两亲分子聚集体荧光传感器的交互响应和指纹图谱识别研究

Amphiphilic aggregates with microheterogeneous structures can dissolve fluorescent probes in aqueous solutions, and enhance emitting and sensing properties of the encapsulated fluorophores, which leads to widespread applications of amphiphilic aggregates in fluorescence sensing. However, amphiphilic aggregates are seldom used in pattern recognition that is advantageous in analyzing complex samples. The few reports involving pattern recognition encounter issues like using multiple fluorophores and tedious data collecting. The present project proposes to design and synthesize a series of pyrene-based derivatives with special structures, to utilize the multiple physicochemical microenvironments of amphiphilic aggregates to modulate the multiple fluorescence signal outputs of the encapsulated pyrene-based fluorophores, and to construct single cross-reactive fluorescent sensors with pattern recognition ability. The project will thoroughly investigate the cross-reactive responses and discriminative ability of such amphiphilic aggregate-based fluorescent sensors to multiple analytes, examine the dependency of its multiple-wavelength cross-reactivity on the molecular structure of fluorescent probes and on the modulation ability of amphiphilic aggregates, and explore the mechanisms of its cross-reactive responses. It is believed that the studies of the above-mentioned scientific issues will deepen the understanding about the interactions between amphiphilic aggregates and the encapsulated fluorophores, widen the designing strategies for constructing sensors with pattern recognition ability, simplify data collecting process, strengthen the high-throughput identification ability of fluorescent sensors, and endow the traditional colloid chemistry with novel applications in the sensing fields.

具有微多相结构特征的两亲分子聚集体可增溶荧光探针分子，改善探针发光和传感性能，因而广泛应用于荧光传感领域。然而，两亲分子聚集体在对复杂样品分析具有优势的指纹图谱识别方面研究较少，仅有的文献报道存在荧光物种多、数据采集复杂等问题。本项目拟设计合成系列具有特定结构的芘荧光衍生物，将其增溶于两亲分子聚集体内，利用两亲分子聚集体多元化的物理化学环境，调控其在聚集体内的微观状态和多重荧光发射，构建基于多波长交互响应的指纹图谱识别型单一荧光传感器。项目将系统考察此类两亲分子聚集体荧光传感器对多分析物的交互响应性和区分识别能力，研究其多波长交互响应性与探针分子结构和聚集体调控作用的依赖关系，揭示其交互响应性的形成机理。相信此项目的开展，有助于加深对两亲分子聚集体与荧光分子相互作用规律的认识，拓展指纹图谱识别传感器的设计思路，简化数据采集过程，增强区分识别能力，推进传统胶体化学在传感领域的新应用。

根据项目计划书的研究任务，围绕两亲分子聚集体光物理调控策略构建交互响应性传感体系开展研究工作。在国家自然科学基金委面上项目的支持下，项目组设计合成了阳离子咪唑、金属离子受体基团、自组装基团胆酸等修饰的单芘衍生物，经极性连接臂介导的双芘衍生物、双发色团探针等具有多种结构特点的荧光探针分子，考察了两亲分子聚集体如SDS、SDBS、DTAB、CTAB等对探针分子的光物理性质特别是发光性能的调控作用，构建了一系列具有多谱带发射的基于两亲分子聚集体和荧光探针的二元荧光传感体系，研究了其对相似分析物或混合样品分析物的交互响应性和区分识别能力，获得了多个可对金属离子、蛋白质、生物硫醇等分析物高通量区分识别的具有多波长交互响应的单一荧光传感体系。项目研究发现，两亲分子聚集体调控策略可扩展至在水中具有良好溶解性的单芘衍生物，分析物受体基团的结合作用与两亲分子聚集体调控作用的结合能够大大提高此类体系的区分识别能力，基于该策略构建的传感体系不但能够实现单一传感体系对相似分析物的区分识别，大大简化数据采集过程，减少样品的消耗，还能够应用于生物体液环境样品的区分与检测，具有良好的应用前景。本项目的开展，既为交互响应性传感体系特别是单一区分识别体系的构建提供了新的策略，还有力地推进了传统胶体化学在传感领域的新应用。项目资助期间发表标注论文15篇，均为SCI收录论文，授权专利4项，培养博士研究生2人，硕士研究生7人。