A New Family of Pyridine-Appended Multidentate Polymers As Hydrophilic Surface Ligands for Preparing Stable Biocompatible Quantum Dots

被引:89
|
作者
Susumu, Kimihiro [1 ,3 ]
Oh, Eunkeu [1 ,3 ]
Delehanty, James B. [2 ]
Pinaud, Fabien [4 ,5 ]
Gemmill, Kelly Boeneman [2 ]
Walper, Scott [2 ]
Breger, Joyce [2 ,6 ]
Schroeder, Maria J. [7 ]
Stewart, Michael H. [1 ]
Jain, Vaibhav [1 ]
Whitaker, Craig M. [7 ]
Huston, Alan L. [1 ]
Medintz, Igor L. [2 ]
机构
[1] US Naval Res Lab, Opt Sci Div, Washington, DC 20375 USA
[2] US Naval Res Lab, Ctr Bio Mol Sci & Engn, Washington, DC 20375 USA
[3] Sotera Def Solut, Columbia, MD 21046 USA
[4] Univ So Calif, Dept Chem, Dept Biol Sci, Los Angeles, CA 90089 USA
[5] Univ So Calif, Dept Phys & Astron, Dana & David Dornsife Coll Letters Arts & Sci, Los Angeles, CA 90089 USA
[6] Amer Soc Engn Educ, Washington, DC 20036 USA
[7] US Naval Acad, Dept Chem, Annapolis, MD 21402 USA
关键词
RESONANCE ENERGY-TRANSFER; PHASE-TRANSFER; ZWITTERIONIC LIGANDS; HIGHLY LUMINESCENT; PHOTOCHEMICAL INSTABILITY; INORGANIC NANOPARTICLES; POLYETHYLENE-GLYCOL; NANOCRYSTALS; SEMICONDUCTOR; WATER;
D O I
10.1021/cm502386f
中图分类号
O64 [物理化学(理论化学)、化学物理学];
学科分类号
070304 ; 081704 ;
摘要
The growing utility of semiconductor quantum dots (QDs) in biochemical and cellular research necessitates, in turn, continuous development of surface functionalizing ligands to optimize their performance for ever more challenging and diverse biological applications. Here, we describe a new class of multifunctional polymeric ligands as a stable, compact and high affinity alternative to multidentate thiolated molecules. The polymeric ligands are designed with a poly(acrylic acid) backbone where pyridines are used as anchoring groups that are not sensitive to degradation by air and light, along with short poly(ethylene glycol) (PEG) pendant groups which are coincorporated for aqueous solubility, biocompatibility and colloidal stability. The percentages of each of the latter functional groups are controlled during initial synthesis along with incorporation of carboxyl groups which serve as chemical handles for subsequent covalent modification of the QD surface. A detailed physicochemical characterization indicates that the multiple pyridine groups are efficiently bound on the QD surface since they provide for relatively small overall hydrodynamic sizes along with good colloidal stability and strong fluorescence over a wide pH range, under high salt concentration and in extremely dilute conditions at room temperature under room light over extended timeframes. Covalent conjugation of dyes and metal-affinity coordination with functional enzymes to the QD surfaces were also demonstrated. Biocompatibility and long-term stability of the pyridine polymer coated QDs were then confirmed in a battery of relevant assays including cellular delivery by both microinjection and peptide facilitated uptake along with intracellular single QD tracking studies and cytotoxicity testing. Cumulatively, these results suggest this QD functionalization strategy is a viable alternative that provides some desirable properties of both compact, discrete ligands and large amphiphilic polymers.
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页码:5327 / 5344
页数:18
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