Facile, versatile prepolymerization and postpolymerization functionalization approaches for well-defined fluorescent conjugated fluorene-based glycopolymers
Facile, versatile prepolymerization and postpolymerization functionalization approaches for well-defined fluorescent conjugated fluorene-based glycopolymers
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DOI：
10.1021/ma060422e
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发表时间：
2006-08-22
期刊：
影响因子：
5.5
通讯作者：
Liu, Haiying
中科院分区：
文献类型：
--
作者：
Xue, Cuihua;Donuru, Venkat R. R.;Liu, Haiying
我们已经开发了简单、通用的预聚合和后聚合功能化方法，通过形成硫醚来制备定义明确的荧光共轭芴基糖共聚物（聚合物A和B）。明确定义的携带葡萄糖的单体（5）和共轭聚合物（聚合物2）是通过将关键前体2，7-二碘-9，9-二（6 ′-溴己基）芴（2）和聚[（9，9-双（6 ′-溴己基）-2，7-亚芴基）-alt-1，4-亚苯基]（聚合物1）分别与过量的1-硫代-β-D-葡萄糖四乙酸酯（3）在碱性条件下反应。在5%CuI、5%Pd（PPh 3）（2）Cl-2和10%PPh3存在下，通过钯催化的Sonogashira偶联聚合单体5与二乙炔基苯，制备了具有全乙酰化葡萄糖残基的定义明确的聚（2，7-芴亚乙炔基）-alt-1，4-（2，5-二甲氧基苯亚乙炔基）（聚合物3）。聚合物2和3在Zemplen条件下在甲醇和含有甲醇钠的二氯甲烷中脱乙酰基，分别得到两种基于芴的共轭糖基共聚物A和B。聚合物A也通过聚合物1与1-硫代-β-D-葡萄糖钠盐水合物（4）在碱性条件下反应而获得。产物的组成和纯度通过1H NMR可靠地分析。采用后聚合功能化方法制备了含葡萄糖侧基和三甘醇侧链的水溶性芴基共轭共聚物（聚合物C）。这种硫醚形成反应提供了一种非常有效的缀合方法，将受保护或未受保护的碳水化合物残基共价连接到荧光缀合聚合物上。
We have developed facile, versatile prepolymerization and postpolymerization functionalization approaches to prepare well-defined fluorescent conjugated fluorene-based glycopolymers ( polymers A and B) through thioether formation. Well-defined glucose-carrying monomer ( 5) and conjugated polymer ( polymer 2) were prepared by coupling the key precursors, 2,7-diiodo-9,9-bis(6'-bromohexyl) fluorene ( 2) and poly[(9,9-bis( 6'-bromohexyl)-2,7-fluorenylene)-alt-1,4-phenylene] (polymer 1) with an excess of 1-thio-beta-D-glucose tetraacetate ( 3) in a basic condition, respectively. A well-defined poly(2,7-fluorenylene-ethynylene)-alt-1,4-(2,5-dimethyoxyphenyleneethynylene) bearing peracetylated glucose residues ( polymer 3) was prepared by a palladium catalyzed Sonogashira coupling polymerization of monomer 5 with a diethynylbenzene in the presence of 5% CuI, 5% Pd(PPh3)(2)Cl-2 and 10% PPh3. Polymers 2 and 3 were deacetylated under Zemplen conditions in methanol and methylene chloride containing sodium methoxide, affording two fluorene-based conjugated glycopolymers A and B, respectively. Polymer A was also obtained by the reaction of polymer 1 with 1-thio-beta-D-glucose sodium salt hydrate ( 4) in a basic condition. The composition and purity of the products were reliably analyzed by 1H NMR. Water-soluble fluorene-based conjugated copolymer bearing glucose pendants with tri(ethylene glycol) tethers ( polymer C) was prepared by the postpolymerization functionalization approach. This thioether formation reaction offers a very effective conjugation method to covalently attach protected or unprotected carbohydrate residues to fluorescent conjugated polymers.