Preparation, Characterization, and Surface Modification of Trifluoroethyl Ester-Terminated Silicon Nanoparticles

W. Biesta, B. van Lagen, V.S. Gevaerts, A.T.M. Marcelis, J.M.J. Paulusse, M.W.F. Nielen, H. Zuilhof

Research output: Contribution to journalArticleAcademicpeer-review

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Abstract

Platinum-catalyzed hydrosilylation of hydrogen-terminated silicon nanoparticles (Si NPs) with 2,2,2-trifluoroethyl 4-pentenoate gave well-defined nanoparticles (NPs) with surface groups that are reactive toward amines. The particles showed a diameter of 1.4 ± 0.2 nm as revealed by transmission electron microscopy (TEM) measurements. Characterization with 1H, 13C and heteronuclear NMR techniques revealed that the trifluoroethyl pentenoate group is attached to the Si NP surface via the terminal carbon atom. The trifluoroethyl ester is reactive toward primary amines, allowing for additional surface functionalization. Modification of the Si NPs was performed with benzylamine, 1,2-diaminoethane, and propargylamine. The modification gave a complete substitution of the trifluoroethyl group to amide groups. The modified Si NPs were characterized in detail by a series of one-dimensional (1-D) and two-dimensional (2-D) NMR techniques and by FT-IR. The propargylamide-terminated Si NPs were further functionalized with an azide-terminated fluorescent dye (Azide-Fluor 585 sulphorhodamine) using a copper-catalyzed azide-alkyne cycloaddition reaction (CuAAC). Gel permeation chromatography and time-resolved fluorescence anisotropy spectroscopy of the dye reveal a significant increase in the hydrodynamic radius upon clicking of the dye. Additionally, NMR spectroscopy reveals the presence of a 1,2,3-triazole ring in the product, which confirms that the increase in the hydrodynamic radius is caused by the attachment of the dye to the Si NP surface via the CuAAC reaction.
Original languageEnglish
Pages (from-to)4311-4318
JournalChemistry of materials
Volume24
Issue number22
DOIs
Publication statusPublished - 2012

Fingerprint

Silicon
Surface treatment
Esters
Nanoparticles
Azides
Dyes
ethylenediamine
Coloring Agents
Amines
Hydrodynamics
Nuclear magnetic resonance
Hydrosilylation
Triazoles
Alkynes
Cycloaddition
Gel permeation chromatography
Platinum
Fluorescent Dyes
Amides
Nuclear magnetic resonance spectroscopy

Keywords

  • quantum dots
  • click chemistry
  • microemulsion synthesis
  • electronic-properties
  • biological detection
  • organic-molecules
  • in-vivo
  • nanocrystals
  • functionalization
  • monolayers

Cite this

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title = "Preparation, Characterization, and Surface Modification of Trifluoroethyl Ester-Terminated Silicon Nanoparticles",
abstract = "Platinum-catalyzed hydrosilylation of hydrogen-terminated silicon nanoparticles (Si NPs) with 2,2,2-trifluoroethyl 4-pentenoate gave well-defined nanoparticles (NPs) with surface groups that are reactive toward amines. The particles showed a diameter of 1.4 ± 0.2 nm as revealed by transmission electron microscopy (TEM) measurements. Characterization with 1H, 13C and heteronuclear NMR techniques revealed that the trifluoroethyl pentenoate group is attached to the Si NP surface via the terminal carbon atom. The trifluoroethyl ester is reactive toward primary amines, allowing for additional surface functionalization. Modification of the Si NPs was performed with benzylamine, 1,2-diaminoethane, and propargylamine. The modification gave a complete substitution of the trifluoroethyl group to amide groups. The modified Si NPs were characterized in detail by a series of one-dimensional (1-D) and two-dimensional (2-D) NMR techniques and by FT-IR. The propargylamide-terminated Si NPs were further functionalized with an azide-terminated fluorescent dye (Azide-Fluor 585 sulphorhodamine) using a copper-catalyzed azide-alkyne cycloaddition reaction (CuAAC). Gel permeation chromatography and time-resolved fluorescence anisotropy spectroscopy of the dye reveal a significant increase in the hydrodynamic radius upon clicking of the dye. Additionally, NMR spectroscopy reveals the presence of a 1,2,3-triazole ring in the product, which confirms that the increase in the hydrodynamic radius is caused by the attachment of the dye to the Si NP surface via the CuAAC reaction.",
keywords = "quantum dots, click chemistry, microemulsion synthesis, electronic-properties, biological detection, organic-molecules, in-vivo, nanocrystals, functionalization, monolayers",
author = "W. Biesta and {van Lagen}, B. and V.S. Gevaerts and A.T.M. Marcelis and J.M.J. Paulusse and M.W.F. Nielen and H. Zuilhof",
year = "2012",
doi = "10.1021/cm302060f",
language = "English",
volume = "24",
pages = "4311--4318",
journal = "Chemistry of materials",
issn = "0897-4756",
publisher = "American Chemical Society",
number = "22",

}

Preparation, Characterization, and Surface Modification of Trifluoroethyl Ester-Terminated Silicon Nanoparticles. / Biesta, W.; van Lagen, B.; Gevaerts, V.S.; Marcelis, A.T.M.; Paulusse, J.M.J.; Nielen, M.W.F.; Zuilhof, H.

In: Chemistry of materials, Vol. 24, No. 22, 2012, p. 4311-4318.

Research output: Contribution to journalArticleAcademicpeer-review

TY - JOUR

T1 - Preparation, Characterization, and Surface Modification of Trifluoroethyl Ester-Terminated Silicon Nanoparticles

AU - Biesta, W.

AU - van Lagen, B.

AU - Gevaerts, V.S.

AU - Marcelis, A.T.M.

AU - Paulusse, J.M.J.

AU - Nielen, M.W.F.

AU - Zuilhof, H.

PY - 2012

Y1 - 2012

N2 - Platinum-catalyzed hydrosilylation of hydrogen-terminated silicon nanoparticles (Si NPs) with 2,2,2-trifluoroethyl 4-pentenoate gave well-defined nanoparticles (NPs) with surface groups that are reactive toward amines. The particles showed a diameter of 1.4 ± 0.2 nm as revealed by transmission electron microscopy (TEM) measurements. Characterization with 1H, 13C and heteronuclear NMR techniques revealed that the trifluoroethyl pentenoate group is attached to the Si NP surface via the terminal carbon atom. The trifluoroethyl ester is reactive toward primary amines, allowing for additional surface functionalization. Modification of the Si NPs was performed with benzylamine, 1,2-diaminoethane, and propargylamine. The modification gave a complete substitution of the trifluoroethyl group to amide groups. The modified Si NPs were characterized in detail by a series of one-dimensional (1-D) and two-dimensional (2-D) NMR techniques and by FT-IR. The propargylamide-terminated Si NPs were further functionalized with an azide-terminated fluorescent dye (Azide-Fluor 585 sulphorhodamine) using a copper-catalyzed azide-alkyne cycloaddition reaction (CuAAC). Gel permeation chromatography and time-resolved fluorescence anisotropy spectroscopy of the dye reveal a significant increase in the hydrodynamic radius upon clicking of the dye. Additionally, NMR spectroscopy reveals the presence of a 1,2,3-triazole ring in the product, which confirms that the increase in the hydrodynamic radius is caused by the attachment of the dye to the Si NP surface via the CuAAC reaction.

AB - Platinum-catalyzed hydrosilylation of hydrogen-terminated silicon nanoparticles (Si NPs) with 2,2,2-trifluoroethyl 4-pentenoate gave well-defined nanoparticles (NPs) with surface groups that are reactive toward amines. The particles showed a diameter of 1.4 ± 0.2 nm as revealed by transmission electron microscopy (TEM) measurements. Characterization with 1H, 13C and heteronuclear NMR techniques revealed that the trifluoroethyl pentenoate group is attached to the Si NP surface via the terminal carbon atom. The trifluoroethyl ester is reactive toward primary amines, allowing for additional surface functionalization. Modification of the Si NPs was performed with benzylamine, 1,2-diaminoethane, and propargylamine. The modification gave a complete substitution of the trifluoroethyl group to amide groups. The modified Si NPs were characterized in detail by a series of one-dimensional (1-D) and two-dimensional (2-D) NMR techniques and by FT-IR. The propargylamide-terminated Si NPs were further functionalized with an azide-terminated fluorescent dye (Azide-Fluor 585 sulphorhodamine) using a copper-catalyzed azide-alkyne cycloaddition reaction (CuAAC). Gel permeation chromatography and time-resolved fluorescence anisotropy spectroscopy of the dye reveal a significant increase in the hydrodynamic radius upon clicking of the dye. Additionally, NMR spectroscopy reveals the presence of a 1,2,3-triazole ring in the product, which confirms that the increase in the hydrodynamic radius is caused by the attachment of the dye to the Si NP surface via the CuAAC reaction.

KW - quantum dots

KW - click chemistry

KW - microemulsion synthesis

KW - electronic-properties

KW - biological detection

KW - organic-molecules

KW - in-vivo

KW - nanocrystals

KW - functionalization

KW - monolayers

U2 - 10.1021/cm302060f

DO - 10.1021/cm302060f

M3 - Article

VL - 24

SP - 4311

EP - 4318

JO - Chemistry of materials

JF - Chemistry of materials

SN - 0897-4756

IS - 22

ER -