本文關(guān)鍵詞： 凝膠 偶氮苯 酰肼 光響應(yīng)性 陰離子響應(yīng)　出處：《吉林大學(xué)》2017年碩士論文　論文類型：學(xué)位論文

【摘要】：小分子有機(jī)凝膠是一種小分子凝膠因子溶解于溶劑中,通過分子間氫鍵作用,π-π相互作用,范德華力等非共價(jià)鍵相互作用相互聚集纏繞形成纖維網(wǎng)絡(luò)結(jié)構(gòu),從而束縛溶劑形成的自組裝軟材料。凝膠因子的分子結(jié)構(gòu)對有機(jī)凝膠的凝膠性能及刺激響應(yīng)性有很大的影響。因此對凝膠因子合理的設(shè)計(jì)、修飾能極大的提高材料的功能性,比如在分子結(jié)構(gòu)中引入對外界光、電、聲、離子、酸堿、溫度等刺激具有響應(yīng)的官能團(tuán),從而實(shí)現(xiàn)有機(jī)凝膠對外界的刺激響應(yīng)性能。基于此,我們選取了基于酰肼基團(tuán)(酰肼基團(tuán)含有豐富的氫鍵)的兩類偶氮苯(偶氮苯基團(tuán)是光響應(yīng)基團(tuán))衍生物Dn、En,研究了它們的有機(jī)凝膠性及其凝膠的多重響應(yīng)性。主要研究內(nèi)容如下:1、研究了含有不同末端烷基鏈長度的Dn(n=7、8、10)的有機(jī)凝膠性和光響應(yīng)性。D7只能在環(huán)己烷中形成有機(jī)凝膠,D8可以在1,2-二氯乙烷和環(huán)己烷中形成凝膠,D10在1,2-二氯乙烷、環(huán)己烷和二甲基亞砜中都能形成凝膠,可以發(fā)現(xiàn)隨著末端烷基鏈增加有利于提高凝膠能力和凝膠的熱力學(xué)穩(wěn)定性。在紫外光照射下,在溶液中,Dn中的偶氮苯發(fā)生光致異構(gòu)化,反式偶氮苯向順式發(fā)生轉(zhuǎn)化,雖然D10的環(huán)己烷溶液光致異構(gòu)化性能最為顯著(反式到順式的轉(zhuǎn)化比率達(dá)到66%),但是凝膠態(tài)下偶氮苯的光致順反異構(gòu)不能誘導(dǎo)凝膠-溶膠的轉(zhuǎn)變。2、研究了含有不同長度柔性間隔基的基于酰肼基團(tuán)的偶氮苯衍生物En(n=5、6、10)的有機(jī)凝膠性能及其多重響應(yīng)性。E6和E10可以在N-N二甲基甲酰胺中形成纖維網(wǎng)絡(luò)聚集的穩(wěn)定凝膠,且E10的臨界凝膠濃度高于E6,然而E5卻不能形成凝膠。這可能是由于含有奇數(shù)間隔基的E5的彎曲構(gòu)型導(dǎo)致E5的偶極矩增加,提高了E5在N-N二甲基甲酰胺(極性溶劑)中的溶解度,從而干擾E5分子的聚集。E6和E10的有機(jī)凝膠對多種環(huán)境刺激(包括溫度,光,陰離子和p H)顯示出刺激響應(yīng)行為。在用UV照射有機(jī)凝膠時(shí),由于偶氮苯基團(tuán)發(fā)生光致異構(gòu)化,從而導(dǎo)致凝膠向沉淀物轉(zhuǎn)變,相應(yīng)的形貌從纖維轉(zhuǎn)變?yōu)榍驙罹奂w。在En凝膠中直接加入陰離子(F~-和Ac O-)時(shí),凝膠迅速坍塌為溶液并伴有顏色變化,通過陰離子滴定的紫外-可見吸收光譜和核磁氫譜證實(shí)是酰肼基團(tuán)發(fā)生了去質(zhì)子化過程導(dǎo)致的響應(yīng)變化。另外,該有機(jī)凝膠還具有PH值響應(yīng)性,加入堿和酸能誘導(dǎo)凝膠-溶膠的可逆轉(zhuǎn)變,同時(shí)伴隨顏色變化。這些研究的結(jié)果可以進(jìn)一步理解小分子凝膠因子結(jié)構(gòu)與性質(zhì)的關(guān)系。3、研究了En和4-poxd-B8雙組份有機(jī)凝膠的陰離子響應(yīng)性質(zhì)。不含有氫鍵的VA唑衍生物4-poxd-B8可以在二甲基亞砜中形成穩(wěn)定凝膠,而E5不能形成有機(jī)凝膠,但具有陰離子響應(yīng)性。E5和4-poxd-B8的混合物能夠在二甲基亞砜中形成穩(wěn)定的凝膠,并且該凝膠對F~-和Ac O-離子的刺激呈現(xiàn)不同的顏色變化,但凝膠狀態(tài)不發(fā)生改變,達(dá)到了檢測陰離子的目的且不會(huì)帶來凝膠的坍塌。
[Abstract]:Small molecular organic gel is a kind of small molecular gel factor dissolved in solvent, intermolecular hydrogen bond interaction, 蟺-蟺 interaction, van der Waals force and other non-covalent bond interaction to form fiber network structure. The molecular structure of the gel factor has a great influence on the gel properties and irritability of organic gels. Therefore, the modification of the gel factors can greatly improve the functionality of the materials. For example, introducing functional groups that are responsive to external stimuli, such as light, electricity, sound, ions, acids and bases, temperature, etc., so as to achieve the external stimuli response of organic gels. Two derivatives of azobenzene (azobenzene are photoresponsive) derivatives based on hydrazide group (acyl hydrazide group containing abundant hydrogen bonds) were selected and their organic gels and their multiple reactivity were studied. To study the content as follows, we have studied the properties of organic gels and photo-responsibility.D7 can only form organic gels D8 in cyclohexane, and can form gels D10 in 1h2- dichloroethane and cyclohexane in 1h2- dichloroethane. Both cyclohexane and dimethyl sulfoxide can form gels. It can be found that with the increase of the terminal alkyl chain, the gel ability and the thermodynamics stability of the gel are improved. Under ultraviolet light irradiation, the azobenzene in the solution is photoisomerized. Trans azobenzene is converted to cis, Although the photoisomerization of D10 solution of cyclohexane was the most remarkable (the conversion ratio of trans-cis to cis was 66%), the photoisomerization of azobenzene in gel state could not induce the conversion of gel to sol. The properties of organic gels and their multiplicity. E6 and E10 can form stable gel aggregates of fiber network in N-N dimethylformamide, which is an azobenzene derivative based on acyl hydrazide group. The critical gel concentration of E10 was higher than that of E6, but E5 could not form the gel. This may be due to the increase of dipole moment of E5 due to the bending configuration of E5 with odd spacers, which increases the solubility of E5 in N-N dimethylformamide (polar solvent). Thus, organic gels that interfere with the aggregation of E5 molecules. E6 and E10 exhibit stimulative responses to a variety of environmental stimuli (including temperature, light, anions and pH). Photoisomerization of azophenyl groups occurs in organic gels irradiated by UV. As a result, the gel changed to precipitate, and the corresponding morphology changed from fiber to spherical aggregate. When anion FF- and Ac O-were added directly into en gel, the gel collapsed into solution and the color changed rapidly. The UV-Vis absorption and nuclear magnetic hydrogen spectra of anionic titration show that the acylhydrazide group deprotonates and the organic gel is also PH responsive. Adding alkali and acid can induce the reversible transition of gel and sol. The results of these studies can further understand the relationship between the structure and properties of small molecular gel factors, and study the anion response properties of en and 4-poxd-B8 bicomponent organic gels. Biological 4-poxd-B8 can form a stable gel in dimethyl sulfoxide. E5 could not form an organic gel, but the mixture with anionic responsiveness. E5 and 4-poxd-B8 could form a stable gel in dimethyl sulfoxide, and the gel showed different color changes in the stimulation of F- and Ac O- ions. However, the gel state does not change, the detection of anions and does not lead to the collapse of the gel.
【學(xué)位授予單位】：吉林大學(xué)
【學(xué)位級(jí)別】：碩士
【學(xué)位授予年份】：2017
【分類號(hào)】：O648.17

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