Syntheses And Supramolecular Property Of Novel Poly-purine Derivatives And Calix[n]Purine

As one of the basic base units in DNA sturctrue, guanine is widely used in molecular recognition and the construction of supramolecular system. The research on macromolecule containing purine not only help understand the behavior of life base, but also provide the theoretical basis for the design of novel supramolecular material.Meanwhile the development of new host-macromolecule system has always been one of the most important research area in supramolecular chemistry, also act as one of the sources for innovation. Basing on the content above, a novel type macromolecule containing purine had been designed and synthesizedin this thesis, and the self-assembly properties had been discussed preliminary. On the other hand, a novel type of macrocyclic compoundconstruct by purine as the unit was synthesized. The structure features and the reaction conditions were studied. The main contents in this thesis are shown as follows. 1. Two kinds of macromolecule containing muti-purine were designed and synthesized using click reaction. The structure is based on pentaerythritol structural framework, and the purine terminal groups are connected by ether oxygen chain. The structures are identified by1H NMR、13C NMR and ESI-TOF. The interaction of the macromolecules with alkali metals in water were further studied. It was found out that the macromolecular containing6-chloro-purine has no selectivity for different metal ions, but the macromolecular containing6-oxy-purine has a specific selectivity for K+ions among other alkali metals ions.2. The supramolecular polymer formed by6-oxy-purine macromolecule with K+ion were studied by SEM characterization. A mechanism was proposed for this supramolecular polymer:there is two trends for the extending of the aggregation, one is extending to all the directions as the4terminalguanines form G-quartet respectively, one is extending in a line as two terminal guanines form G-quartet with two terminal guanines in another macromolecule.As K+ion lies upon the plane of G-quartet other than fit in the cavity because of the size, the whole system is stabilized by the ion-dipole interaction between K+and the G-quartet.3.A novel heterocalixareneblocked by purine was designed and synthesized, and the content "calix[n]purine" was first proposed. The synthesis reaction condition of calix[3]purinewas optimized and discussed.The result showed that alkali metal ions act as a template in the formation of the macrocyclic compound.4. The derivatization reactionsof calix[n]purine were explored, and the structural feature was studied.The synthesis of different types of calix[n]purines were discussed. It was found out that the amino of the purine play an important role in the reaction. Besides, the length of the sulfur ether need to be3-5atoms. The solubility of calix[n]purine was improved by the acylation on amino.