DNA‐Templated Silver Nanorings

Nanostructures of noble metals with well-defined shapes and sizes are increasingly attracting the attention of scientists in the fields of catalysis, electronics, photonics, information storage, optoelectronics, biological labeling, etc. The further development and practical applications of nanostructures are expected to increase rapidly because of their interesting optical, electronic, and magnetic properties. In this context, important knowledge of the direct preparation of metallic nanostructures of controlled size and shape has been developed over the past few years, and various morphologies, such as spherical nanoparticles, nanocubes, nanoprisms, nanoplates, or nanobelts, can now be prepared in a controlled way. However, since these techniques are based on the directed growth of particles in the reaction medium, they can only lead to shapes of a simple topology, such as spheroids, ellipsoids, or polyhedrons. In contrast, nanoparticles with a toroidal shape (nanoring) can not be produced by a direct growth technique. Hence, the only way to produce such a morphology is to use a toroidal template of nanometer-scale dimensions. Elaborate and successful methods to prepare silver or gold rings based on the use of a nanoparticle array or a mesoporous membrane as a primary template, were recently described by Xia and co-workers and Yan and Goedel, respectively. However, these techniques provide rings with a minimal size of 0.5 lm that can not be directly dispersed in an aqueous medium. On the other hand, due to the specific interaction between DNA and silver ions, DNA is an ideal template to build silver nanostructures. This principle has been used successfully to produce nanoparticle arrays on a DNA scaffold, or DNA-templated silver nanowires. However, the ability of DNA chains to form toroidal condensates as a result of the DNA-folding transition (DNA condensation) has not been hitherto noticed by materials scientists. The ability of DNA to condense into well-defined toroids provides a unique opportunity to use them as templates to create silver toroidal nanostructures (nanorings) of controlled shape and dimensions. In this communication, we describe a one-pot, three-step, simple preparation of well-defined silver nanorings (100 nm in diameter) dispersed in water, based on the use of dilute solutions of DNA condensates as nanostructured templates. DNA is a semiflexible, highly charged polyelectrolyte that assumes an elongated-coil conformation in water due to the electrostatic repulsion between the negatively charged monomers. DNA molecules usually fold into tightly packed toroidal condensates with an outer diameter of typically 70–90 nm in the presence of hydrophilic neutral polymers, or upon the addition of a small amount of condensing agent, such as cationic polyamines, multivalent metal cations, and cationic surfactants, to a dilute DNA solution. The role of the condensing agents is to induce an attraction between the DNA monomers (chain neutralization or crowding effect), and the toroidal morphology is adopted because of the native rigidity of the DNA double-stranded chain. Advanced Materials 0000, 00, 0–0 1

[1]  K. Yoshikawa,et al.  Dielectric control of counterion-induced single-chain folding transition of DNA. , 2005, Biophysical journal.

[2]  Can Xue,et al.  Large-scale assembly of single-crystal silver nanoprism monolayers. , 2005, Small.

[3]  Li Wang,et al.  One-step synthesis of silver nanoparticles, nanorods, and nanowires on the surface of DNA network. , 2005, The journal of physical chemistry. B.

[4]  W. Goedel,et al.  The preparation of mesoscopic rings in colloidal crystal templates. , 2005, Angewandte Chemie.

[5]  Younan Xia,et al.  Shape-controlled synthesis of metal nanostructures: the case of silver. , 2005, Chemistry.

[6]  Philip S Lukeman,et al.  Nucleic acid nanostructures: bottom-up control of geometry on the nanoscale , 2005, Reports on progress in physics. Physical Society.

[7]  R. Eritja,et al.  DNA‐Templated Assembly of a Protein‐Functionalized Nanogap Electrode , 2004 .

[8]  Joseph M. McLellan,et al.  Edge spreading lithography and its application to the fabrication of mesoscopic gold and silver rings. , 2004, Journal of the American Chemical Society.

[9]  W. Goedel,et al.  Preparation of Mesoscopic Gold Rings Using Particle Imprinted Templates , 2004 .

[10]  Shiho Tokonami,et al.  Highly Ordered Assemblies of Au Nanoparticles Organized on DNA , 2003 .

[11]  N. Hud,et al.  Controlling the size of nanoscale toroidal DNA condensates with static curvature and ionic strength , 2003, Proceedings of the National Academy of Sciences of the United States of America.

[12]  K. Yoshikawa,et al.  Controlling the intrachain segregation on a single DNA molecule. , 2003, Journal of the American Chemical Society.

[13]  M. Sano,et al.  Elastic response of single DNA molecules exhibits a reentrant collapsing transition. , 2003, Physical review letters.

[14]  Younan Xia,et al.  Shape-Controlled Synthesis of Gold and Silver Nanoparticles , 2002, Science.

[15]  Catherine J. Murphy,et al.  Seed‐Mediated Growth Approach for Shape‐Controlled Synthesis of Spheroidal and Rod‐like Gold Nanoparticles Using a Surfactant Template , 2001 .

[16]  K. Yoshikawa,et al.  Disappearance of the negative charge in giant DNA with a folding transition. , 2001, Biophysical journal.

[17]  K. Yoshikawa,et al.  Formation of a Giant Toroid from Long Duplex DNA , 1999 .

[18]  Charles F. Zukoski,et al.  Formation mechanisms and aggregation behavior of borohydride reduced silver particles , 1998 .

[19]  E. Braun,et al.  DNA-templated assembly and electrode attachment of a conducting silver wire , 1998, Nature.

[20]  Hiroshi Noguchi,et al.  Self-organized nanostructures constructed with a single polymer chain , 1996 .

[21]  J. Pelta,et al.  DNA Aggregation Induced by Polyamines and Cobalthexamine (*) , 1996, The Journal of Biological Chemistry.

[22]  J. Ubbink,et al.  Deformation of toroidal DNA condensates under surface stress , 1996 .

[23]  Kenichi Yoshikawa,et al.  Discrete Coil-Globule Transition of Large DNA Induced by Cationic Surfactant , 1995 .

[24]  Grosberg AYu,et al.  On the compact form of linear duplex DNA: globular states of the uniform elastic (persistent) macromolecule. , 1986, Journal of biomolecular structure & dynamics.

[25]  Jonathan Widom,et al.  Monomolecular condensation of λ‐DNA induced by cobalt hexammine , 1983 .

[26]  R. L. Baldwin,et al.  Cation-induced toroidal condensation of DNA studies with Co3+(NH3)6. , 1980, Journal of molecular biology.

[27]  R. W. Wilson,et al.  Counterion-induced condesation of deoxyribonucleic acid. a light-scattering study. , 1979, Biochemistry.

[28]  J. Schellman,et al.  Compact form of DNA induced by spermidine , 1976, Nature.

[29]  U. K. Laemmli,et al.  Characterization of DNA condensates induced by poly(ethylene oxide) and polylysine. , 1975, Proceedings of the National Academy of Sciences of the United States of America.