CN103467610B - A kind of method that ultrasonic wave added TEMPO prepares starch nanometer granule - Google Patents
A kind of method that ultrasonic wave added TEMPO prepares starch nanometer granule Download PDFInfo
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- CN103467610B CN103467610B CN201310417104.8A CN201310417104A CN103467610B CN 103467610 B CN103467610 B CN 103467610B CN 201310417104 A CN201310417104 A CN 201310417104A CN 103467610 B CN103467610 B CN 103467610B
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Abstract
The invention provides a kind of ultrasonic wave added TEMPO and prepare the new method of starch nanometer granule. The first step, prepares the starch emulsion (100g) of 5%��10%; Second step, 0.01g ~ 0.1g? TEMPO and 0.1g ~ 1g? NaBr is dissolved in 100mL water, transfer to until completely dissolved in starch milk, NaOH and HCl with 1% regulates starch milk pH9.0��10, it is slowly added dropwise the sodium hypochlorite that available chlorine content is over dry starch quality 3%��5%, after dropwising, with 500w, 20kHz ~ 80kHz ultrasound wave ultrasonic reaction 3h��6h at 0 DEG C��10 DEG C, after having reacted, first use 3000r/min low-speed centrifugal, remove bulky grain, then with 10000r/min high speed centrifugation supernatant, be washed to pH7.0; 3rd step, the precipitation that high speed centrifugation obtains is put in refrigerator freezing layer, takes out after 12h, is placed in vacuum freeze drier and dries 24h��36h. Shortcoming that the starch nanometer granule that the method is produced overcomes that the waste liquid of tradition acidified starch is difficult, acidolysis time length, productivity are relatively low etc., makes this kind of biodegradable of starch nanometer granule, nano material that the compatibility is good obtains large-scale production.
Description
Technical field
The present invention provides ultrasonic wave added TEMPO to prepare the new method of starch nanometer granule, belongs to nano structural material technical field.
Background technology
Nanotechnology is successfully used for many fields at present, including medical science, pharmacy, chemistry and biological detection, manufacturing industry, optics and national defence etc., it is one of following most rising material, many countries formulate relevant plans one after another, putting into huge fund and seize the main strategy of nanotechnology, its potential using value is immeasurable. Along with the development of science and technology, people increasingly pay attention to the quick free of contamination preparation method of natural nano-material.
Starch is natural biomacromolecule, has the advantages that wide material sources, biodegradable, good biocompatibility and cost are low. Therefore, the nanotechnology being raw material with starch will become the focus of the research coming years.
The preparation method of nano-starch mainly has following 3 kinds, and the first is to utilize acid hydrolyzation; The second is the crosslinking sedimentation method; The third is to utilize microemulsion method. But there is the shortcomings such as waste liquid is difficult, production cycle length, productivity are relatively low in these 3 kinds of methods.
The preparation method that the present invention will provide for a kind of quick starch nanometer granule, with starch for raw material, through TEMPO oxidation system at 0��10 DEG C, the ultrasonic 3��6h in pH9��10, centrifugal, it is washed to pH7.0, lyophilization prepares nano level starch granules.The technical solution adopted in the present invention is: after starch sonicated auxiliary TEMPO oxidation, centrifugal, lyophilization prepares starch nanometer granule. The starch nanometer granule that the method obtains, has very strong superficial attractive forces and affinity; Production time is short, cost is low, it is little to pollute, easily realize industrialization; The equipment of production is corrosion-free, and production efficiency is high.
Dispersibility that starch nanometer granule has had, adsorptivity, dissolubility, unique physicochemical property such as the digestion that is easily absorbed by the body, can be used for cosmetics face powder, photographic paper powder, paper-making sizing, confection sugar-coat and tablet excipient etc. Nano-scale rice starch particulate water absorbent after gelatinizing is fast, matter structure is soft and smooth like butter, have that delicate mouthfeel, heat be low, low cost and other advantages, it is butter best in the market and butter succedaneum, it is possible to for without cream cheese, low-fat ice cream, production without fat margarine, sauce and salad dressing. It has a extensive future, economic benefits.
Summary of the invention
The preparation method that it is an object of the invention to provide a kind of nano-scale rice starch granule, particle diameter reaches Nano grade, can be used in food, medicine. TEMPO oxidation can destroy the grain structure of starch, makes starch surface be full of hole, then utilizes hyperacoustic mechanical vibration effect and cavitation to be broken up by Oxytarch, forms nano-particle, reaches Nano grade.
Concrete preparation process method is:
(1) starch milk is prepared: weigh 5g waxy corn starch and add in 100mL distilled water, prepare the starch emulsion of 5%, be placed in ultrasound wave, while stirring temperature control 0 DEG C��7 DEG C.
(2) ultrasonic wave added TEMPO prepares starch nanometer granule: 0.048gTEMPO and 0.635gNaBr is dissolved in 100mL water, transfer to until completely dissolved in starch milk, NaOH and HCl with 1% regulates starch milk pH9.0��10, it is slowly added dropwise the sodium hypochlorite that available chlorine content is over dry starch quality 3%��5%, after dropwising, use power 500w, frequency 20kHz ultrasound wave is ultrasonic reaction 3h��6h at 0 DEG C��7 DEG C, after having reacted, first use 3000r/min low-speed centrifugal, remove bulky grain, then supernatant is used 10000r/min high speed centrifugation, and it is washed to pH7.0.
(3) lyophilization: the precipitation that high speed centrifugation obtains is placed in plate, is put in refrigerator freezing layer, takes out after 12 hours, is placed in vacuum freeze drier dry 24��36 hours, obtains starch nanometer granule powder.
Can preparing, according to this step, the starch nanometer granule that particle diameter is stable, this preparation method overcomes the shortcoming such as high energy consumption, time length after mineral acid hydrolysis, is possible not only to realize industrialized production, and the production cycle being greatly shortened.
Detailed description of the invention
Embodiment 1
(1) starch milk is prepared: weigh 7g rice starch and add in 100mL distilled water, prepare the starch emulsion of 7%, be placed in ultrasound wave, while stirring temperature control 5 DEG C��10 DEG C.
(2) ultrasonic wave added TEMPO prepares starch nanometer granule: 0.025gTEMPO and 0.428gNaBr is dissolved in 100mL water, transfer to until completely dissolved in starch milk, NaOH and HCl with 1% regulates starch milk pH9.0��10, it is slowly added dropwise the sodium hypochlorite that available chlorine content is over dry starch quality 3%��5%, after dropwising, use power 500w, frequency 40kHz ultrasound wave is ultrasonic reaction 3h��6h at 5 DEG C��10 DEG C, after having reacted, first use 3000r/min low-speed centrifugal, remove bulky grain, then supernatant is used 10000r/min high speed centrifugation, and it is washed to pH7.0.
(3) lyophilization: the precipitation that high speed centrifugation obtains is placed in plate, is put in refrigerator freezing layer, takes out after 12 hours, is placed in vacuum freeze drier dry 24��36 hours, obtains starch nanometer granule powder.
Embodiment 2
(1) starch milk is prepared: weigh 10g potato starch and add in 100mL distilled water, prepare the starch emulsion of 10%, be placed in ultrasound wave, while stirring temperature control 0 DEG C��10 DEG C.
(2) ultrasonic wave added TEMPO prepares starch nanometer granule: 0.070gTEMPO and 0.950gNaBr is dissolved in 100mL water, transfer to until completely dissolved in starch milk, NaOH and HCl with 1% regulates starch milk pH9.0��10, it is slowly added dropwise the sodium hypochlorite that available chlorine content is over dry starch quality 3%��5%, after dropwising, use power 500w, frequency 20kHz ultrasound wave is ultrasonic reaction 3h��6h at 0 DEG C��10 DEG C, after having reacted, first use 3000r/min low-speed centrifugal, remove bulky grain, then supernatant is used 10000r/min high speed centrifugation, and it is washed to pH7.0.
(3) lyophilization: the precipitation that high speed centrifugation obtains is placed in plate, is put in refrigerator freezing layer, takes out after 12 hours, is placed in vacuum freeze drier dry 24��36 hours, obtains starch nanometer granule powder.
Embodiment 3
(1) starch milk is prepared: weigh the glutinous rice starch of 8g and add in 100mL distilled water, prepare the starch emulsion of 8%, be placed in ultrasound wave, while stirring temperature control 3 DEG C��8 DEG C.
(2) ultrasonic wave added TEMPO prepares starch nanometer granule: 0.038gTEMPO and 0.605gNaBr is dissolved in 100mL water, transfer to until completely dissolved in starch milk, NaOH and HCl with 1% regulates starch milk pH9.0��10, it is slowly added dropwise the sodium hypochlorite that available chlorine content is over dry starch quality 3%��5%, after dropwising, use power 500w, frequency 24kHz ultrasound wave is ultrasonic reaction 3h��6h at 3 DEG C��8 DEG C, after having reacted, first use 3000r/min low-speed centrifugal, remove bulky grain, then supernatant is used 10000r/min high speed centrifugation, and it is washed to pH7.0.
(3) lyophilization: the precipitation that high speed centrifugation obtains is placed in plate, is put in refrigerator freezing layer, takes out after 12 hours, is placed in vacuum freeze drier dry 24��36 hours, obtains starch nanometer granule powder.
Embodiment 4
(1) starch milk is prepared: weigh 5g corn starch and add in 100mL distilled water, prepare the starch emulsion of 5%, be placed in ultrasound wave, while stirring temperature control 3 DEG C��10 DEG C.
(2) ultrasonic wave added TEMPO prepares starch nanometer granule: 0.068gTEMPO and 0.735gNaBr is dissolved in 100mL water, transfer to until completely dissolved in starch milk, NaOH and HCl with 1% regulates starch milk pH9.0��10, it is slowly added dropwise the sodium hypochlorite that available chlorine content is over dry starch quality 3%��5%, after dropwising, use power 500w, frequency 37kHz ultrasound wave is ultrasonic reaction 3h��6h at 3 DEG C��10 DEG C, after having reacted, first use 3000r/min low-speed centrifugal, remove bulky grain, then supernatant is used 10000r/min high speed centrifugation, and it is washed to pH7.0.
(3) lyophilization: the precipitation that high speed centrifugation obtains is placed in plate, is put in refrigerator freezing layer, takes out after 12 hours, is placed in vacuum freeze drier dry 24��36 hours, obtains starch nanometer granule powder.
Embodiment 5
(1) starch milk is prepared: weigh 6g taro starch and add in 100mL distilled water, prepare the starch emulsion of 6%, be placed in ultrasound wave, while stirring temperature control 5 DEG C��10 DEG C.
(2) ultrasonic wave added TEMPO prepares starch nanometer granule: 0.035gTEMPO and 0.550gNaBr is dissolved in 100mL water, transfer to until completely dissolved in starch milk, NaOH and HCl with 1% regulates starch milk pH9.0��10, it is slowly added dropwise the sodium hypochlorite that available chlorine content is over dry starch quality 3%��5%, after dropwising, use power 500w, frequency 20kHz ultrasound wave is ultrasonic reaction 3h��6h at 5 DEG C��10 DEG C, after having reacted, first use 3000r/min low-speed centrifugal, remove bulky grain, then supernatant is used 10000r/min high speed centrifugation, and it is washed to pH7.0.
(3) lyophilization: the precipitation that high speed centrifugation obtains is placed in plate, is put in refrigerator freezing layer, takes out after 12 hours, is placed in vacuum freeze drier dry 24��36 hours, obtains starch nanometer granule powder.
Embodiment 6
(1) starch milk is prepared: weigh 5g tapioca and add in 100mL distilled water, prepare the starch emulsion of 5%, be placed in ultrasound wave, while stirring temperature control 5 DEG C��10 DEG C.
(2) ultrasonic wave added TEMPO prepares starch nanometer granule: 0.065gTEMPO and 0.985gNaBr is dissolved in 100mL water, transfer to until completely dissolved in starch milk, NaOH and HCl with 1% regulates starch milk pH9.0��10, it is slowly added dropwise the sodium hypochlorite that available chlorine content is over dry starch quality 3%��5%, after dropwising, use power 500w, frequency 40kHz ultrasound wave is ultrasonic reaction 3h��6h at 5 DEG C��10 DEG C, after having reacted, first use 3000r/min low-speed centrifugal, remove bulky grain, then supernatant is used 10000r/min high speed centrifugation, and it is washed to pH7.0.
(3) lyophilization: the precipitation that high speed centrifugation obtains is placed in plate, is put in refrigerator freezing layer, takes out after 12 hours, is placed in vacuum freeze drier dry 24��36 hours, obtains starch nanometer granule powder.
Ultrasonic wave added TEMPO is adopted to produce starch nanometer granule, substantially reduce the production cycle, product yield is greatly improved, that reduces chemical reagent especially sulphuric acid, hydrochloric acid etc. makes consumption, reduce the requirement to the equipment of production, being suitable for large-scale industrialized production, the production application for nano material provides efficiently strong approach.
Claims (2)
1. the method that a ultrasonic wave added TEMPO prepares starch nanometer granule, it is characterised in that ultrasonic Treatment combines with TEMPO Oxytarch, the steps include:
(1) adding in distilled water by starch, preparing 100g mass fraction is the starch emulsion of 5%��10%, is placed in ultrasound wave, and temperature control 0 DEG C��10 DEG C, obtain starch milk while stirring;
(2) 0.01g��0.1gTEMPO and 0.1g��1gNaBr is dissolved in 100mL water, transfer to until completely dissolved in starch milk, it is 9.0 that NaOH and HCl with 1% regulates pH value of starch milk, it is slowly added dropwise the sodium hypochlorite that available chlorine content is over dry starch quality 3%��5%, after dropwising, with power 500w, frequency 20kHz��80kHz ultrasound wave ultrasonic reaction 3h��6h at 0 DEG C��10 DEG C, after having reacted, first use 3000r/min low-speed centrifugal, remove bulky grain, then supernatant is used 10000r/min high speed centrifugation, and to be washed to pH value be 7.0;
(3) the precipitation that step (2) high speed centrifugation obtains is placed in plate, is put in refrigerator freezing layer, take out after 12 hours, be placed in vacuum freeze drier dry 24��36 hours, obtain starch nanometer granule powder;
(4) the precipitation of low-speed centrifugal is carried out repeated ultrasonic auxiliary TEMPO process, until producing without bulky grain.
2. the method that a kind of ultrasonic wave added TEMPO according to claim 1 prepares starch nanometer granule, it is characterised in that described starch is corn starch, potato starch, wheaten starch, rice starch or tapioca; The temperature of described ultrasonic reaction is 5 DEG C-7 DEG C; Described hyperacoustic frequency is 20kHz��40kHz.
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Non-Patent Citations (2)
| Title |
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| Starch nanoparticles formation via high power ultrasonication;Haaj et al.;《Carbohydrate Polymers》;20121115;第92卷(第2期);2.2超声环境 * |
| The influence of ultrasound on the degree of oxidation of hypochlorite-oxidized corn starch;Chong et al.;《Food Science and Technology》;20130331;第50卷(第2期);结论部分 * |
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