Study On The Synthesis And Properties Of The Side-chain Polypseudorotaxanes Containing Amine

Cucurbit[6]uril is a nonadecacylic cage compound which has a relatively rigid structure with a hollow core and accessible from the exterior by two carbonyl-fringed portals. Taking advantage of this fact, many researchers have studied rotaxane, polyrotaxanes, molecular necklace and molecular switch using cucurbit[n]uril (CB[n]). In this paper, we synthesized some side chain polyrotaxanes with CB[n]. Different polymers were synthesized with different pseudorotaxane monomer and acrylamide et al. Brief research background of this work is introduced, in which the history and recent progress in cucurbituril and polyelectrolytes as well as the application of CB[6] in polyelectrolytes are reviewed from a worldwide angle of view. The objective and the scientific significance of this doctoral dissertation are also pointed out.(1) A novel side-chain pseudorotaxane monomer N'-(3-vinylbenzyl)-1, 4-diaminobutane dihydrochloride with cucurbit[6]uril threaded (3VBCB) were prepared. We synthesized the side-chain polymers of P3VBCB by free radical polymerization with KPS as initiator in aqueous solution, which was characterized by 1H NMR, FT-IR, elemental analysis, DSC, TGA and static light scattering. At the same time, the interaction between DNA and P3VBCB was studied by gel electrophoresis and UV-Vis.(2) New copolymers of acrylamide and complex pseudorotaxane monomer N'-(3-vinylbenzyl)-1,4-diaminobutane dihydrochloride with cucurbit[6]uril threaded (3VBCB) were prepared via free radical polymerization in aqueous solution, which were characterized by 1H NMR, FT-IR, elemental analysis, and static light scattering. The thermal properties of copolymers were studied by TGA and DSC, and the effects of the copolymer concentration and pH on the average hydrodynamic radius (Rh) of the copolymers were studied by DLS. At the same time, the interaction between DNA and PAM3VBCB was studied by gel electrophoresis and UV-Vis.(3) New side-chain copolymers of acrylamide and complex pseudorotaxane monomer N'-(4-vinylbenzyl)-1,4-diaminobutane dihydrochloride with cucurbit[6]uril threaded (4VBCB) were prepared via free radical polymerization in aqueous solution. The copolymers PAM4VBCB were characterized by 1H NMR, FT-IR, elemental analysis, and static light scattering. Then the as-obtained copolymer PAM4VBCB, HAuCl4 and NaBH4 were used as reactants to obtain uniform Au NPs/carbon film composites via a hydrothermal process, and through tuning the experimental parameters such as reaction time, pH, quantity of HAuCl4 solution, and so on, Au NPs or Au@ carbon spHere core-shell like structures could also be obtained.(4) The side-chain copolymers of N-isopropyl acrylamide (NAM) and complex pseudorotaxane monomer N'-(4-vinylbenzyl)-1,4-diaminobutane dihydrochloride with cucurbit[6]uril (CB[6]) threaded (4VBCB) were prepared via free-radical polymerization in aqueous solution. The copolymers with CB[6] (PNAM4VBCB) were characterized by 1H NMR, FT-IR, elemental analysis, and static light scattering. And both pH and electrical conductivity curves of the solution of PNAM4VBCB-4 have a jump. In addition, the copolymers have thermal sensitivity and their phase-change temperatures could be controlled by adjusting the mole ratio of NAM/4VBCB in the copolymers. At the same time, the as-obtained copolymer PNAM4VBCB, HAuCl4 and NaBH4 were used as reactants to obtain uniform Au NPs/carbon film composites via a hydrothennal process, which was studied by TEM to analyze a distributing of the polymer nano material.(5) The side-chain copolymers DMAA and complex pseudorotaxane monomer N'-(4-vinylbenzyl)-1,4-diaminobutane dihydrochloride with cucurbit[6]uril (CB[6]) threaded (4VBCB) were prepared via free-radical polymerization in aqueous solution. The copolymers with CB[6] (PDMAA4VBCB) were characterized by 1H NMR, FT-IR, elemental analysis, and static light scattering. DLS data show that the copolymers have thennal sensitivity and their phase-change temperatures could be controlled by adjusting the mole ratio of DMAA/4VBCB in the copolymers. We can contral on or out of CB[6] in the pendent by controlling CaCl2 & NaCO3 addition, or BaCl2 & Na2SO4 addition.