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WIREs Nanomed Nanobiotechnol
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DNA‐based programing of quantum dot properties

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Abstract Nucleic acid molecules can serve as robust ligands for aqueous synthesis of semiconductor nanocrystals or quantum dots (QDs). QD properties including size, morphology, dispersity, emission maximum, and quantum yield are highly dependent on the sequences and structures of nucleic acids used for the synthesis. This synthetic strategy provides a novel facile means of constructing compact, stable, and biofunctionalized QDs in one step, which is of particular interest for a variety of applications such as biosensing, bioimaging, and self‐assembly. This article summarizes recent advances in nucleic acid‐templated QD synthesis with an emphasis on the nucleic acids‐based programing of quantum dots properties. A variety of applications based on DNA‐passivated QDs are also discussed. WIREs Nanomed Nanobiotechnol 2013, 5:86–95. doi: 10.1002/wnan.1191 This article is categorized under: Nanotechnology Approaches to Biology > Nanoscale Systems in Biology

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Schematic illustration of nucleic acids‐templated quantum dots (QDs) synthesis. QDs properties including their size and morphology, brightness, and emission wavelength can be tuned by tailoring nucleic acids sequences and structures. These DNA‐passivated QDs are applied to a variety of biological applications and can self‐assemble to high‐order assemblies for light harvesting and pH sensing.

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DNA‐templated CdS QDs growth as a smart gene delivery system. (a) Schematic illustration of DNA plasmid‐templated CdS QDs growth induced DNA packing and glutathione‐mediated intracellular DNA unpacking. (b) Confocal microscopy of EGFP expression in 293T cells transfected with DNA–CdS QDs complex. (c) Relative transfection efficiency of 293T cells transfected with DNA plasmid, DNA–CdS‐3 (three rounds of CdS QDs synthesis), DNA–CdS‐3 with chloroquine, DNA–Lipo (Lipofectamine), and DNA–Lipo with chloroquine. (Reprinted with permission from Ref 49. Copyright 2012 American Chemical Society)

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Representative high‐resolution TEM images of DNA‐programed quantum dot complexes. (a) Quantum dot assemblies built using red dots with valencies of 1–5 and green dots. (b) Symmetric binary system made from the same green dots (top); complex structure made from three different dots: linear ternary complex (middle) and cross‐shaped ternary complex (bottom). Scale bars are 10 nm.

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One‐step synthesis of biofunctionalized CdTe QDs using chimeric DNA molecules. (a) Design of chimeric oligonucleotides with a ligand domain (phosphorothioate, blue) and a recognition domain (phosphate, red). Illustration of one‐step synthesis of DNA‐functionalized CdTe nanocrystals using DNA, CdCl2, NaHTe, and glutathione (GSH) as precursors. The phosphorothioate portion of the sequence (blue) serves as a nanocrystal ligand, while the phosphate portion (red) of the DNA sequence remains free to bind to biomolecular partners. (b) and (c) Specific binding of CdTe nanocrystals functionalized with a cell‐binding aptamer to cognate cells (CCRF‐CEM cells) characterized by flow cytometry (b) and confocal microscopy (c).

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RNA‐templated CdS QDs synthesis. (a) Left: Primary and secondary structure diagrams of wild‐type (WT) Escherichia coli tRNALeu(CUN) depicted in a cloverleaf representation. Right: Primary structure of the mutated (MT) tRNA with disrupted base pairs in all five stems that would cause the tRNA to adopt a linear structure. Inset: L‐shaped tertiary structure of WT tRNAs. (b) Transmission electron microscopy images of CdS QDs synthesized with the WT tRNA template (left panel) or the MT tRNA template (right panel). Scale bars are 5 nm for the upper images and 20 nm for the lower images. (Reprinted with permission from Ref 22. Copyright 2012 American Chemical Society)

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Stability of DNA CdS quantum dots (QDs). (a) Stability of CdS QDs made with UTP, CTP, ATP, and GTP in 0.05 M PbS buffer (data obtained for all nucleotides in H2O are shown for reference by an alternating dotted‐dashed line). (b) 20‐merCdS QDs (A20, T20, C20, and G20) in buffer containing 10 mM phosphate and 50 mM NaCl. (Reprinted with permission from Ref 12. Copyright 2012 American Chemical Society)

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Effect of specific chemical functionalities present on GTP on PbS quantum dot (QD) synthesis. (a) Luminescence spectra obtained when GTP, G, ITP, and 7‐CH3‐GTP were used for PbS synthesis. (b) Proposed roles of phosphate and base functionalities on GTP in nanoparticle nucleation, growth, termination, stabilization, and passivation. (Reprinted with permission from Ref 18. Copyright 2012 American Chemical Society)

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Molecular structures of DNA molecules.

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Energy‐filtered TEM images of PbS quantum dots (QDs) grown on calf thymus DNA molecules. (a) Phosphorus‐enhanced image. (Arrow: QD associated with DNA appear as bright spots.) (b) Enlarged view of a region from (a). (c) Corresponding bright‐field image. (Arrow: electron‐dense QD.) Scale bars are 50 nm. (Reprinted with permission from Ref 14. Copyright 2005 John Wiley & Sons, Inc)

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