【摘要】 利用丙炔胺分别和Boc-L-丙氨酸及丙烯酸反应合成了Boc-L-丙氨酸丙炔酰胺和丙烯酸丙炔酰胺2种单体,即手性单体1和非手性单体2.以(nbd)Rh+[η6-C6H5B-(C6H5)3]为催化剂将2种单体进行共聚制得产率为60%,相对数均分子量Mn=2.0×104的新型螺旋聚合物.圆二色光谱(CD)及紫外-可见(UV-Vis)吸收光谱表征发现聚合物具有很强的光学活性且能形成单一方向的螺旋构象.共聚物的螺旋构象不受非手性单体的影响,共聚物的光学活性及CD吸收峰的强度比均聚物略低.在三氟乙酸/二氯甲烷混合溶液作用下将聚合物侧链上的叔丁氧羰基(Boc)基团脱除得到带有氨基的螺旋聚合物.利用缩合方法将带有氨基的螺旋聚合物接枝到改性后的Si O2纳米粒子表面,经热失重曲线计算得到表面接枝密度σ=2.4μmol/m2.最后采用蒸馏-沉淀聚合方法制备手性荧光聚合物微球,并利用TEM及SEM观察手性荧光聚合物微球的表面形貌及粒径.紫外-可见吸收光谱及荧光光谱表明新型手性荧光聚合物微球具有一定的荧光性能,并将在药物运载、生物标记学领域发挥作用.更多还原

【Abstract】 Two kinds of substituted acetylene monomers were synthesized using propargylamine with Boc-Lalanine and acrylic acid. These two kinds of monomers were separately named as chiral monomers 1 and achiral monomers 2. Then chiral monomers 1 and achiral monomers 2 were polymerized using( nbd) Rh+[η6-C6H5B--( C6H5)3]as catalyst to obtain copolymers with Mn= 2. 0 × 104,yield 60%. CD and UV-Vis spectroscopic data indicated the copolymers and homopolymers exhibited high optical activity and formed stable single helical conformation. And the achiral monomers did not affect the helical structure of the copolymers,but the optical activities and CD intensity of the copolymers were slightly lower than those of the homopolymers. The copolymer2 was prepared in the condition of TFA/CH2Cl2,and then it was grafted to the chemical modified silica nanoparticles by the condensation reaction. The surface grafting density of the silica nanoparticles was 2. 4μmol /m2,which was estimated from the thermo-gravimetric curve. Finally,the chiral fluorescent polymeric microspheres were prepared by the distillation-precipitation polymerization of N-vinylcarbazole. TEM and SEM were used to observe the surface morphology and particle size of polymeric microspheres. UV-Vis and fluorescence spectra showed the chiral fluorescent polymeric microspheres had certain fluorescence properties.They will play an important role in the field of drug delivery and biomarkers.更多还原