"Click" Reactions: Novel Chemistries for Forming Well-defined Polyester Nanoparticles
"Click" Reactions: Novel Chemistries for Forming Well-defined Polyester Nanoparticles
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DOI：
10.1021/ma100711b
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发表时间：
2010-07-13
期刊：
影响因子：
5.5
通讯作者：
Harth, Eva
中科院分区：
文献类型：
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作者：
van der Ende, Alice E.;Harrell, Jameson;Harth, Eva
我们提出了在选定的纳米尺度上通过受控的分子间链交联过程来合成离散的官能化聚酯纳米粒子的方法，所述受控的分子间链交联过程经由诸如铜(I)催化的叠氮化合物的1，3-偶极环加成反应和硫醇-烯反应等化学方法来促进。这两个“点击”反应都导致形成具有窄尺寸分布和选定的纳米尺寸尺寸的明确定义的纳米颗粒。受控偶联涉及炔基官能化聚酯与双叠氮，1，8-二叠氮-3，6-二氧辛烷，和带有3，6-二氧杂-1.8-辛二硫醇的烯丙基功能化聚酯。通过开环共聚，我们发现纳米粒子的形成和对纳米尺寸的控制主要受前体聚合物中实现的炔基或烯丙基实体的程度以及双叠氮化物和二硫醇交联剂的量的影响。这些结果再次强调了分子间链交联反应的多功能性，这种反应不仅限于环氧化物化学，而且可以扩展到TC“点击”反应，以形成具有类似效率的受控纳米颗粒。本工作描述了在选定的纳米范围内，利用炔叠氮和硫醇-烯“点击”化学来促进超分子三维结构的受控组装和交联
We present the synthesis of discrete functionalized polyester nanoparticles in selected nanoscale are dimensions via a controlled intermolecular chain cross-linking process facilitated via "click"-chemistry approaches such as the Cu(I)-catalyzed 1,3-dipolar cycloaddition of azides and thiol-ene reactions Both "click" reactions led to the formation of well-defined nanoparticles with narrow size distribution and selected nanoscopic size dimensions The controlled coupling involves the cross-linking of an alkyne functionalized polyester with a bisazide, 1,8-diazide-3,6-dioxaoctane, and an allyl functionalized polyester with 3,6-dioxa-1.8-octanedithiol The linear functional polyester precursors were synthesized via ring-opening copolymerization of delta-valerolactone and alpha-propargyl-delta-valerolactone as well as with alpha-ally-delta-valerolactone, respectively We found that the nanoparticle formation and the control over the nanoscopic dimension are primarily influenced by the degree of the alkyne or allyl entity implemented in the precursor polymer and the amount of bisazide and dithiol cross-linking reagents These results underline once more the versatility of the intermolecular chain cross-linking reaction which is not limited to epoxide chemistries but can be extended tc "click" reactions to form controlled nanoparticles with comparable efficiencies This work describes the utilization of alkyne azide and thiol-ene "click" chemistries to facilitate the controlled assembly and cross-linking of supramolecular 3-D structures in selected nanoscopic ranges