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Water-soluble PEGylated silicon nanoparticles and their assembly into swellable nanoparticle aggregates

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Abstract

Water-soluble silicon nanoparticles were synthesized by grafting PEG polymers onto functionalized silicon nanoparticles with distal alkyne or azide moieties. The surface-functionalized silicon nanoparticles were produced in one step from the reactive high-energy ball milling (RHEBM) of silicon wafers with a mixture of either 5-chloro-1-pentyne in 1-pentyne or 1,7 octadiyne in 1-hexyne to afford air and water-stable chloroalkyl or alkynyl-terminated nanoparticles, respectively. Nanoparticles with the ω-chloroalkyl substituents were easily converted to ω-azidoalkyl groups through the reaction of the Si nanoparticles with sodium azide in DMF. The azido-terminated nanoparticles were then grafted with mono-alkynyl-PEG polymers using a copper-catalyzed alkyne-azide cycloaddition (CuAAC) reaction to afford core–shell silicon nanoparticles with a covalently attached PEG shell. Covalently linked Si nanoparticle clusters were synthesized via the CuAAC “click” reaction of functional Si NPs with α,ω-functional PEG polymers of various lengths. Dynamic light scattering studies show that the flexible globular nanoparticle aggregates undergo a solvent-dependent change in volume (ethanol > dichloromethane > toluene) similar in behavior to hydrogel nanocomposites.

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Acknowledgments

MJF and BSM are grateful for the support from the National Science Foundation (NSF grant CMMI-0726943).YL, BZ, and SMG acknowledge the financial support of Department of Defense (W81XWH-10-1-0377) and the National Science Foundation under the NSF EPSCoR Cooperative Agreement No. EPS-1003897.

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Authors and Affiliations

  1. Department of Chemistry, Tulane University, New Orleans, LA, 70118, USA

    Zejing Xu, Yejia Li, Boyu Zhang, Tapas Purkait, Scott M. Grayson & Mark J. Fink

  2. Department of Physics and Engineering Physics, Tulane University, New Orleans, LA, 70118, USA

    Alina Alb

  3. Department of Chemical and Biomolecular Engineering, Tulane University, New Orleans, LA, 70118, USA

    Brian S. Mitchell

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  1. Zejing Xu
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  2. Yejia Li
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Correspondence to Mark J. Fink.

Electronic supplementary material

The 1H NMR of all new compounds, as well as the FTIR and EDX spectra of silicon nanoparticle derivatives,are available in the online version of this article. Below is the link to the electronic supplementary material.

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Xu, Z., Li, Y., Zhang, B. et al. Water-soluble PEGylated silicon nanoparticles and their assembly into swellable nanoparticle aggregates. J Nanopart Res 17, 56 (2015). https://doi.org/10.1007/s11051-015-2869-9

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