基于离子自组装策略构筑的刺激响应超分子材料

发布时间：2018-03-14 20:08

本文选题：离子自组装　切入点：表面活性剂　出处：《山东大学》2017年硕士论文　论文类型：学位论文

【摘要】：近年来,超分子材料得到了迅速的发展,超分子凝胶、超分子传感器、超分子聚合物和超分子催化剂等新兴材料层出不穷。其中,刺激响应的超分子材料因其具有通过改变外界条件调节其形貌及性质的特点而备受科研工作者的关注。离子自组装(ionic self-assembly,ISA)作为超分子组装方法之一,具有操作简单、产物纯度高和能够避免复杂的有机合成等优点,因此被广泛应用于微纳米材料的制备。在本论文中,我们基于离子自组装策略,构筑了刺激响应的超分子微纳米材料,并探索了其应用。本论文主要包括以下四个部分:第一章介绍了离子自组装的概念以及近年来国内外在离子自组装和刺激响应的超分子材料方面的研究现状,据此提出了本论文研究思路。第二章通过离子自组装策略,采用偶氮苯类阳离子表面活性剂ETAB(C_2H_5-azobenzene-OC_6H_(12)-N~+(CH_3)3Br-)与多金属氧酸盐制备了光响应超分子纳米材料。(1)在水溶液中,利用ETAB与Keggin构型磷钨酸制备了超分子材料。通过核磁共振(NMR)波谱、傅里叶变换红外(FTIR)光谱、紫外可见(UV-vis)吸收光谱和小角X射线散射(SAXS)等技术,研究了 ETAB/POM复合物形成的驱动力和自组装机制。制备的超分子材料对紫外光照有明显的响应性质:在宏观上表现为光照之后复合物溶液的浊度增加;在微观上由珊瑚状的纳米结构变为单分散的纳米颗粒。(2)在水溶液中,利用含稀土 Eu的多金属氧酸盐(Eu-POM)和ETAB构筑了超分子材料。发现该材料的荧光性质比起Eu-POM有很大的提升,且对紫外光照、溶液pH和外加Cu~(2+)等外界刺激表现出良好的响应性质,在紫外光探测、传感器和光存储等领域有潜在的应用前景。第三章利用光响应的bola型偶氮苯表面活性剂分子BTHA(Br-(CH_3)_3N--C_6H_(12)O-azobenzene-OC_6H_(12)-N~+(CH_3)_3Br~-)和不同取代位的萘磺酸钠(1-NSA、2-NSA)制备了光响应的哑铃型超两亲分子。发现反离子取代基位置的不同对超两亲分子的组装过程以及形成的材料有显著的影响。BTHA/1-NSA形成的是枝晶状结构,而BTHA/2-NSA形成的是菱形片状结构。分别采用XRD技术和量子化学计算软件(Gaussian 09、MOPAC2016)从分子层面上对其组装机理进行了阐释。此外,形成的这两种超两亲分子组装体都表现出了良好的光响应特性,其荧光强度在紫外光照之后不仅得到了增强并且发生了一定程度的偏移,且具有良好的光稳定性,可以应用于构筑荧光开关。第四章通过表面活性离子液体对多金属氧酸盐进行包覆构筑了超分子复合物,并研究了其在生物检测方面的应用。(1)合成了 Gemini型表面活性离子液体—1,2-双(十六烷基咪唑)溴乙烷([C_(16)-2-C_(16)im]Br_2),通过铜离子对Eu-POM/[C_(16)-2-C_(16)im]Br_2超分子复合物进行修饰,制备了一种新颖的超分子荧光探针,并应用于硫化氢的快速检测。尽管铜离子的加入导致Eu-POM/[C_(16)-2-C_(16)im]Br_2纳米颗粒的荧光略微猝灭,但经修饰之后的探针依旧具有非常强的荧光。铜离子修饰的超分子荧光探针(Cu~(2+)-modified supramolecular sensor,CSS)对于硫化氢的快速检测表现出了荧光和紫外吸收的双重信号变化,且具有良好的灵敏性和选择性。我们还探究了 CSS探针对于硫化氢的荧光猝灭机制。此研究对于检测阿尔兹海默症和唐氏综合征等一些相关疾病具有重要意义。(2)利用酰胺功能化的表面活性离子液体—N-十二烷基-N'-乙酰胺溴化咪唑([C_(12)ImCONH_2]Br)和Eu-POM进行自组装,构筑了一种表面活性剂包覆的纳米颗粒。通过等温滴定量热技术测定了材料的生成热及确定了[C_(12)ImCONH_2]Br)和Eu-POM的结合比例。细胞毒理实验显示该超分子纳米颗粒具有良好的生物相容性。通过荧光测试发现,该纳米颗粒的光致发光性质较Eu-POM有显著的增强,并且对双氧水表现出良好的响应性能,有望应用于双氧水的检测。
[Abstract]:In recent years, supramolecular materials have developed rapidly, supramolecular gels, supramolecular sensors, supramolecular polymers and supramolecular catalysts emerge in an endless stream of new materials. Among them, the stimulus response of supramolecular materials because of its characteristics by changing external conditions regulating the morphology and properties has attracted the attention of scientists. Ionic self-assembly (ionic self-assembly ISA) as one of the supramolecular assembly method, has the advantages of simple operation, high product purity and can avoid the advantages of complex organic synthesis, it is widely used in micro nano material preparation. In this thesis, we based on the ionic self-assembly strategy, constructs the stimulus response of supramolecular micro nano materials, and explore its application. The thesis mainly includes the following four parts: the first chapter introduces the concept of ionic self assembly at home and abroad in recent years and the stimulation of ionic self-assembly The research status on response of supramolecular materials, and puts forward the research ideas. The second chapter through ionic self-assembly strategies, using azobenzene cationic surfactant ETAB (C_2H_5-azobenzene-OC_6H_ (12) -N~+ (CH_3) 3Br-) and polyoxometalates were prepared by supramolecular nano materials. The optical response (1) in water in the solution, supramolecular materials were prepared by using ETAB and Keggin configuration of phosphotungstic acid system. By nuclear magnetic resonance (NMR) spectroscopy, Fourier transform infrared (FTIR) spectroscopy, ultraviolet visible (UV-vis) absorption spectroscopy and small angle X ray scattering (SAXS) technique on the formation of the ETAB/POM complex driving force and self assembly the mechanism of preparation of supramolecular materials. There are obvious nature of the response to UV illumination: at the macro level to light after the compound of the turbidity of the solution increases; in the micro nano structure by coral into nanoparticles (2). In aqueous solution, using Polyoxometalates Containing Rare Earth Eu (Eu-POM) and ETAB to build supramolecular materials. It was found that the fluorescence properties of the material is much better than Eu-POM, and the UV light, and the solution of pH plus Cu~ (2+) showed a response to external stimuli such as good quality, in the ultraviolet detection, sensor and optical storage field has potential application prospect. The third chapter uses Bola azobenzene surfactants BTHA light response (Br- (CH_3) _3N--C_6H_ (12) O-azobenzene-OC_6H_ (12) -N~+ (CH_3) _3Br~-) and different substituent the naphthalene sulfonate (1-NSA, 2-NSA) were prepared dumbbell light response of over two Pro molecules. Found counter ion substituents at different positions on the assembly process of over two amphiphilic molecules and the formation of the material has a significant effect of.BTHA/1-NSA is the formation of dendrite structure, and the formation of BTHA/2-NSA diamond sheet structure were used. XRD technology and quantum chemical calculation software (Gaussian 09, MOPAC2016) are elaborated from the molecular level to the assembly mechanism. In addition, the formation of the two super two amphiphilic molecular assemblies have shown a good response after the light, the fluorescence intensity in the UV light not only to enhance and shift to a certain extent, and has good light stability, can be applied to the construction of a fluorescence switch. In the fourth chapter, through the surface activity of ionic liquid on polyoxometalates were coated to build supramolecular complexes, and studied its application in biological detection. (1) Gemini surface active ionic liquid 1,2- double synthesis (sixteen alkylimidazolium) ethane ([C_ (16) -2-C_ (16) im]Br_2), the copper ions on Eu-POM/[C_ (16) -2-C_ (16) im]Br_2 supramolecular complex modification, a novel supramolecular fluorescence probe were prepared, and should For rapid detection of hydrogen sulfide. Although the addition of copper ions in Eu-POM/[C_ (16) -2-C_ (16) fluorescence quenching of im]Br_2 nanoparticles slightly, but the probe after modification still has very strong fluorescence. The supramolecular fluorescence probe modified copper ion (Cu~ (2+) -modified supramolecular sensor, CSS) to change the dual signal of hydrogen sulfide the rapid detection showed fluorescence and UV absorption, and has good selectivity and sensitivity. We also explored the mechanism of fluorescence quenching of CSS probe for hydrogen sulfide. This research is of great significance for the detection of Alzheimer's disease and Down syndrome and other related diseases. (2) using the surface active ionic liquid amide functionalized N- twelve -N'- alkyl imidazole acetamide bromide ([C_ (12) ImCONH_2]Br) and Eu-POM self-assembled nanoparticles to build a surfactant coated by. Isothermal titration calorimetry determination of the heat generating material and determine the [C_ (12) ImCONH_2]Br) with ratio and Eu-POM. Cell toxicity experiment showed that the supramolecular nanoparticles have good biocompatibility. By fluorescence measurements, the photoluminescence properties of nano particles with Eu-POM significantly increased, and the hydrogen peroxide show good response performance, is expected to be applied to the detection of hydrogen peroxide.

【学位授予单位】：山东大学
【学位级别】：硕士
【学位授予年份】：2017
【分类号】：O641.3

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