Although gold is the subject of one of the most ancient themes of investigation in science, its renaissance now leads to an exponentially increasing number of publications, especially in the context of emerging nanoscience and nanotechnology with nanoparticles and self-assembled monolayers (SAMs). We will limit the present review to gold nanoparticles (AuNPs), also called gold colloids. AuNPs are the most stable metal nanoparticles, and they present fascinating aspects such as their assembly of multiple types involving materials science, the behavior of the individual particles, size-related electronic, magnetic and optical properties (quantum size effect), and their applications to catalysis and biology. Their promises are in these fields as well as in the bottom-up approach of nanotechnology, and they will be key materials and building block in the 21st century. Whereas the extraction of gold started in the 5th millennium B.C. near Varna (Bulgaria) and reached 10 tons per year in Egypt around 1200-1300 B.C. when the marvelous statue of Touthankamon was constructed, it is probable that “soluble” gold appeared around the 5th or 4th century B.C. in Egypt and China. In antiquity, materials were used in an ecological sense for both aesthetic and curative purposes. Colloidal gold was used to make ruby glass 293 Chem. Rev. 2004, 104, 293−346

Gold nanoparticles: assembly, supramolecular chemistry, quantum-size-related properties, and applications toward biology, catalysis, and nanotechnology.

Rechargeable solid-state batteries have long been considered an attractive power source for a wide variety of applications, and in particular, lithium-ion batteries are emerging as the technology of choice for portable electronics. One of the main challenges in the design of these batteries is to ensure that the electrodes maintain their integrity over many discharge-recharge cycles. Although promising electrode systems have recently been proposed, their lifespans are limited by Li-alloying agglomeration or the growth of passivation layers, which prevent the fully reversible insertion of Li ions into the negative electrodes. Here we report that electrodes made of nanoparticles of transition-metal oxides (MO, where M is Co, Ni, Cu or Fe) demonstrate electrochemical capacities of 700 mA h g(-1), with 100% capacity retention for up to 100 cycles and high recharging rates. The mechanism of Li reactivity differs from the classical Li insertion/deinsertion or Li-alloying processes, and involves the formation and decomposition of Li2O, accompanying the reduction and oxidation of metal nanoparticles (in the range 1-5 nanometres) respectively. We expect that the use of transition-metal nanoparticles to enhance surface electrochemical reactivity will lead to further improvements in the performance of lithium-ion batteries.

Nano-sized transition-metal oxides as negative-electrode materials for lithium-ion batteries

'Bottom-up fabrication', which exploits the intrinsic properties of atoms and molecules to direct their self-organization, is widely used to make relatively simple nanostructures. A key goal for this approach is to create nanostructures of high complexity, matching that routinely achieved by 'top-down' methods. The self-assembly of DNA molecules provides an attractive route towards this goal. Here I describe a simple method for folding long, single-stranded DNA molecules into arbitrary two-dimensional shapes. The design for a desired shape is made by raster-filling the shape with a 7-kilobase single-stranded scaffold and by choosing over 200 short oligonucleotide 'staple strands' to hold the scaffold in place. Once synthesized and mixed, the staple and scaffold strands self-assemble in a single step. The resulting DNA structures are roughly 100 nm in diameter and approximate desired shapes such as squares, disks and five-pointed stars with a spatial resolution of 6 nm. Because each oligonucleotide can serve as a 6-nm pixel, the structures can be programmed to bear complex patterns such as words and images on their surfaces. Finally, individual DNA structures can be programmed to form larger assemblies, including extended periodic lattices and a hexamer of triangles (which constitutes a 30-megadalton molecular complex).

/pdf/folding-dna-to-create-nanoscale-shapes-and-patterns-1liv7u73y0.pdf

Folding DNA to create nanoscale shapes and patterns

Molecular self-assembly is the spontaneous association of molecules under equilibrium conditions into stable, structurally well-defined aggregates joined by noncovalent bonds. Molecular self-assembly is ubiquitous in biological systems and underlies the formation of a wide variety of complex biological structures. Understanding self-assembly and the associated noncovalent interactions that connect complementary interacting molecular surfaces in biological aggregates is a central concern in structural biochemistry. Self-assembly is also emerging as a new strategy in chemical synthesis, with the potential of generating nonbiological structures with dimensions of 1 to 10(2) nanometers (with molecular weights of 10(4) to 10(10) daltons). Structures in the upper part of this range of sizes are presently inaccessible through chemical synthesis, and the ability to prepare them would open a route to structures comparable in size (and perhaps complementary in function) to those that can be prepared by microlithography and other techniques of microfabrication.

Molecular self-assembly and nanochemistry: A chemical strategy for the synthesis of nanostructures

The specific bonding of DNA base pairs provides the chemical foundation for genetics. This powerful molecular recognition system can be used in nanotechnology to direct the assembly of highly structured materials with specific nanoscale features, as well as in DNA computation to process complex information. The exploitation of DNA for material purposes presents a new chapter in the history of the molecule.

/pdf/dna-in-a-material-world-28gymklany.pdf

DNA in a material world

Molecular self-assembly presents a `bottom-up' approach to the fabrication of objects specified with nanometre precision. DNA
 molecular structures and intermolecular interactions are particularly
 amenable to the design and synthesis of complex molecular objects. We
 report the design and observation of two-dimensional crystalline forms
 of DNA that self-assemble from synthetic DNA double-crossover
 molecules. Intermolecular interactions between the structural units are
 programmed by the design of `sticky ends' that associate according to
 Watson-Crick complementarity, enabling us to create specific periodic
 patterns on the nanometre scale. The patterned crystals have been
 visualized by atomic force microscopy.

https://issg.cs.duke.edu/courses/spring04/cps296.4/papers/WLWS98.pdf

Design and self-assembly of two-dimensional DNA crystals

This paper extends the study and prototyping of unusual DNA motifs, unknown in nature, but founded
on principles derived from biological structures. Artificially designed DNA complexes show promise as building
blocks for the construction of useful nanoscale structures, devices, and computers. The DNA triple crossover
(TX) complex described here extends the set of experimentally characterized building blocks. It consists of
four oligonucleotides hybridized to form three double-stranded DNA helices lying in a plane and linked by
strand exchange at four immobile crossover points. The topology selected for this TX molecule allows for the
presence of reporter strands along the molecular diagonal that can be used to relate the inputs and outputs of
DNA-based computation. Nucleotide sequence design for the synthetic strands was assisted by the application
of algorithms that minimize possible alternative base-pairing structures. Synthetic oligonucleotides were purified,
stoichiometric mixtures were annealed by slow cooling, and the resulting DNA structures were analyzed by
nondenaturing gel electrophoresis and heat-induced unfolding. Ferguson analysis and hydroxyl radical
autofootprinting provide strong evidence for the assembly of the strands to the target TX structure. Ligation
of reporter strands has been demonstrated with this motif, as well as the self-assembly of hydrogen-bonded
two-dimensional crystals in two different arrangements. Future applications of TX units include the construction
of larger structures from multiple TX units, and DNA-based computation. In addition to the presence of reporter
strands, potential advantages of TX units over other DNA structures include space for gaps in molecular arrays,
larger spatial displacements in nanodevices, and the incorporation of well-structured out-of-plane components
in two-dimensional arrays.

Construction, analysis, ligation, and self-assembly of DNA triple crossover complexes

We report the self-assembly of metallic nanoparticle arrays using DNA crystals as a programmable molecular scaffolding. Gold nanoparticles, 1.4 nm in diameter, are assembled in two-dimensional arrays with interparticle spacings of 4 and 64 nm. The nanoparticles form precisely integrated components, which are covalently bonded to the DNA scaffolding. These results show that heterologous chemical systems can be assembled into precise, programmable geometrical arrangements by DNA scaffolding, thereby representing a critical step toward the realization of DNA nanotechnology.

/pdf/selfassembly-of-metallic-nanoparticle-arrays-by-dna-4xjrx6l8ku.pdf

Selfassembly of Metallic Nanoparticle Arrays by DNA Scaffolding

DNA double-crossover (DX) molecules are rigid DNA motifs that contain two double helices linked at two different points. It is possible to form hydrogen-bonded two-dimensional crystals from DX molecules and to observe those arrays by atomic force microscopy (AFM) [Winfree, E.; Liu, F.; Wenzler, L. A.; Seeman, N. C. Nature 1998, 394, 539−544]. The sticky ends that hold the arrays together can be varied, so as to include diverse periodic arrangements of molecules in the crystal. The inclusion of extra DNA hairpins designed to protrude from the plane of the crystal provides a topographic label that is detected readily in AFM images:  By using these labels, it is possible to produce stripes at predicted spacings on the surface of the crystal. The experiments presented here demonstrate that it is possible to modify these patterns, by both enzymatic and nonenzymatic procedures. We show that a hairpin containing a restriction site can be removed quantitatively from the array. We also demonstrate that a sticky en...

Modifying the Surface Features of Two-Dimensional DNA Crystals

Two- and three-dimensional periodic lattices are constructed from repeating units of at least two antiparallel nucleic acid multi-crossover molecules. The repeating units range from single component to multi-component.

Furong Liu

Papers

Design and self-assembly of two-dimensional DNA crystals

Construction, analysis, ligation, and self-assembly of DNA triple crossover complexes

Selfassembly of Metallic Nanoparticle Arrays by DNA Scaffolding

Modifying the Surface Features of Two-Dimensional DNA Crystals

Periodic two and three dimensional nucleic acid structures