PEG支化Polymer用于超长血液循环纳米材料的功能化
PEG Branched Polymer for Functionalization of Nanomaterials with Ultralong Blood Circulation
摘要：
近年来，纳米材料在生物和医学应用中得到了积极的追求。在这里，我们报告了几种新的聚（乙二醇）接枝支链聚合物的功能化的各种纳米材料，包括碳纳米管，金纳米粒子（NP）和金纳米棒（NR）的合成，为这些材料提供高的水溶性和稳定性。我们合成了不同的表面活性剂聚合物基于聚-（g-谷氨酸）（gPGA）和聚（马来酸酐-alt-1-十八烯）（PMHC 18）。我们使用gPGA丰富的游离羧酸基团来连接亲脂性物质，如芘或磷脂，其通过强大的物理吸附与纳米材料结合。此外，gPGA上的剩余羧酸或PMHC 18的胺反应性酸酐然后被PEG化，提供延伸的亲水基团，提供聚合的两亲物。我们表明，由聚合物官能化的单壁碳纳米管（SWNT）、Au NP和NR在不同pH值、高温和血清的水溶液中表现出高稳定性。此外，聚合物包覆的单壁碳纳米管在静脉注射到小鼠体内时表现出显著的长血液循环（t1/2 22.1 h），远远超过了之前的5.4 h记录。超长的血液循环时间表明小鼠网状内皮系统（RES）对纳米材料的清除大大延迟，这是纳米材料体内应用（包括成像和药物递送）的一个非常理想的特性。
英文摘要：
Nanomaterials have been actively pursued for biological and medical applications in recent years. Here, we report the synthesis of several new poly(ethylene glycol) grafted branched-polymers for functionalization of various nanomaterials including carbon nanotubes, gold nanoparticles (NP) and gold nanorods (NRs), affording high aqueous solubility and stability for these materials. We synthesize different surfactant polymers based upon poly-(g-glutamic acid) (gPGA) and poly(maleic anhydride-alt-1-octadecene) (PMHC18). We use the abundant free carboxylic acid groups of gPGA for attaching lipophilic species such as pyrene or phospholipid, which bind to nanomaterials via robust physisorption. Additionally, the remaining carboxylic acids on gPGA or the amine-reactive anhydrides of PMHC18 are then PEGylated, providing extended hydrophilic groups, affording polymeric amphiphiles. We show that single-walled carbon nanotubes (SWNTs), Au NPs and NRs functionalized by the polymers exhibit high stability in aqueous solutions at different pHs, at elevated temperatures and in serum. Morever, the polymer-coated SWNTs exhibit remarkably long blood circulation (t1/2 22.1 h) upon intravenous injection into mice, far exceeding the previous record of 5.4 h. The ultra-long blood circulation time suggests greatly delayed clearance of nanomaterials by the reticuloendothelial system (RES) of mice, a highly desired property for in vivo applications of nanomaterials, including imaging and drug delivery.
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