本文關(guān)鍵詞： 聚集誘導(dǎo)發(fā)光 表面活性劑 復(fù)合材料 自組裝 成像分析　出處：《北京化工大學(xué)》2017年博士論文　論文類型：學(xué)位論文

【摘要】：利用聚集誘導(dǎo)發(fā)光(AIE)現(xiàn)象的光物理過程,以具有AIE特性的發(fā)光團(tuán)為構(gòu)筑單元,合成了一系列具有組裝功能的AIE型發(fā)光材料。它們分別帶有單電荷、雙電荷和多電荷,可以進(jìn)行自組裝、插層組裝以及層層組裝,從而形成高效發(fā)光體系。此外,組裝形式和組裝單元的不同,使這些發(fā)光體系能夠很好地用于成像分析和傳感應(yīng)用。對(duì)于帶有單電荷的AIE型發(fā)光材料,本論文設(shè)計(jì)并合成了以四苯乙烯基團(tuán)(TPE)為核的十二烷基磺酸鈉表面活性劑(TPE-SDS)。通過對(duì)其表面活性、電導(dǎo)率變化、以及形成膠束前后光學(xué)性質(zhì)的研究,證實(shí)TPE-SDS分子是AIE型陰離子表面活性劑。TPE-SDS分子在水溶液中可有序聚集自組裝形成球形膠束產(chǎn)生高效發(fā)光,該現(xiàn)象可以通過熒光共聚焦成像技術(shù)直接觀察到。隨著體系中電解質(zhì)濃度的增加,還可直接觀察到TPE-SDS分子從球形膠束到棒狀膠束、再到蠕蟲狀膠束的轉(zhuǎn)變。另一方面,在助表面活性劑的幫助下,TPE-SDS分子在非極性溶劑中,可以自組裝形成球形反膠束(即油包水微乳液滴)。該微乳液滴的大小與其熒光強(qiáng)度成反比關(guān)系。通過對(duì)微乳液滴幾何模型的分析發(fā)現(xiàn),微乳液滴表面的TPE-SDS分子間距離會(huì)隨著微乳液滴的增大而增大,導(dǎo)致限制分子運(yùn)動(dòng)的能力減弱,這一發(fā)現(xiàn)與AIE的發(fā)光機(jī)理是一致的。本論文還合成出以TPE為核的十二烷基三甲基溴化銨陽(yáng)離子表面活性劑(TPE-DTAB)。將TPE-DTA+陽(yáng)離子通過離子交換的方式插入到蒙脫土(MMT)層間,制備出TPE-DTA+插層的有機(jī)改性蒙脫土(TPE-DTAB-MMT)。粉末X射線衍射技術(shù)、傅立葉變換紅外技術(shù)和表面電勢(shì)測(cè)量等表征可知,TPE-DTA+陽(yáng)離子在蒙脫土層間具有多種有序的排布方式,使得蒙脫土顆粒疏水性增強(qiáng)。此外,在蒙脫土層間的TPE-DTA+陽(yáng)離子,由于其分子運(yùn)動(dòng)能夠被層間的二維限域空間有效抑制,從而減緩了非輻射衰減速率,得到較高的熒光量子產(chǎn)率。得益于TPE-DTAB-MMT顆粒的疏水性和高效發(fā)光特性,TPE-DTAB-MMT顆粒不僅能夠在有機(jī)聚合物中良好分散以制備有機(jī)一無(wú)機(jī)復(fù)合材料,還可以通過熒光共聚焦成像技術(shù)直接觀察到TPE-DTAB-MMT顆粒在復(fù)合材料中的三維分散度。與此類似,對(duì)于TPE-SDS修飾的水滑石顆粒在復(fù)合材料中的三維分散度也可同樣成像分析。相比于電鏡顯微成像技術(shù),基于構(gòu)建高效發(fā)光填料(插層組裝體)的熒光成像分析法具有其沒有的優(yōu)勢(shì),并且為有機(jī)—無(wú)機(jī)復(fù)合材料中無(wú)機(jī)填料的三維分散度評(píng)價(jià)的發(fā)展打開了新思路。對(duì)于帶有雙電荷的AIE型發(fā)光材料,可以在9,10-二苯乙烯基蒽(DSA)兩端修飾兩個(gè)磺酸根基團(tuán)而形成BSDSA。通過與無(wú)機(jī)的水滑石(LDH)納米片進(jìn)行層層組裝,進(jìn)而得到主—客體雜化的BSDSA/LDH發(fā)光薄膜。此外,利用聚苯乙烯磺酸鈉與BSDSA分子共組裝,可以讓LDH納米片上下層間的BSDSA分子構(gòu)象變得更加扭曲,從而實(shí)現(xiàn)發(fā)光顏色從黃色到綠色的調(diào)控。同時(shí),得益于水滑石主體層板的剛性結(jié)構(gòu),BSDSA的分子內(nèi)運(yùn)動(dòng)受到極大限制,從而得到較高的熒光量子產(chǎn)率。在25-85℃溫度范圍內(nèi),BSDSA/LDH發(fā)光薄膜會(huì)隨著溫度升高,而表現(xiàn)出熒光強(qiáng)度下降和發(fā)射波長(zhǎng)藍(lán)移的現(xiàn)象。這項(xiàng)工作中所構(gòu)建的高效發(fā)光薄膜(層層組裝體),能夠衍生出大量的AIE-LDH發(fā)光薄膜,并對(duì)具有發(fā)光可調(diào)或可變特性的固態(tài)發(fā)光材料的發(fā)展起到一定的指導(dǎo)作用。相比于帶有雙電荷的BSDSA分子,具有AIE特性的熒光金納米簇(Y-AuNCs)帶有多電荷,更有利于靜電層層組裝。將石英片交替浸入到聚烯丙胺(PAH)溶液和Y-AuNCs溶液中,制備出具有黃色熒光的Y-AuNCs/PAH薄膜。另一方面,傳統(tǒng)的非AIE型熒光金納米簇(R-AuNCs)同樣與PAH進(jìn)行組裝,可制備出具有紅色熒光的R-AuNCs/PAH薄膜。通過薄膜的吸收光譜、發(fā)射光譜和穩(wěn)態(tài)-瞬態(tài)熒光光譜對(duì)它們的光學(xué)性質(zhì)進(jìn)行表征。正如所料,在Y-AuNCs/PAH薄膜中,Y-AuNCs的熒光量子產(chǎn)率是溶液態(tài)的兩倍。此外,組裝5層的Y-AuNCs/PAH發(fā)光薄膜與組裝25層的R-AuNCs/PAH發(fā)光薄膜相比,二者的熒光強(qiáng)度相當(dāng)�；谶@些現(xiàn)象,以Y-AuNCs/PAH發(fā)光薄膜為傳感單元,R-AuNCs/PAH發(fā)光薄膜為參比單元,構(gòu)筑復(fù)色發(fā)光薄膜,可以實(shí)現(xiàn)對(duì)爆炸物的比率熒光檢測(cè),檢測(cè)限低至10-10M。
[Abstract]:The use of aggregation induced emission (AIE) light physical phenomenon, the light group with the characteristics of AIE as building blocks, a series of AIE type assembling function luminescent materials were synthesized. They are respectively provided with a single charge, double charge and charge, can self assemble, intercalation assembly and self assembly, thus forming high efficiency light emitting system. In addition, the assembly form and assembly unit is different, the light system can be well used for imaging and sensing applications. For the AIE type with a single charge of luminescent materials, this paper designed and synthesized four benzene vinyl group (TPE) twelve sodium dodecyl sulfonate surfactants (nuclear TPE-SDS). Based on its surface activity, conductivity, and optical properties of the micelles formed before and after, confirmed that the TPE-SDS molecule is AIE anionic surfactant.TPE-SDS molecules can self-assembly aggregation in aqueous solution The formation of spherical micelles have high luminescence efficiency, this phenomenon can be through confocal imaging directly observed. With the increase of electrolyte concentration in the system, but also can be directly observed TPE-SDS molecules from spherical micelle to rod, and then to change the wormlike micelles. On the other hand, in the cosurfactant under the help of TPE-SDS molecules in nonpolar solvents, can be self-assembled into spherical micelles (i.e. the microemulsion droplet). The size of the droplets and the fluorescence intensity is inversely proportional to the relationship. Through the analysis of the microemulsion droplet geometry model, TPE-SDS molecular micro emulsion droplets distance increases with the increasing of microemulsion drop, weakened the ability to limit molecular motion, and the luminescence mechanism of AIE this finding is consistent. This paper also synthesized with TPE core twelve alkyl three methyl bromide cationic surfactant ( TPE-DTAB). Insert the TPE-DTA+ cation by ion exchange method to montmorillonite (MMT) layer, preparation of Organic Modified Montmorillonite Intercalated TPE-DTA+ (TPE-DTAB-MMT). Powder X - ray diffraction, Fu Liye transform infrared technology and surface potential measurements showed that, TPE-DTA+ cation has a variety of orderly arrangement in the MMT, the montmorillonite particles increase the hydrophobicity. In addition, the TPE-DTA+ cation between montmorillonite, because its molecular motions can be two-dimensional confinement layer space effectively, thus slowing the rate of nonradiative decay, get higher fluorescence quantum yield. Thanks to the TPE-DTAB-MMT particle hydrophobicity and efficient luminescence properties TPE-DTAB-MMT, not only in organic polymer particles dispersed well prepared organic-inorganic composite materials in the system, but also through the fluorescence confocal imaging technique of direct observation The TPE-DTAB-MMT particles in the composite three-dimensional dispersion. Similarly, the TPE-SDS Modified Hydrotalcite particles in the composite dispersion can also be three-dimensional imaging analysis. Compared to the electron microscopic imaging technology, constructing efficient luminescence based on filler (intercalation assembly) fluorescence imaging analysis method has no the advantages, and opens up new ideas for the development of inorganic filler organic inorganic composite materials in the three-dimensional dispersion evaluation. For the AIE type with double charge luminescent materials, in 9,10- two styrene (DSA) modified anthracene ends two sulfonic acid groups formed by BSDSA. and inorganic nano hydrotalcite (LDH) film layer by layer, and then get the main object of BSDSA/LDH hybrid luminescent films. In addition, a total assembly using sodium polystyrene sulfonate and BSDSA molecules can make LDH nano sheet between the upper and lower BSDSA Conformation is more distorted, so as to realize the light color from yellow to green regulation. At the same time, due to the rigid structure of hydrotalcite main layer, the motion of BSDSA molecules is restricted greatly, resulting in higher fluorescence quantum yield. 25-85 degrees in the temperature range of BSDSA/LDH thin films as the temperature will rise, and show the fluorescence intensity decreased and the emission wavelength blue shift phenomenon. Efficient luminescent films constructed in this work (LbL assembly), can be derived from a large number of AIE-LDH luminescent films, and the development of solid state luminescent materials with light can be adjustable or variable characteristics play a guiding role. Compared to the BSDSA molecule with double the charge of the fluorescent gold nanoclusters with the characteristics of AIE (Y-AuNCs) with charge, more conducive to the electrostatic layer by layer assembly Quartz. Will alternately immersed into polyallylamine (PAH) solution and Y-AuNCs solution In the preparation of Y-AuNCs/PAH film with yellow fluorescence. On the other hand, non AIE type fluorescent gold nanoclusters (R-AuNCs) as the traditional assembly and PAH, prepared R-AuNCs/PAH films with red fluorescence. The absorption spectra of thin films, emission spectra and fluorescence spectra of steady-state transient optical properties of them respectively. As expected, in the Y-AuNCs/PAH film, the fluorescence quantum yield of Y-AuNCs is two times the solution state. In addition, the assembly of the 5 layer Y-AuNCs/PAH thin films with 25 layers of assembled R-AuNCs/PAH thin films compared to the fluorescence intensity of the two. Based on these phenomena, as the sensing unit with Y-AuNCs/PAH luminescence film, R-AuNCs/PAH light the film is a reference unit, build complex color luminescent films, can realize the ratiometric fluorescence detection of explosives, low detection limit to 10-10M.

【學(xué)位授予單位】：北京化工大學(xué)
【學(xué)位級(jí)別】：博士
【學(xué)位授予年份】：2017
【分類號(hào)】：TB33;O657.3

【相似文獻(xiàn)】

相關(guān)期刊論文 前10條

1 李湘洲;;自組裝材料[J];金屬世界;2006年01期

2 滇川;自組裝材料[J];世界科學(xué);1996年02期

3 王秀梅;喬琳;;促血管內(nèi)皮細(xì)胞生長(zhǎng)的功能化自組裝多肽框架材料的篩選和制備[J];中國(guó)組織工程研究與臨床康復(fù);2011年38期

4 李恒,石錦霞,何平笙;亞觀尺度的自組裝[J];化學(xué)通報(bào);2005年02期

5 陳昌盛;李仕穎;王俊;張先正;卓仁禧;;小分子硼酸肽的自組裝[J];中國(guó)材料進(jìn)展;2012年06期

6 王金鳳,賈欣茹,李盈,鐘z，

本文編號(hào)：1552947