新颖阴离子诱导分子内氢转移的受体设计及识别性能研究

The design and synthesis of artificial receptors for sensing and recognition of anions have received considerable attention in supramolecular chemistry because of the essential roles that anions play in a wide variety of biological, clinical and environmental sciences. The usual design principles for anion sensing are through hydrogen-bonding interaction, intermolecular proton-transfer reaction or the Lewis acid/base interactions. Compared to the above traditional methods, the approach based on an irreversible specific chemical reaction has emerged as an active research area of significant importance for high selectivity recently. However, considerable efforts have been devoted to the development of specific chemical reaction, and recognition of anions based on novel anion-induced intramolecular hydrogen transfer has not been developed so far. In this proposal, motivated by previous work, the libraries of novel anion receptors based on anion-induced intramolecular hydrogen transfer is constructed. The effect of receptor configuration to pathway of intramolecular hydrogen transfer would be investigated extensively through the libraries of anion receptors, which would be founded based on the chemical modification of previous lead compound through expanding the electron-deficient organic π-system, introducing the push-pull electron group, changing the space size of H-bond donor motif and increasing the coordination sites. Meanwhile, the QSAR between receptors and anion-induced intramolecular hydrogen transfer would be proposed, and further the approach to rational design the molecules reported in the photo-induced intramolecular hdyrogen atom transfer would be developed so as to achieve more efficient anion receptors. Through this project, we envisioned the feasibility of more broader application of anion-induced intramolecular hydrogen transfer, and possibility of novel anion receptors are highly desirable for application in screening processes and in sciential field work.

阴离子在生命、临床及环境科学中有着重要作用，设计用于识别阴离子的人工合成受体是超分子化学的一个研究热点。识别阴离子的普遍原理主要有氢键作用、质子转移机制、路易斯酸碱作用。相对上述传统方法，近年来基于不可逆特定化学反应的识别方法因其选择性高而备受青睐。尽管已报道一些反应用来识别阴离子，但通过阴离子诱导分子内氢转移反应的识别方法却被较少关注。本项目借鉴前期研究基础旨在组建基于阴离子诱导分子内氢转移的新颖识别受体库。通过对前期所得受体进行共轭体系延展、引入推拉电子体系、改变活泼氢周围的基团尺寸、增加配位位点等策略建立阴离子受体库，详尽阐述分子结构变化对分子内氢转移的光谱影响。同时，探讨构效关系以期发展新方法指导设计修饰光控分子内氢转移主体分子，发现更高效的识别阴离子受体。通过本课题研究期望进一步拓宽分子内氢转移识别方法在阴离子识别中的应用，找到具有潜在应用价值的新颖受体。

阴离子在生命、临床及环境科学中有着重要作用，设计用于识别阴离子的人工合成受体是超分子化学的一个研究热点。本项目主要发展了阴离子诱导脱氢引发脱氰基进而氧化成羰基的新颖识别机理，并首次报道了一类基于共轭延伸片段-荧光团-作用位点的顺反异构受体用于识别氰根离子以及成功构建分子内NH…NH2氢键参与的新颖探针。同时课题组还对萘酐溴与取代的苯乙腈（吸电子，供电子，稠环芳乙腈）的反应，进行了详细的研究，合成了10余个不同取代基的alpha, alpha-萘酐芳基苯乙腈，进而借助氟离子脱氢脱氰基氧化机理，合成了一系列萘酐芳基酮衍生物。此外，项目组通过结合前期结果，巧妙地设计了两类含CHCN及Si-O键、及含CHCN及NH键双作用靶点的受体分子。进一步地， 探讨氟诱导硅氧键断裂，以及氟离子敏感自分解进而串联释放含氧负离子荧光团机制的识别阴离子方法。.经过三年努力，课题组在阴离子识别领域积累了丰富的研究经验以及独特的研究特色，本项目目前已发表SCI论文9篇，其中3篇Chem. Commun. （IF=6.834），申请中国专利3项（授权1项），培养硕士研究生5名毕业。