Transition-Metal-Functionalized DNA Double-Crossover Tiles: Enhanced Stability and Chirality Transfer to Metal Centers.

The double crossover junction (DX) is a fundamental building block for generating complex and varied structures from DNA. However, its implementation in functional devices is limited to the inherent properties of DNA itself. Here, we developed design strategies to generate the first metal-DX DNA tiles (DXM ) by site-specifically functionalizing the tile crossovers with tetrahedral binding pockets that coordinate CuI . These DX junctions bind two CuI ions independently at distinct sites, display greater thermal stability than native DX tiles upon metalation, and melt in a cooperative fashion. In addition, the right-handed helical chirality of DNA is transferred to the metal centers. Our tiles display high metal ion selectivity, such that CuII is spontaneously reduced to CuI in situ. By modifying our design over three generations of tiles, we elucidated the thermodynamic and geometric requirements for the successful assembly of DXM tiles, which have direct applicability in developing robust, stable DNA-based materials with electroactive, photoactive, and catalytic properties.

Ultrastable Gold Nanoparticles Modified by Bidentate N-Heterocyclic Carbene Ligands.

Highly stable gold nanoparticles (Au NPs) functionalized by bidentate N-heterocyclic carbene (NHC) ligands have been synthesized by top-down and bottom-up approaches. A detailed study of the effect of alkylation, denticity, and method of synthesis has led to the production of NHC-stabilized nanoparticles with higher thermal stability than bi- and tridentate thiol-protected Au NPs and than monodentate NHC-stabilized NPs. Importantly, bidentate NHC-protected NPs also displayed unprecedented stability to external thiol, which has been an unsolved problem to date with all nanoparticles. Thus, multidentate NHC ligands are an important, and as yet unrecognized, step forward for the preparation of high stability nanomaterials.

Ultra stable self-assembled monolayers of N-heterocyclic carbenes on gold.

Since the first report of thiol-based self-assembled monolayers (SAMs) 30 years ago, these structures have been examined in a huge variety of applications. The oxidative and thermal instabilities of these systems are widely known, however, and are an impediment to their widespread commercial use. Here, we describe the generation of N-heterocyclic carbene (NHC)-based SAMs on gold that demonstrate considerably greater resistance to heat and chemical reagents than the thiol-based counterparts. This increased stability is related to the increased strength of the gold-carbon bond relative to that of a gold-sulfur bond, and to a different mode of bonding in the case of the carbene ligand. Once bound to gold, NHCs are not displaced by thiols or thioethers, and are stable to high temperatures, boiling water, organic solvents, pH extremes, electrochemical cycling above 0 V and 1% hydrogen peroxide. In particular, benzimidazole-derived carbenes provide films with the highest stabilities and evidence of short-range molecular ordering. Chemical derivatization can be employed to adjust the surface properties of NHC-based SAMs.

Effect of clathrate hydrate formation and decomposition on NMR parameters in THF-D2O solution.

The NMR spin-lattice relaxation time (T(1)), spin-spin relaxation time (T(2)) and the diffusion coefficient D were measured for (1)H in a 1:17 mol % solution of tetrahydrofuran (THF) in D(2)O. The aim of the work was to clarify some earlier points raised regarding the utility of these measurements to convey structural information on hydrate formation and reformation. A number of irregularities in T(1) and T(2) measurements during hydrate processes reported earlier are explained in terms of the presence of interfaces and possible temperature gradients. We observe that T(1) and T(2) in solution are exactly the same before and after hydrate formation, thus confirming that the solution is isotropic. This is inconsistent with the presence of memory effects, at least those that may affect the dynamics to which T(1) and T(2) are sensitive. The measurement of the diffusion coefficient for a number of hours in the subcooled solution before nucleation proved invariant with time, again suggesting that the solution remains isotropic without affecting the guest dynamics and diffusion.