Nontemplated Approach to Tuning the Spectral Propertiesof Cyanine-Based Fluorescent NanoGUMBOS

Journal Article · Fri Jan 01 00:00:00 EST 2010 · Langmuir

DOI:https://doi.org/10.1021/la101463r· OSTI ID:1078209

Das, Susmita ^[1]; Bwambok, David ^[1]; El-Zahab, Bilal ^[1]; Monk, Joshua ^[1]; De Rooy, Sergio ^[1]; Challa, Santhosh ^[1]; Li, Min ^[1]; Hung, Francisco ^[1]; Baker, Gary A ^[2]; Warner, Isiah M ^[2]

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1. Louisiana State University
2. ORNL

Template-free controlled aggregation and spectral properties in fluorescent organic nanoparticles (FONs) is highly desirable for various applications.Herein, we report a nontemplated method for controlling the aggregation in near-infrared (NIR) cyanine-based nanoparticles derived from a group of uniformmaterials based on organic salts (GUMBOS). Cationic heptamethine cyanine dye 1,10,3,3,30,30-hexamethylindotricarbocyanine (HMT) was coupled with five different anions, viz., [NTf2 -], [BETI-], [TFPB-], [AOT-], and [TFP4B-], by an ion-exchange method to obtain the respective GUMBOS. The nanoGUMBOS obtained via a reprecipitation method were primarily amorphous and spherical (30-100 nm) as suggested by selected area electron diffraction (SAED) and transmission electron microscopy (TEM). The formation of tunable self-assemblies within the nanoGUMBOS was characterized using absorption and fluorescence spectroscopy in conjunction with molecular dynamics simulations. Counterion-controlled spectral properties observed in the nanoGUMBOS were attributed to variations in J/H ratios with different anions. Association with the [AOT-] anion afforded predominant J aggregation enabling the highest fluorescence intensity, whereas [TFP4B-] disabled the fluorescence due to predominantHaggregation in the nanoparticles. Analyses of the stacking angle of the cations based on molecular dynamic simulation results in [HMT][NTf2], [HMT][BETI], and [HMT][AOT] dispersed in water and a visual analysis of the representative simulation snapshots also imply that the type of aggregation was controlled through the counterion associated with the dye cation.

• Research Organization: Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States)
• Sponsoring Organization: USDOE Office of Science (SC)
• DOE Contract Number: AC05-00OR22725
• OSTI ID: 1078209
• Journal Information: Langmuir, Vol. 26, Issue 15; ISSN 0743-7463
• Country of Publication: United States
• Language: English