Robust DNA-functionalized core/shell quantum dots with fluorescent emission spanning from UV-vis to near-IR and compatible with DNA-directed self-assembly.

The assembly and isolation of DNA oligonucleotide-functionalized gold nanoparticles (AuNPs) has become a well-developed technology that is based on the strong bonding interactions between gold and thiolated DNA. However, achieving DNA-functionalized semiconductor quantum dots (QDs) that are robust enough to withstand precipitation at high temperature and ionic strength through simple attachment of modified DNA to the QD surface remains a challenge. We report the synthesis of stable core/shell (1-20 monolayers) QD-DNA conjugates in which the end of the phosphorothiolated oligonucleotide (5-10 nucleotides) is "embedded" within the shell of the QD. These reliable QD-DNA conjugates exhibit excellent chemical and photonic stability, colloidal stability over a wide pH range (4-12) and at high salt concentrations (>100 mM Na(+) or Mg(2+)), bright fluorescence emission with quantum yields of up to 70%, and broad spectral tunability with emission ranging from the UV to the NIR (360-800 nm).

[1]  Gregg M. Gallatin,et al.  Nanomanufacturing with DNA Origami: Factors Affecting the Kinetics and Yield of Quantum Dot Binding , 2012 .

[2]  Chad A Mirkin,et al.  Spherical nucleic acids. , 2012, Journal of the American Chemical Society.

[3]  F. Simmel,et al.  DNA-based self-assembly of chiral plasmonic nanostructures with tailored optical response , 2011, Nature.

[4]  Hao Yan,et al.  Challenges and opportunities for structural DNA nanotechnology. , 2011, Nature nanotechnology.

[5]  Chad A. Mirkin,et al.  Nanoparticle Superlattice Engineering with DNA , 2011, Science.

[6]  Grigory Tikhomirov,et al.  DNA-based programming of quantum dot valency, self-assembly and luminescence. , 2011, Nature nanotechnology.

[7]  Nanomaterials: DNA brings quantum dots to order. , 2011, Nature nanotechnology.

[8]  Michael J. Campolongo,et al.  Building plasmonic nanostructures with DNA. , 2011, Nature nanotechnology.

[9]  W. B. Knowlton,et al.  Programmable Periodicity of Quantum Dot Arrays with DNA Origami Nanotubes , 2010, Nano letters.

[10]  Hao Yan,et al.  Aqueous synthesis of zinc blende CdTe/CdS magic-core/thick-shell tetrahedral-shaped nanocrystals with emission tunable to near-infrared. , 2010, Journal of the American Chemical Society.

[11]  Kai Sun,et al.  Light-Controlled Self-Assembly of Semiconductor Nanoparticles into Twisted Ribbons , 2010, Science.

[12]  Hao Yan,et al.  Gold nanoparticle self-similar chain structure organized by DNA origami. , 2010, Journal of the American Chemical Society.

[13]  Hao Yan,et al.  Band gap engineering of quaternary-alloyed ZnCdSSe quantum dots via a facile phosphine-free colloidal method. , 2009, Journal of the American Chemical Society.

[14]  Wenlong Cheng,et al.  Free-standing nanoparticle superlattice sheets controlled by DNA. , 2009, Nature materials.

[15]  M. Mansuripur,et al.  Water-based route to ligand-selective synthesis of ZnSe and Cd-doped ZnSe quantum dots with tunable ultraviolet A to blue photoluminescence. , 2009, Langmuir : the ACS journal of surfaces and colloids.

[16]  Hao Yan,et al.  Control of Self-Assembly of DNA Tubules Through Integration of Gold Nanoparticles , 2009, Science.

[17]  A. Mohs,et al.  Tuning the optical and electronic properties of colloidal nanocrystals by lattice strain. , 2009, Nature nanotechnology.

[18]  B. Dubertret,et al.  Towards non-blinking colloidal quantum dots. , 2008, Nature materials.

[19]  Hao Yan,et al.  DNA-tile-directed self-assembly of quantum dots into two-dimensional nanopatterns. , 2008, Angewandte Chemie.

[20]  J. Vela,et al.  "Giant" multishell CdSe nanocrystal quantum dots with suppressed blinking. , 2008, Journal of the American Chemical Society.

[21]  Hao Yan,et al.  Quantum dot bioconjugation during core-shell synthesis. , 2008, Angewandte Chemie.

[22]  Chad A Mirkin,et al.  Maximizing DNA loading on a range of gold nanoparticle sizes. , 2006, Analytical chemistry.

[23]  Hao Yan,et al.  Periodic square-like gold nanoparticle arrays templated by self-assembled 2D DNA Nanogrids on a surface. , 2006, Nano letters.

[24]  Li Cao,et al.  A new route to zinc-blende CdSe nanocrystals: mechanism and synthesis. , 2005, The journal of physical chemistry. B.

[25]  N. Seeman DNA in a material world , 2003, Nature.

[26]  Chad A. Mirkin,et al.  Programmed Assembly of DNA Functionalized Quantum Dots , 1999 .

[27]  J. Storhoff,et al.  Selective colorimetric detection of polynucleotides based on the distance-dependent optical properties of gold nanoparticles. , 1997, Science.

[28]  P. Schultz,et al.  Organization of 'nanocrystal molecules' using DNA , 1996, Nature.

[29]  J. Storhoff,et al.  A DNA-based method for rationally assembling nanoparticles into macroscopic materials , 1996, Nature.