Growth of In Situ Functionalized Luminescent Silver Nanoclusters by Direct Reduction and Size Focusing

We have used one phase growth reaction to prepare a series of silver nanoparticles (NPs) and luminescent nanoclusters (NCs) using sodium borohydride (NaBH4) reduction of silver nitrate in the presence of molecular scale ligands made of polyethylene glycol (PEG) appended with lipoic acid (LA) groups...

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Bibliographic Details
Published in:ACS nano 2012-10, Vol.6 (10), p.8950-8961
Main Authors: Muhammed, Madathumpady Abubaker Habeeb, Aldeek, Fadi, Palui, Goutam, Trapiella-Alfonso, Laura, Mattoussi, Hedi
Format: Article
Language:English
Subjects:
Chemical Sciences
Crystallization - methods
Focusing
Functional groups
Ligands
Luminescent Measurements - methods
Macromolecular Substances - chemistry
Material chemistry
Materials Testing
Metal Nanoparticles - chemistry
Metal Nanoparticles - ultrastructure
Molecular Conformation
Nanostructure
Particle Size
Polyethylene glycol
Reduction
Silver
Silver - chemistry
Sodium
Solvents
Surface Properties
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Summary:We have used one phase growth reaction to prepare a series of silver nanoparticles (NPs) and luminescent nanoclusters (NCs) using sodium borohydride (NaBH4) reduction of silver nitrate in the presence of molecular scale ligands made of polyethylene glycol (PEG) appended with lipoic acid (LA) groups at one end and reactive (−COOH/–NH2) or inert (−OCH3) functional groups at the other end. The PEG segment in the ligand promotes solubility in a variety of solvents including water, while LAs provide multidentate coordinating groups that promote Ag–ligand complex formation and strong anchoring onto the NP/NC surface. The particle size and properties were primarily controlled by varying the Ag-to-ligand (Ag:L) molar ratios and the molar amount of NaBH4 used. We found that while higher Ag:L ratios produced NPs, luminescent NCs were formed at lower ratios. We also found that nonluminescent NPs can be converted into luminescent clusters, via a process referred to as “size focusing”, in the presence of added excess ligands and reducing agent. The nanoclusters emit in the far red region of the optical spectrum with a quantum yield of ∼12%. They can be redispersed in a number of solvents with varying polarity while maintaining their optical and spectroscopic properties. Our synthetic protocol also allowed control over the number and type of reactive functional groups per nanocluster.
ISSN:1936-0851
1936-086X
DOI:10.1021/nn302954n