本文關(guān)鍵詞：基于螺吡喃的光敏聚合物復(fù)合材料的制備及其應(yīng)用研究　出處：《蘇州大學(xué)》2015年碩士論文　論文類型：學(xué)位論文

  更多相關(guān)文章： 光響應(yīng) 螺吡喃 藥物載體 可控釋放 泡沫吸附材料

【摘要】：螺吡喃(Spiropyran)以及其衍生物是常見(jiàn)的光致變色有機(jī)化合物之一,由于其在光照射前后分子結(jié)構(gòu)和物理化學(xué)性質(zhì)會(huì)發(fā)生明顯的改變,近年來(lái)被引入到各種材料中并廣泛應(yīng)用于生物醫(yī)藥、光電器件等領(lǐng)域。其中基于螺吡喃的光敏聚合物膠束已被開(kāi)發(fā)成生物醫(yī)藥材料,應(yīng)用到抗腫瘤藥物的輸送體系中并實(shí)現(xiàn)了抗腫瘤藥物的光控釋放。然而單一的聚合物膠束在藥物負(fù)載量、生物造影、腫瘤靶向等方面仍存在不足。針對(duì)以上在實(shí)際應(yīng)用過(guò)程中螺吡喃聚合物膠束存在的缺陷,本論文將聚合物膠束與無(wú)機(jī)納米粒子復(fù)合,設(shè)計(jì)制備了兩個(gè)基于螺吡喃聚合物的多功能光控藥物釋放體系:(1)設(shè)計(jì)合成了以中空介孔二氧化硅納米粒子(HMS)為核、兩親性光敏聚合物PRMS-FA為殼的聚合物納米復(fù)合藥物載體(HMS@C18@PRMS-FA)。利用模板法制備合成了HMS,并利用長(zhǎng)烷基鏈C18將其表面修飾成疏水性(HMS@C18)。在AIBN引發(fā)下,疏水單體SPMA、含乙二醇的親水單體MAPEG及羅丹明B衍生物RBM進(jìn)行自由基共聚,然后在側(cè)鏈接上葉酸基團(tuán),得到具有靶向功能的兩親性光敏聚合物PRMS-FA。通過(guò)自組裝的方法,將聚合物PRMS-FA包裹到HMS@C18表面,制備得到核-殼型聚合物納米復(fù)合載體HMS@C18@PRMS-FA。該藥物載體中HMS內(nèi)核的中空介孔結(jié)構(gòu)賦予其75%左右的高效載藥率。選擇阿霉素作為模擬藥物,在藥物載體于癌細(xì)胞內(nèi)靶向富集后,利用紫外光照控制藥物釋放,發(fā)現(xiàn)藥物可有效釋放并殺死癌細(xì)胞。同時(shí),光敏聚合物所具有的熒光共振能量轉(zhuǎn)移(FRET)性能可用于藥物控釋過(guò)程的實(shí)時(shí)監(jiān)控。該核-殼型聚合物納米復(fù)合藥物載體整合了功能聚合物以及無(wú)機(jī)納米粒子的優(yōu)點(diǎn),改善了聚合物膠束藥物載體在主動(dòng)靶向性以及載藥性能等諸多方面的不足。(2)在前一體系基礎(chǔ)上,引入上轉(zhuǎn)換納米粒子(UCNP)作為光電內(nèi)核,并選用980 nm近紅外光代替紫外光作為控釋光源。通過(guò)簡(jiǎn)便的自由基聚合方法制備得到兩親性光敏聚合物PSMN,并接上葉酸基團(tuán),得到具有靶向功能的聚合物PSMN-FA。在UCNP外包裹上可用于載藥的介孔二氧化硅層(MUCNP),并在修飾上C18后通過(guò)自組裝方法得到近紅外光響應(yīng)的核-殼型聚合物納米載體(MUCNP@C18@PSMN-FA)。在近紅外光照射下,UCNP內(nèi)核不僅可以激發(fā)出紫外光,促使光敏聚合物發(fā)生降解,實(shí)現(xiàn)藥物釋放;同時(shí)其自身的熒光可賦予藥物載體生物造影的功能。此外,所用近紅外光光源不僅無(wú)害而且更具組織穿透性,因此無(wú)論在細(xì)胞內(nèi)還是小鼠活體內(nèi),都能有效地控制藥物釋放,達(dá)到殺死癌細(xì)胞抑制腫瘤生長(zhǎng)的目的。引入U(xiǎn)CNP內(nèi)核及選用近紅外光改善了控釋光源的不足,使該藥物載體更具有應(yīng)用價(jià)值。由于螺吡喃及其衍生物在可見(jiàn)光/紫外光照射下,除了分子結(jié)構(gòu)發(fā)生變化,其疏水/親水性質(zhì)也會(huì)發(fā)生相應(yīng)轉(zhuǎn)變,因此近年來(lái)被引入到材料表面潤(rùn)濕性改性等領(lǐng)域。本論文中,我們也將螺吡喃這一特性拓展到油水分離方面,開(kāi)展了多孔泡沫材料表面改性研究:將光敏螺吡喃單體SPMA通過(guò)自由基共聚的方法修飾到兩親性三聚氰胺泡沫(MF Sponge)表面,制備得到超疏水性泡沫吸附材料(SP-MF Sponge)。光敏聚合物的修飾不僅未改變?nèi)矍璋放菽镜臋C(jī)械性能及穩(wěn)定性,還賦予該吸附材料良好的油水選擇性。實(shí)驗(yàn)結(jié)果表明,該SP-MF泡沫吸附材料具有較高的吸附倍率(70-154倍)及良好的熱穩(wěn)定性。同時(shí)表面修飾的光敏聚合物在紫外光照條件下可發(fā)生疏水/親水性質(zhì)的轉(zhuǎn)變,使SP-MF泡沫變成親水性材料,利用油水排斥作用脫附所吸油類等污染物。所設(shè)計(jì)的光控脫附相比于傳統(tǒng)的機(jī)械擠壓脫附更具智能性,具有潛在的應(yīng)用價(jià)值。
[Abstract]:Spiropyran (Spiropyran) and its derivatives is one of the common organic photochromic compounds because of its light, in the light irradiation on the molecular structure and physicochemical properties will change significantly in recent years, is introduced into a variety of materials and is widely used in biomedicine, optoelectronic devices and other areas. The photosensitive polymer micelles based on spiropyran it has been developed into biomedical materials, applied to the delivery system of antineoplastic drugs and optically controlled delivery of anti-cancer drugs. However, single polymer micelles in drug loading, biological imaging, tumor targeting etc. according to the above shortcomings in the actual application process of spiropyran polymer micelles. The polymer micelles and inorganic nanoparticles composite design, preparation of two multifunctional photocontrolled drug release system of spiropyran polymers based on: (1) design. As to the hollow mesoporous silica nanoparticles (HMS) as the core, the two amphiphilic photosensitive polymer PRMS-FA as shell polymer nano drug carrier (HMS@C18@PRMS-FA). The synthesis of HMS by using the template method, and the use of long alkyl chain C18 its surface modification into hydrophobic (HMS@ C18). Under the initiation of AIBN, hydrophobic the hydrophilic monomer SPMA, monomer MAPEG and Luo Danming B of RBM derivatives containing ethylene glycol by free radical copolymerization, and folic acid in the side chain groups, two amphiphilic photosensitive polymer PRMS-FA. by self-assembly method with target function, the polymer PRMS-FA coated on the surface of HMS@C18 prepared mesoporous hollow the structure of core-shell polymer nano composite carrier HMS@C18@PRMS-FA. the drug carrier in the HMS kernel to around 75% of its high rate of drug loaded. Selecting doxorubicin as model drug, the drug carrier in the cancer cell targeted enrichment, The use of UV light controlled drug release, drug release and can effectively kill cancer cells. At the same time, the fluorescence resonance energy transfer of photosensitive polymer (FRET) can be used for real-time monitoring the performance of drug release process. The core-shell polymer nano drug carrier integrated functional polymer and inorganic nanoparticles has the advantages of improving. The polymer micelle drug carrier in active targeting and drug loading properties and many other aspects. (2) in a system based on the introduction of upconversion nanoparticles (UCNP) as a core, and use 980 nm near infrared light instead of UV light source. As a controlled release preparation two amphiphilic photosensitive polymers by free PSMN simple radical polymerization process, and then get folic acid group, PSMN-FA. polymer with target function can be used for drug loaded mesoporous silica layer in the UCNP package (MUCNP), And in the modification of C18 by self-assembly method of core-shell polymer nanoparticles near infrared response (MUCNP@C18@PSMN-FA). In the near infrared light irradiation, the UCNP kernel can not only stimulate UV, prompted photosensitive polymer degradation for drug release; at the same time, its fluorescence can be given drug carrier biological imaging function. In addition, the near infrared light source is not only harmless and more tissue penetration, so no matter in cells or in vivo, and can effectively control the release of drug, to kill cancer cells inhibit tumor growth. The introduction of the UCNP kernel and the selection of near infrared light to improve the controlled release of the light source, so that the drug the carrier has more application value. Because of the spiropyran and its derivatives in the visible / UV irradiation, in addition to molecular structure changes, the hydrophobic / hydrophilic properties will be corresponding Change, so in recent years were introduced to the surface wettability of material modification and other fields. In this thesis, we will expand to the properties of the spiropyran oil-water separation, the surface modification of porous materials: SPMA photosensitive spiropyran monomers by free radical copolymerization method modified by amphiphilic two melamine foam (MF Sponge) surface was prepared by super hydrophobic foam adsorption material (SP-MF Sponge). The modified photosensitive polymer did not change the mechanical properties and stability of melamine foam originally, also gives the good oil water selective adsorption materials. The experimental results show that the adsorption rate of SP-MF foam adsorption material has higher (70-154 times) and good thermal stability. At the same time photosensitive polymer surface modification can change the hydrophobic hydrophilic properties under UV illumination, SP-MF foam into hydrophilic material, use Oil and water repellent desorption oil and other pollutants. The designed light controlled desorption is more intelligent than traditional mechanical extrusion desorption, and has potential application value.

【學(xué)位授予單位】：蘇州大學(xué)
【學(xué)位級(jí)別】：碩士
【學(xué)位授予年份】：2015
【分類號(hào)】：TQ317;TB33

【參考文獻(xiàn)】

相關(guān)期刊論文 前1條

1 李峰;袁哲凡;;智能型聚合物納米藥物載體設(shè)計(jì)的研究進(jìn)展[J];大學(xué)化學(xué);2014年04期

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本文編號(hào)：1421064