基于芘修饰树枝形聚合物的水相温敏荧光传感体系  

Pyrenyl Peripheral-Decorated Polyamidoamine Dendrimer for Fluorescent Temperature Detection in Aqueous Phase

作　　者：秦天依 曾毅[1,2] 陈金平[1] 于天君[1] 李嫕[1,2] Qin Tianyia b Zeng Yia(a Key Laboratory of Photochemical Conversion and Optoelectronic Materials, Technical Institute of Physics and Chemistry, Chinese Academy of Sciences, Beijing 100190 b University of Chinese Academy of Sciences, Beijing 10004)

机构地区：[1]中国科学院理化技术研究所光化学转换与功能材料重点实验室,北京100190 [2]中国科学院大学,北京100049

出　　处：《化学学报》2017年第1期99-104,共6页Acta Chimica Sinica

基　　金：国家自然科学基金(No.21233011);973项目(2013CB834703 and 2013CB834505)资助~~

摘　　要：设计合成了外围芘修饰的质子化二代聚酰胺-胺树枝形聚合物G2 PAMAM-PyH.~1H NMR和紫外可见吸收光谱表征确定芘基团的上载率为100%.吸收光谱、动态光散射(DLS)和透射电子显微镜(TEM)研究结果表明,G2 PAMAMPy H在水中形成平均粒径为184 nm双分子膜囊泡结构.水相中G2 PAMAM-Py H囊泡体系呈现芘单体和激基缔合物的双荧光发射,1~70℃范围内,随温度升高芘单体荧光逐渐增强,而芘激基缔合物发光单调减弱,荧光颜色由绿变蓝,芘激基缔合物与芘单体发光比(I_(495 nm)/I_(398 nm))随温度变化具有良好的可重复性,符合公式I_(495 nm)/I_(398 nm)=28.23-0.68t+3.21×10^(-3)t^2+1.83×10^(-5)t^3,可用于水相体系内部温度梯度的表征,在1~70℃范围温度测量灵敏度高于0.9℃.本工作为温度荧光探针传感体系的构筑提供了一种新方法.A protonated polyamidoamine（PAMAM） dendrimer of generation 2 with pyrenyl attached to its periphery（G2 PAMAM-Py H） was designed and synthesized. G2 PAMAM-Py was synthesized by a condensation of the terminal amino group of the PAMAM dendrimer and the aldehyde group of 1-pyrenecarboxaldehyde followed by a reduction of Schiff base through ＂one pot＂ reaction. G2 PAMAM-Py was further protonated by adding HCl, giving the target product G2 PAMAMPy H. The structure of G2 PAMAM-Py H was characterized by NMR, FTIR, and MS. The functionalization extent of the peripheral amino groups of PAMAM by pyrenyl is 100% according to the ^1H NMR and UV-visible spectra. The amphiphilic G2 PAMAM-Py H is soluble in water with a critical aggregation concentration of 3.3×10^-7 mol·dm^-3. Absorption, dynamic light scattering（DLS）, and transmission electronic microscopy（TEM） studies demonstrate that G2 PAMAM-Py H exists as vesicle with a bilayer membrane and an average hydrodynamic diameter of ca. 184 nm in aqueous phase. G2 PAMAM-Py H in aqueous phase exhibits dual fluorescence, pyrenyl monomer and excimer emission. The pyrenyl monomer fluorescence increases slightly and the pyrenyl excimer emission decreases monotonically upon temperature raising from 1 to 70 ℃. Meanwhile, the fluorescence color changes from green（low temperature） to blue（high temperature）. The monomer emission enhancement is mainly attributed to less formation of excimer when rising temperature. The fluorescence intensity ratio of pyrenyl excimer to pyrenyl monomer（I495 nm/I398 nm） changes with varying temperature recoverably, and the relationship between I495 nm/I398 nm and temperature can be expressed as I495 nm/I398 nm=28.23-0.68t＋3.21×10^-3t^2＋1.83×10^-5t^3. The accuracy for the measurement of the temperature is better than 0.9 ℃ in the temperature range of 1~70 ℃, facilitating in situ gradient temperature measurement. The temperature gradient of aqueous phase in a glass tube is investigated by using G2 PAMAM-Py H, which i

关 键 词：温度检测 荧光传感 聚酰胺-胺树枝形聚合物 芘 

分 类 号：O657.3[理学—分析化学] O631.3[理学—化学]