No abstract

The formation of traditional ionic materials occurs principally via joint accumulation of both anions and cations. Herein, we describe a previously unreported phenomenon by which macroscopic liquid-like thin layers with tunable self-organization properties form through accumulation of stable complex ions of one polarity on surfaces. Using a series of highly stable molecular anions we demonstrate a strong influence of the internal charge distribution of the molecular ions, which is usually shielded by counterions, on the properties of the layers. Detailed characterization reveals that the intrinsically unstable layers of anions on surfaces are stabilized by simultaneous accumulation of neutral molecules from the background environment. Different phases, self-organization mechanisms and optical properties are observed depending on the molecular properties of the deposited anions, the underlying surface and the coadsorbed neutral molecules. This demonstrates rational control of the macroscopic properties (morphology and size of the formed structures) of the newly discovered anion-based layers.

Scanning tunneling microscopy (STM) is employed to demonstrate that the presence of the vanadyl ion (VO 2+ ) in the 2,9,16,23-tetraphenoxy-29H,31H-phthalocyanine complex (VOPcPhO) has a pronounced effect on the organization of the complex at the highly oriented pyrolytic graphite (HOPG)-n-alkyl benzene (n ) 6, 7, 8, and 10) interface. VOPcPhO forms at least three different stable architectures, as compared to only one type of structure resulting from the adsorption of the metal-free tetraphenoxyphthalocyanine analog (H 2 PcPhO) on HOPG under conditions similar to VOPcPhO. All three observed VOPcPhO monolayer structures have high packing density and are commensurate with the underlying graphite lattice, whereas H 2 PcPhO forms a lower packing density incommensurate adlayer. The VOPcPhO structures display a small rectangular unit cell (1 molecule/cell) with lattice vector lengths of 1.28 and 1.48 nm, a larger rectangular unit cell (6 molecules/ cell) with lattice vector lengths of 4.43 nm 2.98 nm, and an oblique unit cell (2 molecules/cell and R ) 84.7°) with lattice vector lengths of 1.48 and 2.99 nm. As a second layer begins to form, it preferentially adds to the large unit cell, keeping those lattice parameters, but with only four molecules per cell. The H 2 PcPhO adlayer achieves an oblique unit cell (R ) 74°and 1 molecule/cell) with 1.58 and 1.68 nm length lattice vectors. On the basis of combined experimental results and theoretical calculations, we propose models for the observed molecular organizations.

Mineral nucleation can be catalyzed by the presence of mineral substrates; however, the mechanisms of heterogeneous nucleation remain poorly understood. A combination of in situ time-sequenced measurements and nanomanipulation experiments were performed using atomic force microscopy (AFM) to probe the mechanisms of heteroepitaxial nucleation of otavite (CdCO 3 ) on calcite (CaCO 3 ) single crystals that exposed the (101̅ 4) surface. Otavite and calcite are isostructural carbonates that display a 4% lattice mismatch, based on their (101̅ 4) surface areas. AFM observations revealed a two-stage process in the nucleation of cadmium carbonate surface precipitates. As evidenced by changes in the height, shape, growth behavior, and friction signal of the precipitates, a precursor phase was observed to initially form on the surface and subsequently undergo an epitaxy-mediated phase transformation to otavite, which then grew epitaxially. Nanomanipulation experiments, in which the applied force was increased progressively until precipitates were removed from the surface, showed that adhesion of the precursor phase to the substrate was distinctively weaker than that of the epitaxial phase, consistent with that of an amorphous phase. These findings demonstrate that heterogeneous mineral nucleation can follow a nonclassical pathway like that found in homogeneous aqueous conditions.

Dendrimers have shown great potential in drug delivery because of their enhancement of drug solubility in aqueous media, leading to an increase in in vivo circulation and efficacy to targets. The structure of drug-dendrimer complexes however, is not well-known owing to the difficulties associated with visualizing individual drug molecules attached to dendrimers. Scanning tunneling microscopy (STM) enables visualization of dendrimer intramolecular structures using our approach of metal ion tagging. This work extends the approach to reveal the hierarchical structure of indomethacin-loaded poly(amidoamine) hydroxyl-terminated dendrimers. STM imaging provides structural information such as their height, lateral dimensions, and volume. High-resolution STM images enable the identification and count of individual indomethacin molecules bound to the anterior of dendrimers. Removal of drug molecules by the STM tip allows the calculation of individual drug-dendrimer binding energy, which is consistent with 1-3 hydrogen bonds. These investigations provide new insight into the hierarchical structure and nature of indomethacin-dendrimer interactions and deepen our understanding of the stability and pharmacokinetic behavior of dendrimer-based drug delivery vehicles.