Journal
ACS NANO
Volume 11, Issue 4, Pages 3463-3475Publisher
AMER CHEMICAL SOC
DOI: 10.1021/acsnano.6b07697
Keywords
gold nanorods; cetyltrimethylammonium bromide; glutathione oligomer; chirality; plasmonic
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Funding
- National Natural Science Foundation of China [21534004, 21474040, 21674042]
- China's Thousand Talent Plan
- International Postdoctoral Exchange Fellowship Program - Office of China Postdoctoral Council [20130036]
- China Postdoctoral Science Foundation [2013M540249, 2014-T70281]
- National Science Foundation of China [21403085]
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Gold nanorods are excellent anisotropic building blocks for plasmonic chiral nanostructures. The near-infrared plasmonic band of nanorods makes them highly desirable for biomedical applications such as chiral bioimaging and sensing, in which a strong circular dichroism (CD) signal is required. Chiral assemblies of gold nanorods induced by self-associating peptides are especially attractive for this purpose as they exhibit plasmonic-enhanced chiroptical activity. Here, we showed that the presence of cetyltrimethylammonium bromide (CTAB) micelles in a gold nanorod solution promoted the self-association of L-/D-glutathione (GSH) and significantly enhanced the chirality of the resulting plasmonic nano chains. Chiroptical signals for the ensemble in the presence of CTAB micelles were 20 times greater than those obtained below the critical micelle concentration of CTAB. The strong optical activity was attributed to the formation of helical GSH oligomers in the hydrophobic core of the CTAB micelles. The helical GSH oligoniers led the nanorods to assemble in a chiral, end-to-end crossed fashion. The CD signal intensities were also proportional to the fraction of nanorods in the nanochains. In addition, finite-difference time-domain simulations agreed well with the experimental extinction and CD spectra. Our work demonstrated a substantial effect from the CTAB micelles on gold nanoparticle assemblies induced by biomolecules and showed the importance of size matching between the inorganic nanobuilding blocks and the chiral molecular templates (i.e., the GSH oligomers in the present case) in order to attain strong chiroptical activities.
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