本文關(guān)鍵詞： 葡萄糖雙子表面活性劑 卵白蛋白 膠束 囊泡 納米凝膠 姜黃素 兒茶素酯 魚油　出處：《浙江大學(xué)》2017年博士論文　論文類型：學(xué)位論文

【摘要】：本文以葡萄糖雙子表面活性劑和卵白蛋白為主要壁材,構(gòu)建了膠束、囊泡、聚電解質(zhì)包覆囊泡、納米顆粒、納米凝膠和微乳液等一系列生物活性物質(zhì)載運(yùn)體系。在此基礎(chǔ)上,研究了它們對(duì)姜黃素、兒茶素酯和魚油等生物活性物質(zhì)的載運(yùn)能力以及穩(wěn)定性、功能性調(diào)控作用,并探討了相關(guān)機(jī)理,主要結(jié)論如下:(1)制備了葡萄糖雙子表面活性劑/季銨鹽表面活性劑混合膠束,并考察了混合膠束包埋對(duì)負(fù)三價(jià)姜黃素(Cur~(3-))的穩(wěn)定性提高作用。結(jié)果表明,由于混合膠束分子之間的靜電斥力比季銨鹽表面活性劑膠束分子之間的靜電斥力弱,混合膠束的柵欄層更加致密且疏水性更強(qiáng)。另外,與季銨鹽表面活性劑膠束相比,混合膠束與Cur~(3-)的靜電相互作用較弱但疏水相互作用更強(qiáng),使得Cur~(3-)更容易進(jìn)入混合膠束柵欄層內(nèi)部。因此,混合膠束可以更加有效地將Cur~(3-)與外界環(huán)境隔離并抑制其降解。(2)研究了以十二醇葡萄糖雙子表面活性劑(Gemini-C12)為主要壁材的類脂質(zhì)囊泡對(duì)兒茶素酯的載運(yùn)能力和抗氧化活性提高作用。結(jié)果表明,兒茶素酯在囊泡雙分子層中采取了垂直定位的方式,因此它在囊泡中的有效載量較高。在一定的載量范圍內(nèi),兒茶素酯可以提高囊泡雙分子層的有序性和相變溫度。當(dāng)超過這個(gè)范圍時(shí),兒茶素酯荷載增加了雙層膜的流動(dòng)性并且降低了其熱穩(wěn)定性。囊泡包封兒茶素酯在脂質(zhì)體模型中的抗脂質(zhì)氧化的能力高于游離兒茶素,這可能與兒茶素酯傾向于定位在磷脂雙分子層中有關(guān)。(3)通過靜電修飾的方法構(gòu)建了羧甲基纖維素鈉(CMC-Na)包覆囊泡,并研究了 CMC-Na包覆對(duì)囊泡穩(wěn)定性的提高作用。結(jié)果表明,CMC-Na與囊泡的結(jié)合是一個(gè)自發(fā)的吸熱過程,由熵變驅(qū)動(dòng)。通過控制CMC-Na濃度可以獲得尺寸小、性質(zhì)穩(wěn)定的包覆囊泡,并且實(shí)驗(yàn)獲得的CMC-Na最佳濃度與經(jīng)驗(yàn)?zāi)Ｐ皖A(yù)測(cè)的CMC-Na飽和濃度基本吻合。CMC-Na修飾提高了囊泡的pH穩(wěn)定性、熱穩(wěn)定性和鹽穩(wěn)定性,并提高了芯材兒茶素酯在熱處理?xiàng)l件下的保留率。(4)研究了 Gemini-C12與熱變性卵白蛋白(OVA)的相互作用并探討了Gemini-C12濃度對(duì)Gemini-C12-OVA復(fù)合物包覆小麥醇溶蛋白(gliadin)納米顆粒性質(zhì)的調(diào)控機(jī)理。結(jié)果表明,當(dāng)OVA-Gemini-C12混合溶液中Gemini-C12濃度低于臨界膠束濃度(CMC)時(shí),游離Gemini-C12傾向于吸附在顆粒-水界面。此時(shí),Gemini-C12可以提高反溶劑過程中的成核速率,從而減小gliadin納米顆粒的尺寸;另一方面,它可以填充顆粒表面OVA吸附層留下的空隙,從而提高了納米顆粒的貯藏穩(wěn)定性和再分散性。當(dāng)Gemini-C12濃度高于CMC時(shí),表面活性劑分子傾向于定位在膠束中而不是吸附在固-液界面上,從而增加了 gliadin納米顆粒的尺寸并降低了其貯藏穩(wěn)定性和再分散性。(5)結(jié)合美拉德反應(yīng)和等電點(diǎn)加熱凝膠法制備了卵白蛋白-葡聚糖納米凝膠,并評(píng)價(jià)了納米凝膠包封對(duì)姜黃素生物利用率的提高作用。卵白蛋白-葡聚糖納米凝膠主要呈球形結(jié)構(gòu),其pH穩(wěn)定性、貯藏穩(wěn)定性和再分散性均較好。通過pH驅(qū)動(dòng)法實(shí)現(xiàn)了納米凝膠對(duì)姜黃素的荷載,納米凝膠在包封姜黃素后理化性質(zhì)無明顯變化。卵白蛋白-葡聚糖納米凝膠和卵白蛋白納米顆粒包封均可以提高姜黃素在模擬消化中的轉(zhuǎn)化率(transformation)和生物可給率(bioaccessibility)。納米凝膠包封姜黃素比納米顆粒包封姜黃素的轉(zhuǎn)化率更高,而兩者之間的生物可給率無顯著差異,這可能和它們?cè)谀M消化后相似的理化性質(zhì)有關(guān)。(6)通過自由基枝接法制備了卵白蛋白與兒茶素的共價(jià)結(jié)合物,并研究了卵白蛋白和三種共價(jià)結(jié)合物對(duì)魚油乳液的穩(wěn)定作用。由于酚羥基的引入,卵白蛋白的自由基清除能力得到了提高。兒茶素枝接改變了卵白蛋白的二級(jí)結(jié)構(gòu),并提高了其表面疏水性和三級(jí)構(gòu)象柔順性。與卵白蛋白魚油乳液相比,卵白蛋白-兒茶素共價(jià)結(jié)合物魚油乳液的脂滴更小、貯藏穩(wěn)定性更好、粘度更低并且氧化穩(wěn)定性更高。總體而言,魚油乳液在pH 3.5條件下的氧化穩(wěn)定性比pH 7.0條件下高,這可能主要與pH3.5條件下帶正電的脂滴對(duì)過渡金屬的排斥作用有關(guān)。
[Abstract]:In this paper, glucose Gemini surfactants and ovalbumin as main wall material, construction of the micelles, vesicles, polyelectrolyte coated vesicles, nano particles, nano and micro emulsion gel and a series of bioactive substances carrying system. On this basis, the research on carrying capacity of curcumin, catechin esters and other fish biology active substance and stability, functional regulation, the relevant mechanism and discussion, the main conclusions are as follows: (1) glucose Gemini Surfactant / quaternary ammonium surfactant mixed micelles were prepared, and the effects of the mixed micelle entrapped curcumin on negative trivalent (Cur~ (3-)) improved the stability. Results show that due to the electrostatic repulsion between molecules in the mixed micelles than the electrostatic repulsion between quaternary ammonium surfactant molecules is weak, the palisade layer of the mixed micelle is more dense and more hydrophobic. In addition, with quaternary ammonium salts Compared with micelles, mixed micelles with Cur~ (3-) electrostatic interaction but weak hydrophobic interaction is stronger, the Cur~ (3-) are more likely to enter the mixed micellar palisade layer. Therefore, the mixed micelles can effectively isolate Cur~ (3-) and isolated from the external environment and inhibit its degradation (2) study. With twelve alcohol and glucose Gemini surfactant (Gemini-C12) lipid vesicles as main wall material of bubble of catechin ester carrying capacity and antioxidant activity were improved. Results show that catechin ester global vertical positioning way take double molecular layer in the capsule, so it's in vesicles in effective load high load. In a certain range of catechin ester can improve the vesicle bilayer ordering and phase transition temperature. When more than this range, catechin ester loading increased the liquidity of the bilayer membrane and decrease the thermal stability. The vesicle encapsulation. Lipid peroxidation ability of catechin esters in liposome in the model is higher than that of free catechin, which may be related to catechin ester tended to locate in the phospholipid bilayer. (3) modified by electrostatic method construction of sodium carboxymethyl cellulose (CMC-Na) coated vesicles, and study the role of CMC-Na coated capsule to improve the global stability. The results showed that CMC-Na and vesicle binding was a spontaneous endothermic process driven by entropy. By controlling the concentration of CMC-Na can be obtained in small size, stable properties of coated vesicles, predicting the optimum concentration of CMC-Na and the empirical model and obtained the CMC-Na saturation concentration is consistent with the modified.CMC-Na increased the stability of pH vesicles, thermal stability and salt stability, and improve the retention rate of the core material of catechin ester under heat treatment conditions. (4) of Gemini-C12 and heat denatured ovalbumin (OVA) and to explore the interaction For the Gemini-C12 concentration of Gemini-C12-OVA composite coating of wheat gliadin (gliadin) mechanism characteristics of nanoparticles. The results show that when the Gemini-C12 OVA-Gemini-C12 mixed solution concentration is lower than the critical micelle concentration (CMC), free Gemini-C12 tends to be adsorbed on particle water interface. At this point, Gemini-C12 can increase the nucleation rate of anti solvent process in, so as to reduce the size of gliadin nanoparticles; on the other hand, it can fill the void left by OVA particle surface adsorption layer, thereby improving the storage stability of nano particles and re dispersion. When the concentration of Gemini-C12 is higher than CMC, in the positioning in the micelles rather than adsorption at the solid-liquid interface surface active agent the molecular tendency, thus the size of gliadin nanoparticles increased and reduced its storage stability and redispersibility. (5) combining with Maillard reaction and isoelectric point heating gel method Ovalbumin dextran nanogels were prepared and evaluated nano gel entrapment can improve the bioavailability of curcumin. Ovalbumin dextran nanogels were mainly spherical structure, the pH stability, storage stability and redispersibility were good. The load of curcumin nano gel by pH driving method. Nano gel entrapment in curcumin after physicochemical properties have no obvious change. Ovalbumin dextran nanogels and ovalbumin nanoparticles encapsulated curcumin can improve the conversion rate of digestion in the simulation (transformation) and bioavailability rate (bioaccessibility). The nano gel entrapment ratio of curcumin nanoparticles encapsulated curcumin conversion between the two and higher bioavailability was no significant difference, and this may be in simulating digestion similar physical and chemical properties. (6) were prepared by free radical grafting With ovalbumin and catechin covalent and studied ovalbumin and three covalent conjugates of fish oil emulsion stability. Due to the introduction of phenolic hydroxyl groups, free radical scavenging ability of ovalbumin was improved. Catechin grafting changed two level structure of ovalbumin, and increased its surface hydrophobicity and three conformational flexibility. Compared with the ovalbumin fish oil emulsion, lipid droplets were combined with smaller fish oil emulsion of ovalbumin - catechin covalently, better storage stability, lower viscosity and higher oxidation stability. Overall, oxidation stability under the condition of pH 3.5 oil emulsion than pH 7 under the condition of high, this may be related to with pH3.5 under the condition of positively charged lipid droplets of transition metal repulsion.

【學(xué)位授予單位】：浙江大學(xué)
【學(xué)位級(jí)別】：博士
【學(xué)位授予年份】：2017
【分類號(hào)】：TS201.21;O647.2
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本文編號(hào)：1518788