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Surface-initiated ring-opening metathesis polymerization (SI-ROMP) to attach a tethered organic corona onto CdSe/ZnS core/shell quantum dots

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Abstract

Core–shell CdSe/ZnS quantum dots (QDs) are useful as tunable photostable fluorophores for multiple applications in industry, biology, and medicine. However, to achieve the optimum optical properties, the surface of the QDs must be passivated to remove charged sites that might bind extraneous substances and allow aggregation. Here we describe a method of growing an organic polymer corona onto the QD surface using the bottom-up approach of surface-initiated ring-opening metathesis polymerization (SI-ROMP) with Grubbs catalyst. CdSe/ZnS QDs were first coated with mercaptopropionic acid by displacing the original tri-octylphosphine oxide layer, and then reacted with 7-octenyl dimethyl chlorosilane. The resulting octenyl double bonds allowed the attachment of ruthenium alkylidene groups as a catalyst. A subsequent metathesis reaction with strained bicyclic monomers (norbornene-dicarbonyl chloride (NDC), and a mixture of NDC and norbornenylethylisobutyl-polyhedral oligomeric silsesquioxane (norbornoPOSS)) allowed the construction of tethered organic homo-polymer or co-polymer layers onto the QD. Compounds were characterized by FT-IR, 1H-NMR, X-ray photoelectron spectroscopy, differential scanning calorimetry, and transmission electron microscopy. Atomic force microscopy showed that the coated QDs were separate and non-aggregated with a range of diameter of 48–53 nm.

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Acknowledgments

MRH was supported by the US NIH grant R01AI050875.

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Authors and Affiliations

  1. Wellman Center for Photomedicine, Massachusetts General Hospital, Boston, MA, 02114, USA

    Fatma Vatansever & Michael R. Hamblin

  2. Department of Dermatology, Harvard Medical School, Boston, MA, 02115, USA

    Fatma Vatansever & Michael R. Hamblin

  3. Harvard-MIT Division of Health Sciences and Technology, Boston, MA, 02139, USA

    Michael R. Hamblin

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  1. Fatma Vatansever
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Correspondence to Fatma Vatansever or Michael R. Hamblin.

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Vatansever, F., Hamblin, M.R. Surface-initiated ring-opening metathesis polymerization (SI-ROMP) to attach a tethered organic corona onto CdSe/ZnS core/shell quantum dots. J Nanopart Res 18, 302 (2016). https://doi.org/10.1007/s11051-016-3328-y

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