production-and-targeting-of-monovalent-quantum-dots

Production and Targeting of Monovalent Quantum Dots

The multivalent nature of commercial quantum dots (QDs) and the difficulties associated with producing monovalent dots have limited their applications in ...

University of California, San Francisco

University of California, Berkeley

Lawrence Berkeley National Laboratory

We report the shape and size control of polyhedral gold nanocrystals by a modified polyol process. The rapid reduction of gold precursors in refluxing 1,5-pentanediol has successfully provided a series of gold nanocrystals in the shape of octahedra, truncated octahedra, cuboctahedra, cubes, and higher polygons by incremental changes of silver nitrate concentration. All nanocrystals were obtained quantitatively and were uniform in shape and size in the range of approximately 100 nm. Smaller octahedra and cubes were also prepared by using large amounts of PVP. Silver species generated from AgNO3 seemed to determine the final nanocrystal morphology by the selective growth of {111} and/or the restriction of {100}. The shape evolution of the particles was addressed by quenching the reactions at different time intervals. The approximately 60 nm seeds were generated rapidly and grown slowly with simultaneous edge sharpening. Aging the reaction mixture focused the size and shape of the nanocrystals by Ostwald ripening. We believe that our selective growth conditions can be applied to other shapes and compositions of face-centered cubic metals.

Polyhedral gold nanocrystals with O h symmetry: from octahedra to cubes.

Directed surface overgrowth and morphology control of polyhedral gold nanocrystals.

Ag-Au-Ag heterometallic nanorods formed through directed anisotropic growth.

A shape auxiliary approach for the synthesis of shape-controlled gold nanocrystals with functional moieties is established; carboxylate-functionalized gold polyhedra were successfully synthesized in a one-pot reaction in the presence of poly(dimethylaminoethyl methacrylate), which contains the dimethylaminoethyl group as a shape auxiliary.

Shape auxiliary approach for carboxylate-functionalized gold nanocrystals.

An asymmetric single hollow structure was generated from Ag-Au-Ag heterometal nanorods by a partial galvanic replacement reaction for the first time. The C(2)-symmetry breaking took place because of the random generation of a single pit on only one end of the silver domain at an early stage of the reaction. Careful control of the reaction kinetics could also yield a double-hollow structure on both ends of the silver domain. The resulting single- and double-hollow nanorods exhibited characteristic extinctions in the near-IR range.

Asymmetric hollow nanorod formation through a partial galvanic replacement reaction.

PVP (poly(vinyl pyrrolidone)) is a common polymer that behaves as a surface-regulating agent that shapes metal nanocrystals in the polyol process. We have used different polymers containing tertiary amide groups, namely PVCL (poly(vinyl caprolactam)) and PDMAm (poly(N,N-dimethyl acrylamide)), for the synthesis of gold polyhedrons, including octahedrons, cuboctahedrons, cubes, and higher polygons, under the present polyol reaction conditions. The basicity and surface coordination power of the polymers are in the order of PVCL, PVP, and PDMAm. A correlation is observed between the coordination power of the polymers and the resulting gold nanocrystal size. Strong coordination and electron donation from the polymer functional groups to the gold surface restrict particle growth rates, which leads to small nanocrystals. The use of PVCL can yield gold polyhedral structures with small sizes, which cannot be achieved in the reactions with PVP. Simultaneous hydrolysis of the amide group in PDMAm leads to carboxylate functionality, which is very useful for generating chemical and bioconjugates through the formation of ester and amide bonds.

Coordination power adjustment of surface-regulating polymers for shaping gold polyhedral nanocrystals.

Plasmonic nanostructures such as gold nanoparticles are very useful for monitoring chemical reactions because their optical properties are highly dependent upon the environment surrounding the particle surface. Here, we designed the catalytic structure composed of platinized cadmium sulfide with gold domains as a sensitive probe, and we monitored the photocatalytic decomposition of lactic acid to generate hydrogen gas in situ by single-particle dark-field spectroscopy. The plasmon band shift of the gold probe throughout the reaction exhibits significant particle-to-particle variation, and by simulating the reaction kinetics, the rate constant and structural information (including the diffusion coefficient through the shell and the relative arrangement of the active sites) can be estimated for individual catalyst particles. This approach is versatile for the monitoring of various heterogeneous reactions with distinct components at a single-particle level.

Plasmonic monitoring of catalytic hydrogen generation by a single nanoparticle probe.

In the present study, we demonstrate the precise tuning of surface plasmon resonance over the full visible range by compositional variation of the nanoparticles. The addition of sulfide ions into the Au@Ag core-shell nanocubes generates stable Au@Ag/Ag(2)S core-shell nanoparticles at room temperature, and the plasmon extinction maximum shifts to the longer wavelength covering the entire visible range of 500-750 nm. Based on the optical property, the Au@Ag core-shell nanocubes are employed as a colorimetric sensing framework for sulfide detection in water. The detection limit is measured to be 10 ppb by UV-vis spectroscopy and 200 ppb by naked eyes. Such nanoparticles would be useful for decoration and sensing purposes, due to their precise color tunability and high stability.

Full-color tuning of surface plasmon resonance by compositional variation of Au@Ag core-shell nanocubes with sulfides.

We investigated the localized surface plasmon resonances of individual AgAuAg nanorods (NRs) using the dark-field spectro-microscopy technique. We find that the scattering spectra of such hetero-NRs show longitudinal resonance wavelengths that are nearly insensitive to the relative composition of Ag and Au. Instead, the resonance is mostly governed by the overall length of the nanorod. This shows that the plasmons oscillate along the entire length of the NR without the significant perturbation at the Ag-Au interfaces. The results demonstrate that the overall geometry as well as the composition determine the tunability of the hetero-metallic nanostructures, and provide an important design rule for the composition-tunable bimetallic plasmon structures.

Localized plasmon resonances of bimetallic AgAuAg nanorods.

Gold nanoparticles with suitable surface functionalities have been widely used as a versatile nanobioplatform. However, functionalized gold nanoparticles using thiol-terminated ligands have a tendency to aggregate, particularly in many enzymatic reaction buffers containing biological thiols, because of ligand exchange reactions. In the present study, we developed a one-step synthesis of poly(ethylene glycol) (PEG)ylated gold nanoparticles using poly(dimethylaminoethyl methacrylate) (PDMAEMA) in PEG as a polyol solvent. Because of the chelate effect of polymeric functionalities on the gold surface, the resulting PEGylated gold nanoparticles (Au@P-PEG) are very stable under the extreme conditions at which the thiol-monolayer-protected gold nanoparticles are easily coagulated. Using the solvent mixture of PEG and ethylene glycol (EG) and subsequent hydrolysis, gold nanoparticles bearing mixed functionalities of PEG and carboxylate are generated. The resulting particles exhibit selective adsorption of positively charged chymotrypsin (ChT) without nonselective adsorption of bovine serum albumin (BSA). The present nanoparticle system has many advantages, including high stability, simple one-step synthesis, biocompatibility, and excellent binding specificity; thus, this system can be used as a versatile platform for potential bio-related applications, such as separation, sensing, imaging, and assays.

Poly(ethylene glycol)- and carboxylate-functionalized gold nanoparticles using polymer linkages: single-step synthesis, high stability, and plasmonic detection of proteins.

Precise control over interfacial chemistry between nanoparticles and other materials remains a major challenge that limits broad application of nanotechnology in biology. To address this challenge, we used 'steric exclusion' to completely convert commercial quantum dots (QDs) into monovalent imaging probes by wrapping each QD with a functionalized oligonucleotide. We demonstrated the utility of these QDs as modular and nonperturbing imaging probes by tracking individual Notch receptors on live cells.

Formation of targeted monovalent quantum dots by steric exclusion.

Caspases are proteases involved in cell death, where caspase-3 is the chief executioner that produces an irreversible cutting event in downstream protein substrates and whose activity is desired in the management of cancer. To determine such activity in clinically relevant samples with high signal-to-noise, plasmon rulers are ideal because they are sensitively affected by their interparticle separation without ambiguity from photobleaching or blinking effects. A plasmon ruler is a noble metal nanoparticle pair, tethered in close proximity to one another via a biomolecule, that acts through dipole-dipole interactions and results in the light scattering to increase exponentially. In contrast, a sharp decrease in intensity is observed when the pair is confronted by a large interparticle distance. To align the mechanism of protease activity with building a sensor that can report a binary signal in the presence or absence of caspase-3, we present a caspase-3 selective plasmon ruler (C3SPR) composed of a pair of Zn0.4Fe2.6O4@SiO2@Au core-shell nanoparticles connected by a caspase-3 cleavage sequence. The dielectric core (Zn0.4Fe2.6O4@SiO2)-shell (Au) geometry provided a brighter scattering intensity versus solid Au nanoparticles, and the magnetic core additionally acted as a purification handle during the plasmon ruler assembly. By monitoring the decrease in light scattering intensity per plasmon ruler, we detected caspase-3 activity at single molecule resolution across a broad dynamic range. This was observed to be as low as 100 fM of recombinant material or 10 ng of total protein from cellular lysate. By thorough analyses of single molecule trajectories, we show caspase-3 activation in a drug-treated chronic myeloid leukemia (K562) cancer system as early as 4 and 8 h with greater sensitivity (2- and 4-fold, respectively) than conventional reagents. This study provides future implications for monitoring caspase-3 as a biomarker and efficacy of drugs.

Article	Year
Polyhedral gold nanocrystals with O h symmetry: from octahedra to cubes. Journal of the American Chemical Society\| PubMed ID: 17105296	2006
Directed surface overgrowth and morphology control of polyhedral gold nanocrystals. Angewandte Chemie (International ed. in English)\| PubMed ID: 18181259	2008
Ag-Au-Ag heterometallic nanorods formed through directed anisotropic growth. Journal of the American Chemical Society\| PubMed ID: 18281994	2008
Shape auxiliary approach for carboxylate-functionalized gold nanocrystals. Chemical communications (Cambridge, England)\| PubMed ID: 19240898	2009
Asymmetric hollow nanorod formation through a partial galvanic replacement reaction. Journal of the American Chemical Society\| PubMed ID: 19994851	2009
Coordination power adjustment of surface-regulating polymers for shaping gold polyhedral nanocrystals. Chemistry (Weinheim an der Bergstrasse, Germany)\| PubMed ID: 21656861	2011
Plasmonic monitoring of catalytic hydrogen generation by a single nanoparticle probe. Journal of the American Chemical Society\| PubMed ID: 22176153	2012
Full-color tuning of surface plasmon resonance by compositional variation of Au@Ag core-shell nanocubes with sulfides. Langmuir : the ACS journal of surfaces and colloids\| PubMed ID: 22304325	2012
Localized plasmon resonances of bimetallic AgAuAg nanorods. Physical chemistry chemical physics : PCCP\| PubMed ID: 23247539	2013
Poly(ethylene glycol)- and carboxylate-functionalized gold nanoparticles using polymer linkages: single-step synthesis, high stability, and plasmonic detection of proteins. Langmuir : the ACS journal of surfaces and colloids\| PubMed ID: 24090031	2013
Formation of targeted monovalent quantum dots by steric exclusion. Nature methods\| PubMed ID: 24122039	2013
Sensitive and selective plasmon ruler nanosensors for monitoring the apoptotic drug response in leukemia. ACS nano\| PubMed ID: 25166742	2014

Daeha Seo

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