本文選題：熱力學(xué) + 膽汁酸鹽��； 參考：《河南師范大學(xué)》2017年碩士論文

【摘要】：表面活性劑聚集體對于藥物具有緩釋或定向釋放功能,是極具特色的仿生藥物載體。因此對于聚集體的組成、穩(wěn)定性、微結(jié)構(gòu)調(diào)控研究具有重要意義。本論文通過兩種以上混合的表面活性劑構(gòu)建雙親分子聚集體(膠束,囊泡),利用熱力學(xué)研究的主要手段?等溫滴定量熱(ITC)和差式掃描量熱(DSC)與熒光、濁度以及低溫透射電鏡(cryo-TEM)方法相結(jié)合,研究雙親分子聚集體與脫氧膽酸鈉(Na DCA)、膽酸鈉(Na CA)及含類固醇結(jié)構(gòu)的改性葡聚糖的分子間相互作用的熱力學(xué)及聚集行為。詳細討論了雙親分子疏水側(cè)鏈、表面活性劑的極性頭(化學(xué)官能團及電荷)、溶液的組成及濃度等因素,對由兩種或兩種以上表面活性劑構(gòu)成的復(fù)雜體系分子聚集過程的影響,討論了雙親分子間的協(xié)同作用,分析了陽離子季按鹽型gemini(C_(12)C_SC_(12)Br_2,S=3,10)表面活性劑的間隔基團(spacer)在相反電荷的表面活性劑混合囊泡聚集過程中的作用。結(jié)合這些復(fù)雜混合體系的熱力學(xué)性質(zhì),研究了聚合物側(cè)鏈膽汁酸基團及骨架對囊泡聚集形態(tài)的影響。研究內(nèi)容和結(jié)果如下:1. 相反電荷的兩種雙親分子體系——C_(12)C_SC_(12)Br_2/Na DCA與對于gemini/Na DCA混合體系,利用穩(wěn)態(tài)熒光探針法測定了混合體系C_(12)C_SC_(12)Br_2(S=2,6,10)/Na DCA的臨界膠束濃度(cmc_(mix))。用ITC方法測定了在C_(12)C_6C_(12)Br_2與Na DCA相互作用過程中各種相變發(fā)生的臨界濃度(C_P,C_R,C_M)及相應(yīng)的焓變。將這些參數(shù)與C_(12)C_SC_(12)Br_2/Na CA的混合體系比較,由于膽汁酸鹽結(jié)構(gòu)的不同,C_(12)C_SC_(12)Br_2/Na DCA比C_(12)C_SC_(12)Br_2/Na CA有更寬的液晶相組成區(qū)間。對于C_(12)C_6C_(12)Br_2/Dex-15CACOONa混合體系,從其相互作用的觀測焓(ΔH_(obs))和濁度(OD)隨gemini的濃度(C_(gemini))變化曲線得到了相反電荷體系各種相變的臨界濃度和焓變化。通過Cryo-TEM觀測了各相中聚集體的形態(tài)。由于gemini表面活性劑雙極性頭和雙疏水鏈的存在,使gemini可以用作分子交聯(lián)劑,在遠遠小于等電荷比的gemini濃度下使由Dex-15CACOONa側(cè)鏈形成的聚集體之間發(fā)生交聯(lián),此時游離的gemini濃度幾乎為零,聚集體帶負電荷。通過分析C_(12)C_6C_(12)Br_2/Dex-15CACOONa相互作用中涉及的各種因素(兩親分子的類型,聚電解質(zhì)的構(gòu)象,嫁接基團的性質(zhì))推測混合聚集體形成的驅(qū)動力,并提出了相互作用的熱力學(xué)模型。2.三種雙親分子Na DCA/DDAB/SDS和Dex-3DCA/DDAB/SDS的混合體系制備了陰陽離子表面活性劑混合囊泡(DDAB/SDS(x _(SDS)=0.6)),通過ITC方法測定了Na DCA與DDAB/SDS混合囊泡的相互作用焓變化,并用Cryo-TEM表征了混合囊泡的多分散性。發(fā)現(xiàn)混合囊泡的形態(tài)和尺寸依賴于Na DCA的摩爾分數(shù)。進一步通過DSC方法測定了Na DCA/DDAB/SDS混合體系的凝膠到液晶的相變溫度(T_m),發(fā)現(xiàn)Na DCA的加入降低了DDAB/SDS混合囊泡的T_m,表明Na DCA在調(diào)控混合囊泡尺寸和形態(tài)的同時使囊泡的穩(wěn)定性降低。對于Dex-3DCA/DDAB/SDS混合體系,由于葡聚糖骨架的限制,Dex-3DCA對DDAB/SDS混合囊泡的調(diào)控不同于上述包含自由的Na DCA的情況。側(cè)鏈(-DCA)插入到混合囊泡雙層中,同時聚合物鏈包裹在囊泡外表面,導(dǎo)致囊泡的大小和形狀發(fā)生變化,凝膠向液晶的相轉(zhuǎn)變溫度(T_m)增大,因此Dex-3DCA能夠提高DDAB/SDS混合囊泡的穩(wěn)定性。3.三種雙親分子Na DCA/C_(12)C_SC_(12)Br_2/SDS和Dex-3DCA/C_(12)C_SC_(12)Br_2/SDS的混合體系選取C_(12)C_3C_(12)Br_2/SDS與C_(12)C_(10)C_(12)Br_2/SDS兩種混合體系制備囊泡,研究了gemini的間隔基團(spacer)對混合囊泡形態(tài)的影響。C_(12)C_3C_(12)Br_2/SDS體系形成小的球形囊泡,而對于gemini的間隔基團烷基鏈較長的C_(12)C_(10)C_(12)Br_2/SDS體系形成大的多層多核囊泡。Na DCA可以調(diào)控C_(12)C_3C_(12)Br_2/SDS混合囊泡從球形囊泡到橢球型囊泡的轉(zhuǎn)變,脫氧膽酸改性的聚合物(Dex-3DCA)可以調(diào)控C_(12)C_3C_(12)Br_2/SDS混合囊泡從球形囊泡到棒狀聚集體的轉(zhuǎn)變。對于C_(12)C_(10)C_(12)Br_2/SDS體系,Dex-3DCA能夠調(diào)節(jié)C_(12)C_(10)C_(12)Br_2/SDS聚集體的形狀與大小,而游離的Na DCA能夠溶解囊泡膜,改變多層、多核囊泡的層數(shù)。這些結(jié)果對于進一步深入擴展此類復(fù)雜體系的理論與應(yīng)用研究有著重要的指導(dǎo)意義。生物相容性的膽汁酸鹽及含類固醇結(jié)構(gòu)的改性聚合物對囊泡聚集體的功能化調(diào)控在藥物的包埋和釋放方面的研究具有重要的理論和實際意義。
[Abstract]:The surfactant polymer is a highly characteristic biomimetic drug carrier for drug release or directional release. Therefore, it is of great significance for the study of the composition, stability and microstructural regulation of the aggregates. In this paper, the construction of amphiphilic polymer aggregates (micelles, vesicles) by more than two kinds of mixed surfactants is used in this paper, and thermodynamics is used. The main means of the study, isothermal titration calorimetry (ITC) and differential scanning calorimetry (DSC), were combined with fluorescence, turbidity and low temperature transmission electron microscopy (cryo-TEM) to study the thermodynamics and aggregation behavior of the intermolecular interaction of amphiphilic molecule aggregates and sodium deoxycholate (Na DCA), sodium cholate (Na CA) and modified glucan containing steroid structure. The hydrophobic side chain of the parent molecules, the polar head (chemical functional group and charge) of surfactant, the composition and concentration of the solution, and the influence on the molecular aggregation process of complex systems composed of two or more than two kinds of surfactants were discussed in detail. The synergistic action between the two parent molecules was discussed, and the cationic season was analyzed by the salt type Gemini (C_). 12) the effect of the spacer group (spacer) of C_SC_ (12) Br_2, S=3,10 on the aggregation of the mixed vesicles of the surface active agent of the opposite charge. The effects of the bile acid group and skeleton on the morphology of the vesicles in the polymer side chain are studied. The contents and results are as follows: 1. the contrary is the contrary. The two parent molecular systems of charge - C_ (12) C_SC_ (12) Br_2/Na DCA and the mixed system of gemini/Na DCA have been used to determine the critical micelle concentration of C_ (12) C_SC_ (12) Br_2 (S=2,6,10) /Na DCA by the steady-state fluorescence probe method. The critical concentration of change (C_P, C_R, C_M) and corresponding enthalpy change. Comparing these parameters with the mixture of C_ (12) C_SC_ (12) Br_2/Na CA, C_ (12) C_SC_ (12) Br_2/Na DCA has a wider range of liquid crystal phase than C_ (12) because of the structure of bile salts. The observation enthalpy (delta H_ (OBS)) and turbidity (OD) of the interaction with the concentration of Gemini (C_ (Gemini)) obtained the critical concentration and enthalpy change of the various phase transitions in the opposite charge system. The morphology of the aggregates in each phase was observed by Cryo-TEM. The Gemini can be used as a fraction because of the existence of the bipolar head and the double hydrophobic chain of the gemini surface active agent. Sub crosslinker, crosslinked by a Gemini concentration of Dex-15CACOONa side chain at a concentration of Gemini far less than the equal charge ratio, when the free Gemini concentration is almost zero and the aggregate is negatively charged. By analyzing the various factors involved in the interaction of C_ (12) C_6C_ (12) Br_2/Dex-15CACOONa (two parent molecules, polyelectrolytes) Conformation of the conformation, the properties of the graft group) speculates the driving force of the formation of the mixed aggregates, and proposes a thermodynamic model for interaction between three parent molecules, Na DCA/DDAB/SDS and Dex-3DCA/DDAB/SDS, to prepare the mixed vesicles (DDAB/SDS (x) =0.6) of the Yin and Yang surfactant (DDAB/SDS (SDS) =0.6), and the Na DCA and DDAB/SDS are measured by the ITC method. The interaction enthalpy of the mixed vesicles is changed and the polydispersity of the mixed vesicles is characterized by Cryo-TEM. It is found that the morphology and size of the mixed vesicles depend on the mole fraction of the Na DCA. The phase transition temperature (T_m) of the Na DCA/DDAB/SDS mixture gel to the liquid crystal (T_m) is further determined by the DSC method. It is found that the addition of Na DCA reduces the mixing of DDAB/SDS. The T_m of the vesicle indicates that Na DCA reduces the stability of the vesicles while regulating the size and morphology of the mixed vesicles. For the Dex-3DCA/DDAB/SDS mixed system, the regulation of DDAB/SDS mixed vesicles by Dex-3DCA is different from that of the free Na DCA. The side chain (-DCA) is inserted into the mixed vesicle double layer. When the polymer chain is wrapped on the outer surface of the vesicle, the size and shape of the vesicles are changed, the phase transition temperature of the gel is increased to the liquid crystal (T_m), so Dex-3DCA can improve the stability of the DDAB/SDS mixed vesicles, and the mixed system of.3. three parent molecules Na DCA/C_ (12) C_SC_ (12) Br_2/SDS and Dex-3DCA/C_ (12) C_SC_ (12) Br_2/SDS is selected for C_ (12). C_3C_ (12) Br_2/SDS and C_ (12) C_ (10) C_ (12) Br_2/SDS were used to prepare the vesicles. The effect of the Gemini spacer group (spacer) on the morphology of the mixed vesicles was studied. The.C_ (12) C_3C_ (12) Br_2/SDS system formed a small spherical vesicle, and a large multilayer for the longer alkyl chain (12) of the septum group (10) (12) of Gemini was formed. .Na DCA can regulate the transformation of C_ (12) C_3C_ (12) Br_2/SDS mixed vesicles from spherical vesicles to ellipsoidal vesicles. Deoxycholic acid modified polymer (Dex-3DCA) can regulate the transformation of C_ (12) C_3C_ (12) Br_2/SDS mixed vesicles from spherical vesicles to rod like aggregates. For C_ (12) C_ (10) C_ (12) system, it can regulate The shape and size of (12) C_ (10) C_ (12) Br_2/SDS aggregates, while free Na DCA can dissolve the vesicle and change the number of layers and multicore vesicles. These results have important guiding significance for the further expansion of the theoretical and Application Research of such complex systems. The functional regulation of polymers on vesicle aggregates is of great theoretical and practical significance in drug entrapment and release.

【學(xué)位授予單位】：河南師范大學(xué)
【學(xué)位級別】：碩士
【學(xué)位授予年份】：2017
【分類號】：O647.2

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