發(fā)布時(shí)間：2018-12-30 10:54

【摘要】：聚(N-異丙基丙烯酰胺)又稱PNIPAM是一種溫敏性的高分子聚合物,對(duì)溫度具有很好的刺激響應(yīng)性。在最低臨界溶解溫度(LCST)處會(huì)發(fā)生構(gòu)象轉(zhuǎn)變,若溫度在LCST以下,PNIPAM通過(guò)酰胺基與水形成氫鍵,使其可以在水中穩(wěn)定存在,水分子包圍在疏水基團(tuán)周?chē)?此時(shí)PNIPAM具有親水性,其在水溶液中為自由伸展態(tài);若溫度在LCST以上,氫鍵斷裂,PNIPAM自身的酰胺基之間形成氫鍵,使其內(nèi)部坍塌,由伸展態(tài)轉(zhuǎn)為球形結(jié)構(gòu)。若加以改性,可拓寬溫敏性聚合物材料的研究領(lǐng)域,使其在藥物負(fù)載運(yùn)輸,基因傳遞,化學(xué)分析等領(lǐng)域里發(fā)揮更大的應(yīng)用價(jià)值。論文基于可逆加成斷裂鏈轉(zhuǎn)移聚合(RAFT)聚合原理及乙醇胺氨解作用制備PNIPAM-Au NPs復(fù)合物,研究各種鹽離子對(duì)PNIPAM-Au NPs復(fù)合物的鹽效應(yīng),基于電子轉(zhuǎn)移活化催化劑的原子自由基聚合(AGET ATRP)聚合原理及點(diǎn)擊化學(xué)(Click)反應(yīng)原理,制備PNIPAM-DNA嵌段共聚物,研究DNA構(gòu)象變化引起的PNIPAM-DNA共聚物L(fēng)CST變化情況。主要的研究?jī)?nèi)容如下:1.采用氰基戊酸二硫代苯甲酸(CPADB)作鏈轉(zhuǎn)移劑、偶氮二異丁氰(AIBN)作引發(fā)劑,在N,N-二甲基甲酰胺(DMF)溶劑中通過(guò)RAFT聚合制備PNIPAM-COOH,合成的PNIPAM-COOH具有可控分子量且分子量多分散性較低;同時(shí)采用溴異丁酸乙酯(EBIB)/五甲基二乙烯三胺(PMDETA)/溴化銅作引發(fā)催化劑、抗壞血酸作還原劑,通過(guò)AGET ATRP聚合合成了PNIPAM-Br,表征結(jié)果表明合成的PNIPAM-COOH及PNIPAM-Br均具有明確結(jié)構(gòu)。2.利用乙醇胺的氨解作用,將PNIPAM-COOH聚合物一端的二硫酯鍵還原為巰基,然后將其嫁接到納米金表面,制備PNIPAM-AuNPs復(fù)合物。水溶液中聚合物穩(wěn)定存在,而不同鹽離子對(duì)其有不同的鹽效應(yīng),實(shí)驗(yàn)發(fā)現(xiàn),低溫時(shí)受離子所帶電荷及復(fù)合物與鹽離子的絡(luò)合作用的綜合影響,影響效果為Hg2+Cu2+Zn2+Ni2+Pb2+Na+;高溫時(shí),熱效應(yīng)和鹽效應(yīng)的共同作用使得復(fù)合物在很低的鹽離子濃度時(shí)即可聚集,影響效果為Cu2+Pb2+Zn2+Ni2+Hg2+Na+,同時(shí)離子的絡(luò)合作用很微弱,但離子所帶電荷影響效果卻依然很強(qiáng),從而使得Cu2+與Pb2+作用效果相近,Zn2+稍次,Hg2+和Ni2+相近,Na+鹽溶液對(duì)其的影響依然最低。3.通過(guò)疊氮化鈉將PNIPAM-Br末端溴基置換為疊氮基,利用click反應(yīng)嫁接末端為炔基的DNA,制備PNIPAM-DNAC和PNIPAM-DNAT嵌段共聚物,分別檢測(cè)不同溫度下,PNIPAM-DNAC在酸堿性溶液中及PNIPAM-DNAT在汞離子加入前后的溶液透過(guò)率,研究DNA構(gòu)象變化引發(fā)的共聚物L(fēng)CST變化情況。結(jié)果發(fā)現(xiàn),DNAC在酸性溶液中(pH6.0)由單鏈結(jié)構(gòu)轉(zhuǎn)為四面體結(jié)構(gòu),DNAT在汞離子存在下通過(guò)T-Hg2+-T結(jié)構(gòu)雜交為雙鏈,這些構(gòu)象變化可使得DNA上帶有的負(fù)電荷增多、鏈間斥力加強(qiáng),使PNIPAM-DNA嵌段共聚物相轉(zhuǎn)變溫度范圍變寬、變化平緩、動(dòng)力學(xué)半徑降低、溶液透過(guò)率提高。
[Abstract]:Poly (N-isopropyl acrylamide), also known as PNIPAM, is a kind of high molecular polymer with temperature sensitivity, which has a good stimulus response to temperature. At the lowest critical solution temperature (LCST), conformational transition occurs. If the temperature is below LCST, PNIPAM forms a hydrogen bond with water through the amide group, so that it can exist stably in water, and the water molecules are surrounded by hydrophobic groups, so that PNIPAM is hydrophilic. It is a free extensional state in aqueous solution. If the temperature is above LCST, the hydrogen bond breaks, and the hydrogen bond between the amide groups of PNIPAM itself is formed, which causes the internal collapse of the bond and changes from the extensional state to the spherical structure. If modified, it can broaden the research field of thermo-sensitive polymer materials and make it play a more important role in drug loading, gene transmission, chemical analysis and other fields. Based on the principle of reversible addition chain transfer polymerization (RAFT) polymerization and ethanolamine ammonolysis, PNIPAM-Au NPs complexes were prepared. The salt effects of various salt ions on PNIPAM-Au NPs complexes were studied. PNIPAM-DNA block copolymers were prepared by atom radical polymerization of (AGET ATRP) and click-chemical (Click) reaction on the basis of electron transfer activation catalyst. The LCST changes of PNIPAM-DNA copolymers induced by conformation change of DNA were studied. The main research contents are as follows: 1. Using dithiobenzoic acid (CPADB) as chain transfer agent and (AIBN) as initiator, PNIPAM-COOH, was prepared by RAFT polymerization in the solvent of N- dimethylformamide (DMF). The synthesized PNIPAM-COOH has controllable molecular weight and low molecular weight polydispersity. At the same time, PNIPAM-Br, was synthesized by AGET ATRP polymerization with ethyl bromide (EBIB) / (PMDETA) / copper bromide as initiator and ascorbic acid as reducing agent. The characterization results show that the synthesized PNIPAM-COOH and PNIPAM-Br have clear structures. 2. Based on the ammonolysis of ethanolamine, the dithioester bond at one end of PNIPAM-COOH polymer was reduced to mercapto group, and then it was grafted onto the surface of nanometer gold to prepare PNIPAM-AuNPs complex. The polymer exists stably in aqueous solution, but different salt ions have different salt effect on it. It is found that at low temperature, the polymer is affected by the charge of ions and the complex complexation with salt ions, and the effect is Hg2 Cu2 Zn2 Ni2 Pb2 Na. At high temperature, the interaction of thermal effect and salt effect makes the complex gather at very low salt ion concentration, the effect is Cu2 Pb2 Zn2 Ni2 Hg2 Na, and the complexation effect of ion is very weak. However, the effect of ion charge is still very strong, so that the effect of Cu2 and Pb2 is similar, Zn2 is less, Hg2 and Ni2 are close, and the effect of Na salt solution is still the lowest. The PNIPAM-Br terminal bromine group was replaced with azide group by sodium azide. The block copolymers of PNIPAM-DNAC and PNIPAM-DNAT were prepared by click reaction grafting DNA, with acetylene group. The results showed that the PNIPAM-DNAC and PNIPAM-DNAT block copolymers were tested at different temperatures. The transmittance of PNIPAM-DNAC in acid-base solution and PNIPAM-DNAT in the solution before and after the addition of mercuric ion was studied to study the change of LCST induced by the conformation change of DNA. The results showed that DNAC changed from single strand structure to tetrahedron structure in acid solution (pH6.0), and DNAT was hybridized into double strand by T-Hg2 T structure in the presence of mercury ion. These conformational changes resulted in the increase of negative charge on DNA. The repulsive force between chains increases the temperature range of phase transition of PNIPAM-DNA block copolymers, the change is gentle, the kinetic radius is decreased, and the transmittance of the solution is increased.
【學(xué)位授予單位】：魯東大學(xué)
【學(xué)位級(jí)別】：碩士
【學(xué)位授予年份】：2017
【分類(lèi)號(hào)】：O633.22

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