Versatile "click chemistry" approach to functionalizing silicon quantum dots: applications toward fluorescent cellular imaging.

In this study, we describe a solution procedure for the preparation and surface modification of photostable colloidal silicon quantum dots (SiQDs) for imaging of cancer cells. Photoluminescent SiQDs were synthesized by reduction of halogenated silane precursors using a microemulsion process. It was shown that 1,8-nonadiyne molecules could be grafted onto the surface of hydrogen-terminated SiQDs via ultraviolet (UV)-promoted hydrosilylation, demonstrated by Fourier transform infrared spectroscopy (FTIR) measurements. In addition, various azide molecules were coupled onto nonadiyne-functionalized particles, rendering particles dispersible in selected polar and nonpolar solvents. The photoluminescence of functionalized SiQDs was stable against photobleaching and did not vary appreciably within biologically applicable pH and temperature ranges. To demonstrate compatibility with biological systems, water-soluble SiQDs were used for fluorescent imaging of HeLa cells. In addition, the SiQDs were shown to be non-cytotoxic at concentrations up to 240 μg/mL. The results presented herein provide good evidence for the versatility of functionalized SiQDs for fluorescent bioimaging application.

[1]  L. Ruizendaal,et al.  Biofunctional silicon nanoparticles by means of thiol-ene click chemistry. , 2011, Chemistry, an Asian journal.

[2]  M. Swihart,et al.  Surface functionalization of silicon nanoparticles produced by laser-driven pyrolysis of silane followed by HF-HNO3 etching. , 2004, Langmuir : the ACS journal of surfaces and colloids.

[3]  S. Bhatia,et al.  Probing the Cytotoxicity Of Semiconductor Quantum Dots. , 2004, Nano letters.

[4]  Yadong Yin,et al.  Colloidal nanocrystal synthesis and the organic–inorganic interface , 2005, Nature.

[5]  Ken-Tye Yong,et al.  Biocompatible luminescent silicon quantum dots for imaging of cancer cells. , 2008, ACS nano.

[6]  Susan M. Kauzlarich,et al.  Synthesis of Alkyl-Terminated Silicon Nanoclusters by a Solution Route , 1999 .

[7]  D. Bouwmeester,et al.  Self-tuned quantum dot gain in photonic crystal lasers. , 2005, Physical review letters.

[8]  Uwe R. Kortshagen,et al.  Silicon nanocrystals with ensemble quantum yields exceeding 60 , 2006 .

[9]  Hong Ding,et al.  Bioconjugation of luminescent silicon quantum dots for selective uptake by cancer cells. , 2011, Bioconjugate chemistry.

[10]  C. Hessel,et al.  Hydrogen Silsesquioxane: A Molecular Precursor for Nanocrystalline Si−SiO2 Composites and Freestanding Hydride-Surface-Terminated Silicon Nanoparticles , 2006 .

[11]  S. Gambhir,et al.  Quantum Dots for Live Cells, in Vivo Imaging, and Diagnostics , 2005, Science.

[12]  S. Kauzlarich,et al.  A low-temperature solution phase route for the synthesis of silicon nanoclusters , 1996 .

[13]  Richard K. Baldwin,et al.  Solution reduction synthesis of surface stabilized silicon nanoparticles. , 2002, Chemical communications.

[14]  Uwe R. Kortshagen,et al.  Plasma‐Assisted Synthesis of Silicon Nanocrystal Inks , 2007 .

[15]  C. Hessel,et al.  An investigation of the formation and growth of oxide-embedded silicon nanocrystals in hydrogen silsesquioxane-derived nanocomposites , 2007 .

[16]  Susan M. Kauzlarich,et al.  Chemical insight into the origin of red and blue photoluminescence arising from freestanding silicon nanocrystals. , 2013, ACS nano.

[17]  Mark T Swihart,et al.  Efficient surface grafting of luminescent silicon quantum dots by photoinitiated hydrosilylation. , 2005, Langmuir : the ACS journal of surfaces and colloids.

[18]  Weidong Yang,et al.  Shape control of CdSe nanocrystals , 2000, Nature.

[19]  Ruiqin Q. Zhang,et al.  Photo and pH stable, highly-luminescent silicon nanospheres and their bioconjugates for immunofluorescent cell imaging. , 2009, Journal of the American Chemical Society.

[20]  M. Kovalenko,et al.  Prospects of colloidal nanocrystals for electronic and optoelectronic applications. , 2010, Chemical reviews.

[21]  Gang-yu Liu,et al.  Room temperature solution synthesis of alkyl-capped tetrahedral shaped silicon nanocrystals. , 2002, Journal of the American Chemical Society.

[22]  Hong Ding,et al.  In vivo targeted cancer imaging, sentinel lymph node mapping and multi-channel imaging with biocompatible silicon nanocrystals. , 2011, ACS nano.

[23]  A. Nozik Quantum dot solar cells , 2002 .

[24]  C. Fan,et al.  Ultrastable, highly fluorescent, and water-dispersed silicon-based nanospheres as cellular probes. , 2009, Angewandte Chemie.

[25]  M. Nielen,et al.  Preparation, Characterization, and Surface Modification of Trifluoroethyl Ester-Terminated Silicon Nanoparticles , 2012 .

[26]  U. Kortshagen,et al.  High-yield plasma synthesis of luminescent silicon nanocrystals. , 2005, Nano letters.

[27]  Akiyoshi Hoshino,et al.  Water-soluble photoluminescent silicon quantum dots. , 2005, Angewandte Chemie.

[28]  Alexander M. Spokoyny,et al.  A “click-based” porous organic polymer from tetrahedral building blocks , 2011 .

[29]  Alexander Eychmüller,et al.  Chemistry and photophysics of thiol-stabilized II-VI semiconductor nanocrystals , 2000 .

[30]  R. Tilley,et al.  Chemical reactions on surface molecules attached to silicon quantum dots. , 2010, Journal of the American Chemical Society.

[31]  D. Balding,et al.  HLA Sequence Polymorphism and the Origin of Humans , 2006 .

[32]  J. Kelly,et al.  An investigation into near-UV hydrosilylation of freestanding silicon nanocrystals. , 2010, ACS nano.

[33]  M. Fleischauer,et al.  Size-dependent reactivity in hydrosilylation of silicon nanocrystals. , 2011, Journal of the American Chemical Society.

[34]  Ning-Bew Wong,et al.  Silicon quantum dots: a general photocatalyst for reduction, decomposition, and selective oxidation reactions. , 2007, Journal of the American Chemical Society.

[35]  P. Lai,et al.  Sized controlled synthesis, purification, and cell studies with silicon quantum dots. , 2011, Nanoscale.

[36]  Louis E. Brus,et al.  Luminescence Photophysics in Semiconductor Nanocrystals , 1999 .

[37]  Yao He,et al.  One-pot microwave synthesis of water-dispersible, ultraphoto- and pH-stable, and highly fluorescent silicon quantum dots. , 2011, Journal of the American Chemical Society.

[38]  A. Alivisatos Perspectives on the Physical Chemistry of Semiconductor Nanocrystals , 1996 .

[39]  Kenji Yamamoto,et al.  The Microemulsion Synthesis of Hydrophobic and Hydrophilic Silicon Nanocrystals , 2006 .

[40]  Matthew P. Augustine,et al.  NMR Study of the Synthesis of Alkyl-Terminated Silicon Nanoparticles from the Reaction of SiCl4 with the Zintl Salt, NaSi , 2001 .

[41]  J Justin Gooding,et al.  Colloidal silicon quantum dots: from preparation to the modification of self-assembled monolayers (SAMs) for bio-applications. , 2014, Chemical Society reviews.

[42]  F. Marshall,et al.  In vivo molecular and cellular imaging with quantum dots. , 2005, Current opinion in biotechnology.

[43]  R. Nitschke,et al.  Quantum dots versus organic dyes as fluorescent labels , 2008, Nature Methods.

[44]  Isao Matsui,et al.  Micro-emulsion synthesis of monodisperse surface stabilized silicon nanocrystals. , 2005, Chemical communications.

[45]  J. Gooding,et al.  One-pot synthesis of colloidal silicon quantum dots and surface functionalization via thiol-ene click chemistry. , 2012, Chemical communications.

[46]  X. Ji,et al.  Large-scale aqueous synthesis of fluorescent and biocompatible silicon nanoparticles and their use as highly photostable biological probes. , 2013, Journal of the American Chemical Society.

[47]  G. Ozin,et al.  Small Silicon, Big Opportunities: The Development and Future of Colloidally‐Stable Monodisperse Silicon Nanocrystals , 2012, Advanced materials.

[48]  Zhenhui Kang,et al.  A polyoxometalate-assisted electrochemical method for silicon nanostructures preparation: from quantum dots to nanowires. , 2007, Journal of the American Chemical Society.