Title: Direct Functionalization of an Acid-Terminated Nanodiamond with Azide: Enabling Access to 4-Substituted-1,2,3-Triazole-Functionalized Particles

Abstract

Azides on the periphery of nanodiamond materials (ND) are of great utility because they have been shown to undergo Cu-catalyzed and Cu-free cycloaddition reactions with structurally diverse alkynes, affording particles tailored for applications in biology and materials science. However, current methods employed to access ND featuring azide groups typically require either harsh pretreatment procedures or multiple synthesis steps and use surface linking groups that may be susceptible to undesirable cleavage. Here in this paper we demonstrate an alternative single-step approach to producing linker-free, azide-functionalized ND. Our method was applied to low-cost, detonation-derived ND powders where surface carbonyl groups undergo silver-mediated decarboxylation and radical substitution with azide. ND with directly grafted azide groups were then treated with a variety of aliphatic, aromatic, and fluorescent alkynes to afford 1-(ND)-4-substituted-1,2,3-triazole materials under standard copper-catalyzed cycloaddition conditions. Surface modification steps were verified by characteristic infrared absorptions and elemental analyses. High loadings of triazole surface groups (up to 0.85 mmol g^–1) were obtained as determined from thermogravimetric analysis. The azidation procedure disclosed is envisioned to become a valuable initial transformation in numerous future applications of ND.

Authors:

Kennedy, Zachary C. ^[1]; Barrett, Christopher A. ^[1]; Warner, Marvin G.  ^[1]

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+ Show Author Affiliations

1. Pacific Northwest National Lab. (PNNL), Richland, WA (United States)

Publication Date:

Wed Mar 01 00:00:00 EST 2017

Research Org.:

Pacific Northwest National Laboratory (PNNL), Richland, WA (United States)

Sponsoring Org.:

USDOE

OSTI Identifier:

1347713

Report Number(s):

PNNL-SA-122913
Journal ID: ISSN 0743-7463; TRN: US1700665

Grant/Contract Number:  

AC06-76RL01830

Resource Type:

Accepted Manuscript

Journal Name:

Langmuir

Additional Journal Information:

Journal Volume: 33; Journal Issue: 11; Journal ID: ISSN 0743-7463

Publisher:

American Chemical Society

Country of Publication:

United States

Language:

English

Subject:

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY