Analytical Sciences

Plasmonic Fluorescent Nanocomposites of Cyanines Self-assembled upon Gold Nanoparticle Scaffolds

Komandoor E. ACHYUTHAN,*1 Ann M. ACHYUTHAN,*2 Susan M. BROZIK,*1 Shawn M. DIRK,*3 Tracy R. LUJAN,*2 Janet M. ROMERO,*2 and Jason C. HARPER*4

*1 Biosensors and Nanomaterials Department, Sandia National Laboratories, Albuquerque, NM 87185, USA
*2 Biology Department, Northern New Mexico College, Espanola, NM 87532, USA
*3 Organic Materials Department, Sandia National Laboratories, Albuquerque, NM 87185, USA
*4 Bioenergy and Defense Technology Department, Sandia National Laboratories, Albuquerque, NM 87185, USA

Plasmonic fluorescent nanocomposites are difficult to prepare due to strong quenching effects on fluorophores in the vicinity of noble metal nanoparticles such as gold (AuNPs). We successfully prepared plasmonic fluorescent nanocomposites of two cyanines (1 and 2) aggregating upon 2 – 40 nm AuNPs or streptavidin-conjugated 10 nm AuNPs. We used high throughput screening (HTS) for the first time to characterize the spectral properties, aggregation kinetics, aggregation density and photostability of the nanocomposites. Fluorescence from nanocomposites declined inversely with AuNPs size: 40 nm ≥ 20 nm > 10 nm > 5 nm > 2 nm. Sensitivity (limit of detection, LOD, 10⁵ – 10¹¹ AuNPs/mL), brightness of the nanocomposites and surface coverage of AuNPs by cyanine aggregates were all influenced by five factors: 1) AuNPs size; 2) cyanine type (1 or 2); 3) aggregate density; 4) distance between aggregates and AuNPs surface; and 5) streptavidin protein conjugation to AuNPs. We propose a model for plasmonic fluorescent nanocomposites based on these observations. Our plasmonic fluorescent nanocomposites have applications in chemical and biological assays.

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