 hours at -60 DEG C.
Embodiment 4
The oxidized starch nano particle that effective chlorine is 4% is prepared in accordance with the following steps
(1) preparation of starch nanometer granule：It is made into ADSP (28.4g/L) and citric acid (19.2g/L)
PH=5.5 phosphate buffer, a certain amount of degreasing waxy corn starch is accurately weighed, adds buffer solution to be tuned into 15% starch milk
(m/v), boiling water bath 60min makes its gelatinization complete, is stirred in boiling, can occasional agitation after sticky.It is cooled to after the completion of gelatinization
60 DEG C, add Pullulanase (30ASPU/g) and carry out de- branch, water-bath 12h.7000r/min centrifugations 2min, discards lower floor after de- branch
Precipitation obtains supernatant, 20min boiling water bath enzyme deactivations, and centrifugation again discards cotton-shaped fermentoid.Room temperature is cooled to, then is placed in 4 DEG C of ice
Case 12h retrogradation recrystallizations, after through washing 3 times, 8Pa will be deposited in, 48 hours are freezed at -70 DEG C to obtaining starch nanometer granule
(SNPs)。
The preparation of (2) 4% effective chlorine oxidized starch nano particles：5g SNPs are weighed in 200ml beakers, add deionization
Water is made into 5% starch slurry, ultrasonic 4min, is placed in constant-temperature heating magnetic stirring apparatus to gross weight 100g, and temperature is set to 40 DEG C,
Because of oxidation reaction heat release, during need between or close heating power supply.First starch slurry pH is adjusted with 0.4mol/l NaOH extremely
10.5, sodium hypochlorite 2g (0.2g effective chlorine/5g starch, effective chlorine 4%), are added slowly in starch slurry, add 0.4mol/L
It is 10.5 that HCl, which keeps pH, and after sodium hypochlorite adds, with the progress of oxidation reaction, hydroxyl is oxidized to carbonyl and carboxyl, under pH
Drop, then add NaOH to adjust pH to 10.5.The timing from being added sodium hypochlorite, 4h is aoxidized, then adjusts pH7.0 terminating reactions with HCl,
10000r/min centrifugations 5min must be precipitated, and be washed 3 times, will be deposited in 8Pa, freezed 48 hours at -70 DEG C and obtain 4% effective chlorine oxygen
The starch nanometer granule of change.
Embodiment 5
The oxidized starch nano particle that effective chlorine is 5% is prepared in accordance with the following steps
(1) preparation of starch nanometer granule：It is made into ADSP (28.4g/L) and citric acid (19.2g/L)
PH=5 phosphate buffer, a certain amount of degreasing waxy corn starch is accurately weighed, adds buffer solution to be tuned into 10% starch milk
(m/v), boiling water bath 60min makes its gelatinization complete, is stirred in boiling, can occasional agitation after sticky.It is cooled to after the completion of gelatinization
65 DEG C, add Pullulanase (30ASPU/g) and carry out de- branch, water-bath 10h.8000r/min centrifugations 2min, discards lower floor after de- branch
Precipitation obtains supernatant, 20min boiling water bath enzyme deactivations, and centrifugation again discards cotton-shaped fermentoid.Room temperature is cooled to, then is placed in 4 DEG C of ice
Case 10h retrogradation recrystallizations, after through washing 4 times, 8Pa will be deposited in, 48 hours are freezed at -80 DEG C to obtaining starch nanometer granule
(SNPs)。
The preparation of (2) 5% effective chlorine oxidized starch nano particles：5g SNPs are weighed in 200ml beakers, add deionization
Water is made into 5% starch slurry, ultrasonic 5min, is placed in constant-temperature heating magnetic stirring apparatus to gross weight 100g, and temperature is set to 35 DEG C,
Because of oxidation reaction heat release, during need between or close heating power supply.Starch slurry pH to 11 is adjusted with 0.4mol/l NaOH first,
Sodium hypochlorite 2.5g (0.25g effective chlorine/5g starch, effective chlorine 5%), is added slowly in starch slurry, adds 0.4mol/L HCl
It is 11 to keep pH, and after sodium hypochlorite adds, with the progress of oxidation reaction, hydroxyl is oxidized to carbonyl and carboxyl, and pH declines, then adds
NaOH adjusts pH to 11.The timing from being added sodium hypochlorite, 4h is aoxidized, then adjust pH7.0 terminating reactions, 10000r/min with HCl
Centrifugation 5min must be precipitated, and be washed 3 times, will be deposited in 8Pa, freezed the 48 hours starch for obtaining 5% effective oxychloride at -80 DEG C and receive
Rice grain.
Embodiment 6
The oxidized starch nano particle that effective chlorine is 10% is prepared in accordance with the following steps
(1) preparation of starch nanometer granule：It is made into ADSP (28.4g/L) and citric acid (19.2g/L)
PH=4.6 phosphate buffer, a certain amount of degreasing waxy corn starch is accurately weighed, adds buffer solution to be tuned into 12% starch milk
(m/v), boiling water bath 40min makes its gelatinization complete, is stirred in boiling, can occasional agitation after sticky.It is cooled to after the completion of gelatinization
58 DEG C, add Pullulanase (30ASPU/g) and carry out de- branch, water-bath 10h.8000r/min centrifugations 2min, discards lower floor after de- branch
Precipitation obtains supernatant, 20min boiling water bath enzyme deactivations, and centrifugation again discards cotton-shaped fermentoid.Room temperature is cooled to, then is placed in 4 DEG C of ice
Case 10h retrogradation recrystallizations, after through washing 4 times, 8Pa will be deposited in, 72 hours are freezed at -80 DEG C to obtaining starch nanometer granule
(SNPs)。
The preparation of (2) 10% effective chlorine oxidized starch nano particles：5g SNPs are weighed in 200ml beakers, add deionization
Water is made into 4% starch slurry, ultrasonic 3min, is placed in constant-temperature heating magnetic stirring apparatus to gross weight 125g, and temperature is set to 35 DEG C,
Because of oxidation reaction heat release, during need between or close heating power supply.Starch slurry pH to 10 is adjusted with 0.3mol/l NaOH first,
Sodium hypochlorite 5g (0.5g effective chlorine/5g starch, effective chlorine 10%), is added slowly in starch slurry, adds 0.3mol/L HCl to protect
It is 11 to hold pH, and after sodium hypochlorite adds, with the progress of oxidation reaction, hydroxyl is oxidized to carbonyl and carboxyl, and pH declines, then adds
NaOH adjusts pH to 10.The timing from being added sodium hypochlorite, aoxidize 4h, then with HCl adjust pH7.0 terminating reactions, 9000r/min from
Heart 5min must be precipitated, and be washed 3 times, will be deposited in 8Pa, freezed the 72 hours starch for obtaining 10% effective oxychloride at -80 DEG C and receive
Rice grain.
Embodiment 7
1~10% effective oxychloride that the starch nanometer granule obtained to the step of embodiment 1 (1) obtains with embodiment 1-6
Starch nanometer granule carry out performance evaluation
(1) detection of carboxyl and carbonyl content：Carboxyl is determined with carbonyl content by titration.It the results are shown in Table 1.
The content of carboxyl and carbonyl in the starch nanometer granule of table 1
By oxidation reaction, starch nanometer granule part of hydroxyl is converted into carboxyl and carbonyl, and effective chlorine dosage directly affects
Both growing amounts.With the increase of effective chlorine, carboxyl and carbonyl content gradually increase (p<0.05), carboxyl-content increase is very fast
And it is higher than carbonyl content, when effective chlorine is more than 5%, carboxyl is not notable with carbonyl content increase.
(2) particle diameter and potentiometric analysis：Precise 5mg samples add 10ml ultra-pure water (dilution factors in centrifuge tube
0.05%), ultrasonic 3min makes it be uniformly dispersed, and surveys particle diameter and current potential.Potential diagram when Fig. 1 is different effective chlorine (0~10%),
Current potential increases and increased with effective chlorine, but when effective chlorine is more than 5%, current potential does not dramatically increase, it is contemplated that arriving environmental protection and effect
Rate problem, the starch nanometer granule of weight analysis ative starch nano particle and 1~5% effective oxychloride.Fig. 2 is different effective chlorine
Grain size distribution when (0~5%).Fig. 2A is the grain size distribution of ative starch nano particle, and Fig. 2 B are when effective chlorine is 1%
Grain size distribution, grain size distribution when Fig. 2 C effective chlorine is 2%, grain size distribution when Fig. 2 D effective chlorine is 3%, Fig. 2 E have
Imitate grain size distribution when chlorine is 4%, grain size distribution when Fig. 2 F effective chlorine is 5%.A, B, C, D, E, F average grain diameter point
Yue Wei not 406,308,277,213,267 and 205nm.Increase with effective chlorine, current potential increase, electrostatic repulsion causes between particle not
Easily aggregation, causes smaller grain diameter.
(3) pattern of nano particle：The dilution process of sample in the step of reference implementation example 6 (2), carry out transmission electron microscope sight
Examine.Transmission electron microscope picture when Fig. 3 is different effective chlorine, A, B, C, D, E, F be respectively effective chlorine be 0,1,2,3,4 and 5% when
Transmission electron microscope picture.Fig. 3 A ative starch nanoparticle aggregate most serious, increases with effective chlorine, and clustering phenomena mitigates, Fig. 3 F effective chlorine
For 5% when nano particle have little aggregates, grain diameter is between 40-120nm.
(4) differential scanning calorimeter is analyzed：Sample 1:2 add water in small crucible, more than equilibrium at room temperature 4h, obtain starting paste
Change temperature To, peak value gelatinization point Tp, terminate gelatinization point Tc, enthalpy Δ H and sweep enthalpy Δ H againre.It the results are shown in Table 2.
The thermal characteristic parameter value of the modified starch nano particle of table 2
As shown in Table 2, after starch nanometer granule oxidation order reduce, it is necessary to heat enthalpy value reduce, cool quick retrogradation,
Molecular rearrangement, crystalline texture are more perfect.
(5) Detection of Stability：Sample is made into 0.4% suspension in 10ml transparent vials, ultrasonic disperse is uniform, room
Temperature places observation, places 30s, 4h, 8h, 10h, 24h, during 48h, takes pictures.Fig. 4 is the stability sight that sample places different time
Examine, a, b, c, d, e, f are respectively the sample of effective chlorine 0,1,2,3,4 and 5%.In the same time, degree of oxidation high sample point
Scattered stability is preferable, and oxidation significantly improves the dispersion stabilization of nano particle, when effective chlorine is 5%, places 48h nano particles
Still keep certain stability.
(6) metal adsorption ability detects：Prepare 100mg L-1Pb2+And Cu2+Storing solution, 2mgmL-1Starch nano
Particulate samples are added in metal ion solution, room temperature 200rpm reaction 2h, afterwards, centrifugation, are determined metal ion in supernatant and are contained
Amount.It the results are shown in Table 3.
The modified starch nano particle of table 3 is to Pb2+And Cu2+Adsorption capacity
| Effective chlorine (%) | Pb2+(mg/g) | Cu2+(mg/g) |
| 0 | 22.07±2.23d | 21.43±2.02d |
| 1 | 27.94±2.03c | 25.53±1.67cd |
| 2 | 31.12±1.71bc | 27.90±1.55bc |
| 3 | 33.14±2.23b | 29.06±1.85bc |
| 4 | 34.17±2.86b | 31.75±1.06ab |
| 5 | 40.53±1.10a | 34.39±2.28a |
| 10 | 41.84±0.55a | 34.63±1.03a |
Due to the increase of modified current potential, compared to ative starch nano particle, suction of the modified starch nano particle to metal ion
Attached ability dramatically increases, to Pb2+Adsorption capacity be better than Cu2+, the nanometer of 10% effective oxychloride and 5% effective oxychloride
Grain is compared, and the adsorption capacity of metal ion is not apparent from improving.
Prepare 20~200mg L-1Pb2+And Cu2+Storing solution, 2mgmL-1Ative starch nano particle and 5% effective chlorine
The starch nanometer granule of oxidation is added in metal ion solution, room temperature 200rpm reaction 2h, is centrifuged afterwards, is determined gold in supernatant
Belong to ion concentration.Fig. 5 is the starch nanometer granule of ative starch nano particle and 5% effective oxychloride to 20~200mg L-1's
Pb2+And Cu2+Energy of adsorption try hard to, with the increase of metal ion solution concentration, adsorption capacity improves, and concentration is 20~100mg L-1When, adsorption capacity increase is very fast, increases afterwards with concentration, adsorption capacity increase is slower.
Described above is only the preferred embodiment of the present invention, it is noted that for the ordinary skill people of the art
For member, under the premise without departing from the principles of the invention, some improvements and modifications can also be made, these improvements and modifications also should
It is considered as protection scope of the present invention.
Claims (10)
1. a kind of method of modifying of starch nanometer granule, it is characterised in that comprise the following steps：
Starch nanometer granule and water are configured to the starch slurry that concentration is 3~5wt%；
The starch slurry is mixed with sodium hypochlorite, is 30~40 DEG C in temperature, pH value is oxidation reaction 2 under conditions of 9~11
After~4h, the pH value of solution is adjusted to 6.0~7.0 terminating reactions；The dosage of the sodium hypochlorite accounts for the shallow lake based on effective chlorine
The 0.5~10% of powder nano particle butt quality；
The solution centrifugal that the oxidation reaction is obtained, the obtained precipitation that centrifuges are modified through washing and being freeze-dried
Starch nanometer granule.
2. method of modifying according to claim 1, it is characterised in that the starch nanometer granule is starch through digesting de- branch
It is prepared.
3. method of modifying according to claim 2, it is characterised in that the preparation method of the starch nanometer granule include with
Lower step：
(1) starch is mixed with the phosphate buffer that pH value is 4.0~5.5, boiling water bath gelatinization, the starch after being gelatinized
Breast；
(2) according to 10~30ASPU/g of enzyme dosage, the starch milk after the gelatinization is mixed with Pullulanase, at 50~65 DEG C
6~12h is digested, obtains enzymolysis liquid；
(3) enzymolysis liquid is centrifuged, obtained supernatant is placed at 4 DEG C to bring back to life through 6~12h and recrystallized, by the recrystallization
Starch nanometer granule is obtained after product is lyophilized.
4. method of modifying according to claim 3, it is characterised in that in step (1), the quality before the starch milk gelatinization
Volumetric concentration is 5~15%.
5. method of modifying according to claim 3, it is characterised in that in step (3), the enzymolysis liquid also wraps before centrifugation
The step of including enzyme deactivation.
6. method of modifying according to claim 1, it is characterised in that the starch slurry before sodium hypochlorite reaction with also wrapping
Include：By starch slurry ultrasound, the ultrasonic time is 1~5min.
7. method of modifying according to claim 1, it is characterised in that during starch slurry and sodium hypochlorite reaction,
PH value with NaOH solution or HCl solution adjustment reaction solution is 9~11.
8. method of modifying according to claim 7, it is characterised in that the NaOH or described HCl molar concentration is independent
Ground is 0.2~0.4mol/L.
9. method of modifying according to claim 1, it is characterised in that the condition of the freeze-drying includes：Vacuum 5~
10Pa, temperature -80~-60 DEG C, 48~72 hours time.
10. the modified starch nano particle that claim 1~9 any one methods described is prepared is in absorption heavy metal ion
In application.
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