玉米淀粉修飾及其納米顆粒制備與表征
發(fā)布時間：2018-08-09 18:05
【摘要】：淀粉作為可生物降解和再生的高分子材料而備受關(guān)注，但原淀粉固有特性的不足限制了其應(yīng)用，各種改性手段被用來對淀粉結(jié)構(gòu)中活潑的多羥基官能團進行修飾，以增強淀粉材料的應(yīng)用性。近年來，納米材料的研究方興未艾，淀粉納米材料與其它人工高分子材料相比具有一系列的優(yōu)點，尤其在藥物載體和吸附劑等應(yīng)用方面更表現(xiàn)出較強的優(yōu)異性能。本文以淀粉為研究對象，從宏觀和微觀兩個層次來研究淀粉，宏觀上，，通過化學(xué)改性對淀粉進行琥珀�；男揎�，引入陰離子基團，改善淀粉的親水性能來獲得更多優(yōu)良性質(zhì)，其后以淀粉和改性淀粉為原料通過沉降法制備納米顆粒；從微觀上，調(diào)控淀粉分子的凝聚態(tài)結(jié)構(gòu)，探索淀粉納米材料新的制備工藝，具體研究內(nèi)容如下： 1.以淀粉為原料，琥珀酸酐為酯化劑，采用半干法工藝制備琥珀酸玉米淀粉酯，系統(tǒng)研究了影響淀粉酯化反應(yīng)的不同因素，在單因素的基礎(chǔ)上，利用響應(yīng)面分析法，采用多元二次回歸方程擬合反應(yīng)因素與響應(yīng)值之間的函數(shù)關(guān)系建立數(shù)學(xué)模型，并通過對響應(yīng)值分析獲得最優(yōu)工藝參數(shù)，方差分析表明模型具有較高的擬合度。此外，還通過紅外光譜(FT-IR)、X-射線衍射(XRD)、掃描電鏡(SEM)等表征手段對制備的典型樣品進行了結(jié)構(gòu)分析。FT-IR分析表明，琥珀酰酯化反應(yīng)將陰離子基團引入了淀粉分子結(jié)構(gòu)中，XRD證實酯化反應(yīng)主要發(fā)生在淀粉的無定形區(qū)，典型的晶體結(jié)構(gòu)沒有被破壞，SEM顯示改性后的淀粉顆粒形貌保持完整。 2.選用DMSO為溶劑，淀粉充分溶解后，滴加到不良溶劑中利用沉淀技術(shù)制備水分散性納米粒子，實驗詳細(xì)考察了良溶劑與不良溶劑的選取及它們的比例，淀粉液的濃度及其他影響制備納米粒徑的因素，并對制備的納米顆粒在不同介質(zhì)中分散性能進行了研究。通過動態(tài)光散射（DLS）、SEM、XRD等表征手段對制備的納米顆粒進行了結(jié)構(gòu)分析。結(jié)果表明：通過改變實驗參數(shù)，可制備和調(diào)控尺寸為納米級的淀粉粒子，實驗發(fā)現(xiàn)，制備的納米顆粒在不加分散劑的情況下，可以在較長時間內(nèi)保持穩(wěn)定，化學(xué)結(jié)構(gòu)沒有發(fā)生變化，晶體形態(tài)發(fā)生改變，顆粒形態(tài)呈球形。 3.以玉米淀粉為原料，采用水或堿水為溶劑，利用沉淀法制備淀粉納米顆粒，當(dāng)?shù)矸酆旱稳氩涣既軇┮掖贾袝r，淀粉分子通過分子間或者分子內(nèi)氫鍵相互作用重新裝配聚合，形成納米沉淀顆粒。實驗考察了淀粉乳濃度、體系的pH、不良溶劑的量、堿液濃度、尿素含量、表面活性劑的用量等因素對淀粉納米顆粒粒徑的影響，并采用DLS、XRD、SEM對制備的粒子性能結(jié)構(gòu)進行了分析，分析結(jié)果顯示當(dāng)不良溶劑中含有Tween80時，制備的淀粉納米顆粒尺寸會隨Tween80濃度增加而增大。 4.通過化學(xué)方法對淀粉進行改性，制備帶有正負(fù)電荷的陽離子淀粉和陰離子淀粉，然后通過沉淀法利用已合成的改性淀粉制備淀粉納米顆粒，研究了改性淀粉納米顆粒的制備和結(jié)構(gòu)表征。陽離子淀粉納米粒子的δ-電位隨取代度的增加而增高。電位均為正值，表明粒子表面帶有正電荷，因此可用來負(fù)載或吸附負(fù)電荷分子，而陰離子淀粉制備的陰離子淀粉納米顆粒則帶有明顯的負(fù)電荷，F(xiàn)T-IR分析表明改性淀粉化學(xué)結(jié)構(gòu)均發(fā)生了變化，可在相應(yīng)的區(qū)域發(fā)現(xiàn)改性基團的特征峰，XRD證實改性淀粉納米粒子無晶體峰，SEM顯示制備的粒子出現(xiàn)了一定聚集，干粉狀態(tài)下顆粒聚集現(xiàn)象更明顯。
[Abstract]:Starch has attracted much attention as a biodegradable and regenerated polymer material, but the deficiency of the intrinsic properties of the original starch restricts its application. Various modification methods are used to modify the active polyhydroxy functional groups in the starch structure in order to enhance the application of starch materials. In recent years, the research of nanomaterials is in the ascendant and the starch nanometer is in the ascendant. The material has a series of advantages compared with other artificial polymer materials, especially in the application of drug carrier and adsorbent. The starch is used as the research object. The starch is studied from the macro and microcosmic two levels. On the macroscopic, the starch is modified by the modification of the succinyl group by chemical modification. The anionic groups can improve the hydrophilic properties of starch to obtain more excellent properties. Then, the nanoparticles are prepared by sedimentation method with starch and modified starch as raw materials. From the microcosmic, the condensed structure of starch molecules is regulated and the new preparation technology of starch nanomaterials is explored. The specific contents are as follows:
1. succinic acid corn starch ester was prepared by semi dry process with starch as raw material and succinic anhydride as the esterifying agent. The different factors affecting starch esterification were studied systematically. On the basis of single factor, the response surface analysis method was used to fit the function relationship between the inverse and response values, and the mathematical model was set up by the multiple regression equation. The optimal process parameters were obtained by the analysis of the response value. The variance analysis showed that the model had a higher fitting degree. In addition, the structure analysis of the typical samples was analyzed by infrared spectroscopy (FT-IR), X- ray diffraction (XRD), scanning electron microscope (SEM) and so on. The analysis showed that the succinyl esterification reacted the anion group to the anionic group. In the molecular structure of starch, XRD confirmed that esterification mainly occurred in the amorphous region of starch, and the typical crystal structure was not destroyed. SEM showed that the morphologies of the modified starch granules remained intact.
2. when DMSO is used as solvent, after the starch is dissolved, the water dispersible nanoparticles are prepared by precipitation in the bad solvent. The selection of good solvent and bad solvent and their proportion, the concentration of starch and other effects on the preparation of nanoparticles are investigated in detail, and the prepared nanoparticles are divided into different media. The dispersive properties were studied. The structure of the prepared nanoparticles was analyzed by means of dynamic light scattering (DLS), SEM and XRD. The results showed that the nanometer sized starch particles could be prepared and regulated by changing the experimental parameters. It was found that the prepared nanoparticles could be used for a long time without the dispersing agent. The crystal morphology was changed and the particle morphology was spherical.
3. starch nanoparticles were prepared by precipitation method using corn starch as the raw material, using water or alkaline water as the solvent. When starch gelatinization solution was dripped into the bad solvent ethanol, the starch molecules were reassembled and polymerized through intermolecular or intramolecular interaction of hydrogen bonds to form nanoscale particles. The concentration of starch milk, the pH of the system, and the bad effect were investigated. The effect of the amount of solvent, the concentration of alkaline solution, the content of urea, the dosage of the surfactant and other factors on the particle size of the starch nanoparticles was investigated. The properties of the prepared particles were analyzed by DLS, XRD and SEM. The results showed that the size of the prepared starch nanoparticles would increase with the increase of Tween80 concentration when Tween80 was contained in the bad solvent.
4. the cationic starch and anionic starch with positive and negative charges were prepared by chemical method, and then the prepared starch nanoparticles were prepared by precipitation method. The preparation and structure characterization of the modified starch nanoparticles were studied. The delta potential of the cationic starch nanoparticles was increased with the increase of the degree of substitution. The potential is positive, indicating that the surface of the particle has positive charge, so it can be used to load or adsorb negative charge molecules, and the anionic starch nanoparticles prepared by anionic starch have obvious negative charge. FT-IR analysis shows that the chemical structure of the modified starch has been changed, and the characteristics of the modified group can be found in the corresponding region. XRD showed that the modified starch nanoparticles had no crystal peak, SEM showed that the prepared starch nanoparticles had some aggregation, and the aggregation phenomenon was more obvious in dry powder state.
【學(xué)位授予單位】：吉林大學(xué)
【學(xué)位級別】：博士
【學(xué)位授予年份】：2015
【分類號】：TS236.9;TB383.1
本文編號：2174877
[Abstract]:Starch has attracted much attention as a biodegradable and regenerated polymer material, but the deficiency of the intrinsic properties of the original starch restricts its application. Various modification methods are used to modify the active polyhydroxy functional groups in the starch structure in order to enhance the application of starch materials. In recent years, the research of nanomaterials is in the ascendant and the starch nanometer is in the ascendant. The material has a series of advantages compared with other artificial polymer materials, especially in the application of drug carrier and adsorbent. The starch is used as the research object. The starch is studied from the macro and microcosmic two levels. On the macroscopic, the starch is modified by the modification of the succinyl group by chemical modification. The anionic groups can improve the hydrophilic properties of starch to obtain more excellent properties. Then, the nanoparticles are prepared by sedimentation method with starch and modified starch as raw materials. From the microcosmic, the condensed structure of starch molecules is regulated and the new preparation technology of starch nanomaterials is explored. The specific contents are as follows:
1. succinic acid corn starch ester was prepared by semi dry process with starch as raw material and succinic anhydride as the esterifying agent. The different factors affecting starch esterification were studied systematically. On the basis of single factor, the response surface analysis method was used to fit the function relationship between the inverse and response values, and the mathematical model was set up by the multiple regression equation. The optimal process parameters were obtained by the analysis of the response value. The variance analysis showed that the model had a higher fitting degree. In addition, the structure analysis of the typical samples was analyzed by infrared spectroscopy (FT-IR), X- ray diffraction (XRD), scanning electron microscope (SEM) and so on. The analysis showed that the succinyl esterification reacted the anion group to the anionic group. In the molecular structure of starch, XRD confirmed that esterification mainly occurred in the amorphous region of starch, and the typical crystal structure was not destroyed. SEM showed that the morphologies of the modified starch granules remained intact.
2. when DMSO is used as solvent, after the starch is dissolved, the water dispersible nanoparticles are prepared by precipitation in the bad solvent. The selection of good solvent and bad solvent and their proportion, the concentration of starch and other effects on the preparation of nanoparticles are investigated in detail, and the prepared nanoparticles are divided into different media. The dispersive properties were studied. The structure of the prepared nanoparticles was analyzed by means of dynamic light scattering (DLS), SEM and XRD. The results showed that the nanometer sized starch particles could be prepared and regulated by changing the experimental parameters. It was found that the prepared nanoparticles could be used for a long time without the dispersing agent. The crystal morphology was changed and the particle morphology was spherical.
3. starch nanoparticles were prepared by precipitation method using corn starch as the raw material, using water or alkaline water as the solvent. When starch gelatinization solution was dripped into the bad solvent ethanol, the starch molecules were reassembled and polymerized through intermolecular or intramolecular interaction of hydrogen bonds to form nanoscale particles. The concentration of starch milk, the pH of the system, and the bad effect were investigated. The effect of the amount of solvent, the concentration of alkaline solution, the content of urea, the dosage of the surfactant and other factors on the particle size of the starch nanoparticles was investigated. The properties of the prepared particles were analyzed by DLS, XRD and SEM. The results showed that the size of the prepared starch nanoparticles would increase with the increase of Tween80 concentration when Tween80 was contained in the bad solvent.
4. the cationic starch and anionic starch with positive and negative charges were prepared by chemical method, and then the prepared starch nanoparticles were prepared by precipitation method. The preparation and structure characterization of the modified starch nanoparticles were studied. The delta potential of the cationic starch nanoparticles was increased with the increase of the degree of substitution. The potential is positive, indicating that the surface of the particle has positive charge, so it can be used to load or adsorb negative charge molecules, and the anionic starch nanoparticles prepared by anionic starch have obvious negative charge. FT-IR analysis shows that the chemical structure of the modified starch has been changed, and the characteristics of the modified group can be found in the corresponding region. XRD showed that the modified starch nanoparticles had no crystal peak, SEM showed that the prepared starch nanoparticles had some aggregation, and the aggregation phenomenon was more obvious in dry powder state.
【學(xué)位授予單位】：吉林大學(xué)
【學(xué)位級別】：博士
【學(xué)位授予年份】：2015
【分類號】：TS236.9;TB383.1
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