Azide-derivatized gold nanorods: functional materials for "click" chemistry.
We describe herein the synthesis of functional gold nanorods suitable for carrying out "click" chemistry reactions. Gold nanorods modified with a copolymer containing sulfonate and maleic acid groups have been conjugated to a bifunctional azide molecule (amine-PEG-azide). The maleic acid molecules in the copolymer participate in carbodiimide-mediated amide bond formation with amine groups of the azide linker, whereas the sulfonate groups prevent nanorod aggregation in water. Spectroscopic and zeta-potential measurements have been used to confirm the successful surface modification of the gold nanorods. These azide-functionalized nanorods can carry out chemical reactions based on click chemistry. As a case study, we have demonstrated the "clicking" of azide-nanorods to an acetylene-functionalized enzyme, trypsin, by a copper-catalyzed 1,3-dipolar cycloaddition reaction. The enzyme is not only stable after bioconjugation but is also biologically active, as demonstrated by its digestion of the protein casein. For comparison, the biological activity of trypsin conjugated to gold nanorods by two other commonly used methods (carbodiimide-mediated covalent attachment via amide bond formation and simple electrostatic adsorption) has been studied. The enzyme conjugated by click chemistry demonstrates improved biological activity compared with other forms of bioconjugation. This general and simple approach is easy, specific with higher yields, environmentally benign, and applicable to a wide range of analytes and biomolecules.
Department of Chemistry and Biochemistry and The W. M. Keck Open Laboratory for Bionanoparticle Technology, Discovery and Development, University of South Carolina, Columbia, SC 29208, USA. gole@mail.chem.sc.edu
Anand
A
Gole
Catherine J
CJ
Murphy
D000042:Absorption; D000327:Adsorption; D000577:Amides / Q000737:chemistry; D000588:Amines / Q000737:chemistry; D001386:Azides / Q000737:chemistry*; D001672:Biocompatible Materials / Q000138:chemical synthesis*; D002384:Catalysis; D003300:Copper / Q000737:chemistry; D004563:Electrochemistry; D006046:Gold / Q000737:chemistry*; D007094:Imides / Q000737:chemistry; D008298:Maleates / Q000737:chemistry; D043942:Nanotubes / Q000737:chemistry*; D011092:Polyethylene Glycols / Q000737:chemistry; D013057:Spectrum Analysis; D055672:Static Electricity; D013451:Sulfonic Acids / Q000737:chemistry; D013499:Surface Properties; D014357:Trypsin / Q000737:chemistry / Q000378:metabolism
D000577:Amides; D000588:Amines; D001386:Azides; D001672:Biocompatible Materials; D007094:Imides; D008298:Maleates; D013451:Sulfonic Acids; D011092:Polyethylene Glycols; D006046:Gold; D003300:Copper; C030272:maleic acid; D014357:Trypsin