Z-Group ketone chain transfer agents for RAFT polymer nanoparticle modification via hydrazone conjugation.
Z-Group ketone chain transfer agents for RAFT polymer nanoparticle modification via hydrazone conjugation.
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DOI：
10.1021/ma301536f
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发表时间：
2012-09-11
期刊：
影响因子：
5.5
通讯作者：
Bong D
中科院分区：
文献类型：
--
作者：
Bandyopadhyay S;Xia X;Maiseiyeu A;Mihai G;Rajagopalan S;Bong D
合成了一种含缩酮的三硫代羰基化合物，并将其表征为可逆加成裂解转移(RAFT)聚合中的链转移剂(CTA)。缩酮官能团不会干扰丙烯酸酯单体的RAFT聚合，如前所述，RAFT聚合可生成大分子CTA聚合物和嵌段共聚物。聚合后的缩酮裂解揭示了两亲性嵌段共聚聚合物的极性末端的酮功能。在有机溶液和形成聚合物纳米颗粒组装的水相缓冲液中，均能很容易地形成肼，这表明共轭/末端功能化的产率为40-50%。荧光素、生物素和Gd-DOTA的衍生物证实了偶联作用，虽然三硫代碳酸酯的连接是不稳定的，但我们在pH 7.4时观察到了几天的稳定偶联。和预期的那样，链霉亲和素与生物素化聚合物胶束结合，当Gd-DOTA酰肼与聚合物胶束连接时，观察到基于尺寸变化的驰豫增加。荧光标记的聚合物胶束的细胞摄取也很容易被FACS和荧光显微镜跟踪。这些聚合物衍生物展示了这种易于获得的酮-CTA的一系列潜在的治疗/生物技术应用，其中包括基于配体的纳米颗粒靶向和荧光/磁共振纳米颗粒造影剂。
A ketal-containing trithiocarbonyl compound has been synthesized and characterized as a chain transfer agent (CTA) in Reversible Addition Fragmentation Transfer (RAFT) polymerization. The ketal functionality does not interfere with RAFT polymerization of acrylate monomers, which proceeds as previously reported to yield macro-CTA polymers and block co-polymers. Post-polymerization ketal cleavage revealed ketone functionality at the polar terminus of an amphiphilic block co-polymer. Hydrazone-formation was facile in both organic solution as well as in aqueous buffer where polymer nanoparticle assemblies were formed, indicating a conjugation/end-functionalization yield of 40–50%. Conjugation was verified with fluorescein, biotin and Gd-DOTA derivatives, and though the trithiocarbonate linkage is hydrolytically labile, we observed stable conjugation for several days at pH 7.4. and 37°C. As expected, streptavidin binding to biotinylated polymer micelles was observed, and size-change based relaxivity increases were observed when Gd-DOTA hydrazide was conjugated to polymer micelles. Cell-uptake of fluorescently labeled polymer micelles was also readily tracked by FACS and fluorescence microscopy. These polymer derivatives demonstrate a range of potential theranostic/biotechnological applications for this conveniently accessible keto-CTA, which include ligand-based nanoparticle targeting and fluorescent/MR nanoparticle contrast agents.
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DOI：
10.1021/jp8108286
发表时间：
2009-05-07
期刊：
The journal of physical chemistry. B
影响因子：
--
作者：
Briley-Saebo KC;Geninatti-Crich S;Cormode DP;Barazza A;Mulder WJ;Chen W;Giovenzana GB;Fisher EA;Aime S;Fayad ZA
通讯作者：
Fayad ZA
影响因子：
5.2
作者：
Coster, MJ;De Voss, JJ
通讯作者：
De Voss, JJ
影响因子：
16.6
作者：
Lee, Sang-Min;Song, Ying;Hong, Bong Jin;MacRenaris, Keith W.;Mastarone, Daniel J.;O'Halloran, Thomas V.;Meade, Thomas J.;Nguyen, SonBinh T.
通讯作者：
Nguyen, SonBinh T.
影响因子：
46.2
作者：
Elsabahy M;Wooley KL
通讯作者：
Wooley KL
影响因子：
16.1
作者：
Janib, Siti M.;Moses, Ara S.;MacKay, J. Andrew
通讯作者：
MacKay, J. Andrew