本文選題：光響應 + 螺吡喃��； 參考：《北京科技大學》2018年博士論文

【摘要】：螺吡喃類衍生物是典型的光響應分子,具有光致異構化性能,并且在不同光照下螺吡喃基團會呈現(xiàn)不同的親/疏結構。螺吡喃分子有兩種狀態(tài):閉環(huán)狀態(tài)(SP,螺吡喃結構)與開環(huán)狀態(tài)(MC,部花菁結構)。在黑暗或者可見光(Vis)照射下,螺吡喃分子以疏水的SP結構存在。而在紫外光(UV)照射下,螺吡喃分子又以親水的MC結構存在。除了光刺激,pH刺激也能使螺吡喃分子發(fā)生質子化或去質子化過程,產生結構變化。利用螺吡喃光照前后分子結構轉變和光化學性質的變化,可將其廣泛應用于光記錄材料,光學器件,化學傳感,藥物控制釋放等領域。本文合成了螺吡喃激光響應聚合物納米粒子,并研究其在不同外界刺激下的釋放性能與規(guī)律。研究內容分為四部分:第一部分是紫外光、pH、溫度三重響應螺吡喃基聚合物膠束納米粒子的制備及性能研究。利用無規(guī)共聚的方法結合光響應基團螺吡喃和溫度響應基團異丙基丙烯酰胺,成功制備了聚(異丙基丙烯酰胺-共-螺吡喃酯)兩親性聚合物。在水溶液中該兩親性聚合物可以通過自組裝過程形成外殼親水內核疏水的膠束型納米粒子。本部分系統(tǒng)研究了溫度、pH以及協(xié)同刺激對該納米粒子形貌與性能的影響,揭示了不同刺激與客體分子釋放速率之間的規(guī)律,實現(xiàn)了對模型分子香豆素102高效快速的可控釋放。并在溫和的外場協(xié)同刺激下,實現(xiàn)了納米粒子對客體分子的有效控制釋放。實驗結果表明該納米粒子可作為性能優(yōu)良的智能釋放體系。第二部分是近紅外光和pH雙重響應螺吡喃基聚合物-UCNPs復合納米粒子的制備及性能研究。在水溶液中,兩親性螺吡喃基聚合物(異丙基丙烯酰胺-共-螺吡喃酯)通過自組裝的過程形成膠束型納米粒子,其中螺吡喃基疏水部分組成該納米粒子的核,聚異丙基丙烯酰胺親水部分組成該納米粒子的殼。伴隨該聚合物自組裝的過程,疏水的上轉換納米粒子(UCNPs)和客體分子可以被包載到納米自組裝體的核中,并形成聚合物-UCNPs(UCNPs@Polymer)復合納米粒子。在近紅外光照射時,UCNPs可以同時發(fā)射出紫外光和可見光,并且發(fā)出的紫外光能夠引起疏水分子螺吡喃(SP)異構化為親水分子部花菁(MC)。本部分系統(tǒng)研究了近紅外光、pH以及協(xié)同刺激對該納米復合物形貌與性能的影響,揭示了不同刺激與客體分子釋放速率之間的規(guī)律,實現(xiàn)了對模型分子高效快速的可控釋放。并在溫和的外場協(xié)同刺激下,實現(xiàn)了納米粒子對客體分子有效的控制釋放。體外細胞活性實驗的結果表明:在外場協(xié)同刺激下,納米復合物能有效的控制釋放包載的藥物并成功的殺死癌細胞,表明該納米復合物可作為性能優(yōu)良的智能藥物釋放體系。第三部分是光、pH以及還原物質三重響應螺吡喃基聚合物納米凝膠的制備及性能研究。利用乳液聚合的方法結合光響應分子螺吡喃、酸響應分子丙烯酸和還原物質響應交聯(lián)劑成功制備了一種新型的光、pH以及還原物質三重刺激響應的納米凝膠。本部分系統(tǒng)研究了不同刺激對納米凝膠形貌與性能的影響:在紫外光照射下,納米凝膠上SP異構化為MC使其內部的親-疏水平衡被打破,使納米凝膠略有膨脹;在酸性環(huán)境刺激下,納米凝膠上的丙烯酸發(fā)生質子化,使納米凝膠快速膨脹;在還原物質刺激下,納米凝膠上的交聯(lián)劑被切斷,使納米凝膠迅速解散。進一步研究外場協(xié)同刺激對納米凝膠形貌與性能的影響,探究了客體分子可控釋放的內在原理,實現(xiàn)了溫和條件下納米凝膠對客體分子有效的控制釋放。體外細胞活性實驗的結果表明:在外場協(xié)同刺激時,納米凝膠能有效的控制釋放包載藥物并成功的殺死癌細胞,表明該納米凝膠可作為性能優(yōu)良的智能藥物釋放體系。第四部分是近紅外光、pH、氧化還原三重響應螺吡喃基聚合物-UCNPs復合納米凝膠的制備及性能研究。通過乳液聚合法成功制備了一種新型的近紅外光、pH以及還原物質三重刺激響應的聚合物-UCNPs復合納米凝膠。利用包載的UCNPs吸收近紅外光轉換為紫外光,使復合納米凝膠上的SP基團可以在近紅外光照刺激下可逆的異構化為MC基團。本部分系統(tǒng)研究了近紅外光、pH、氧化還原物質以及協(xié)同刺激對該復合納米凝膠形貌與性能的影響,揭示了不同刺激與客體分子釋放速率之間的規(guī)律,實現(xiàn)了對裝載藥物高效快速的可控釋放。并在協(xié)同刺激時,實現(xiàn)了溫和條件下復合納米凝膠對藥物有效的控制釋放。結果表明該復合納米凝膠可作為性能優(yōu)良的智能釋放體系。
[Abstract]:Spiroparan derivatives are typical photoresponsive molecules with photoisomerization properties, and the spiroparan groups present different parent / sparse structures under different illumination. Spiroparan molecules have two states: closed loop state (SP, spiropran structure) and open loop state (MC, cyanine structure). Spiroparan under dark or visible light (Vis) irradiation. Under the ultraviolet (UV) irradiation, the spiroparan molecule is in the presence of a hydrophilic MC structure. In addition to the light stimulation, the pH stimulates the protonalization or deprotonation process of the spiroparan molecules, resulting in structural changes. The changes in the molecular structure transition and photochemical properties of the spiroparan before and after illumination can be widely used. For light recording materials, optical devices, chemical sensing, drug control release and other fields. This paper syntheses the spiroparan laser response polymer nanoparticles and studies its release properties and laws under different external stimuli. The research content is divided into four parts: the first part is ultraviolet light, pH, and temperature three heavy response of spiroparan polymer micelles. Preparation and properties of rice particles. The two amphiphilic polymer of poly (isopropylacrylamide - Co spironyl) was prepared by using the method of random copolymerization combining light response group spirono and temperature response group isopropyl acrylamide. In aqueous solution, the two amphiphilic polymer can form the hydrophilic core of the shell through the self-assembly process. The effect of temperature, pH and synergistic stimulation on the morphology and properties of the nanoparticles was systematically investigated, and the regularity between the different stimuli and the release rate of the guest molecules was revealed. The effective and rapid release of the model molecule coumarin 102 was realized. The nanoparticles can be effectively controlled and released on the guest molecules. The experimental results show that the nanoparticles can be used as a good intelligent release system. The second part is the preparation and performance study of the dual response spiran based polymer -UCNPs composite nanoparticles with near infrared light and pH. In aqueous solution, the two Pro propyl propyl polymer (isopropyl C) A micelle type nanoparticle is formed through the process of self-assembly, in which the hydrophobic part of the spironyl group consists of the core of the nanoparticle, and the hydrophilic part of the polyisopropylacrylamide consists of the shell of the nanoparticles. With the self-assembly process of the polymer, the hydrophobic upconversion nanoparticles (UCNPs) and the guest molecules can be used. The polymer -UCNPs (UCNPs@Polymer) composite nanoparticles are loaded into the core of the nano self assembled body. The ultraviolet and visible light can be emitted by UCNPs at the same time in the near infrared light, and the ultraviolet light can cause the hydrophobicity of the spiran (SP) isomerization to the hydrophilic molecular part of the cyanine (MC). This part studies the near red system. The effect of external light, pH and synergistic stimulation on the morphology and properties of the nanocomposites reveals the laws between the different stimuli and the release rates of the guest molecules, realizing the efficient and rapid controlled release of the model molecules. And under the mild synergistic stimulation of the external field, the effective release of nanoparticles to the guest molecules is realized. The experimental results show that nanocomposites can effectively control the release of encapsulated drugs and kill cancer cells successfully under the synergistic stimulation of external field, indicating that the nanocomposite can be used as an intelligent drug release system with excellent performance. The third part is the preparation of light, pH and reductive substances in the preparation of spirono based polymer nanosels with three heavy responses. A new type of nanosels of light, pH and reductive substances were successfully prepared by the method of emulsion polymerization in combination with light response molecular spiroparan, acid response molecular acrylic acid and reductive substance response crosslinking agent. The effects of different spines on the morphology and properties of nanosels were studied in this part. Under the light of external light, the SP isomerization of the nanosels to MC makes the hydrophobic equilibrium inside the gel broken and the nano gel expands slightly. Under the acid environment, the acrylic acid on the nanosels is protonated and the nano gel expands rapidly. Under the stimulation of the reductive substance, the crosslinking agent on the nanosels is cut off and the nanosels can be solved quickly. The effect of the synergistic stimulation on the morphology and performance of nanosels was further studied, and the intrinsic principle of controlled release of the guest molecules was explored. The effective control release of nanosels to the guest molecules under mild conditions was realized. The results of cell activity experiments in vitro showed that the nanorels could be effectively controlled and released when the external field was stimulated. The fourth part is the preparation and performance study of the near infrared light, pH, redox three heavy response spiran based polymer -UCNPs composite nanosels. A new type of near infrared (NIR) is successfully prepared by emulsion polymerization. The polymer -UCNPs composite nanosels of light, pH and reductive substances with three heavy stimulus response are used to convert the SP group on the composite nanosels to the MC group in a reversible isomerization under the near infrared light stimulation. This part systematically studies the near infrared light, pH, redox material and the compound nanosels. The effect of synergistic stimulation on the morphology and properties of the composite nanosels revealed the regularity between the different stimuli and the release rates of the guest molecules and realized the efficient and rapid controlled release of the loaded drugs. The gel can be used as an intelligent release system with excellent performance.

【學位授予單位】：北京科技大學
【學位級別】：博士
【學位授予年份】：2018
【分類號】：O633.5;TB383.1

【參考文獻】

相關碩士學位論文 前1條

1 曹建蕾;新型螺吡喃類化合物的合成及其凝膠性能的研究[D];河北師范大學;2011年

，

本文編號：1797096