A Chemical Template for Synthesis of Molecular Sheets of Calcium Carbonate.

Inspired by the discovery of graphene and its unique properties, we focused our research to develop a scheme to create nacre like lamellar structures of molecular sheets of CaCO3 interleaved with an organic material, namely carbon. We developed a facile, chemical template technique, using a formulation of poly(acrylic) acid (PAA) and calcium acetate to create lamellar stacks of single crystal sheets of CaCO3, with a nominal thickness of 17 Å, the same as a unit-cell dimension for calcite (c-axis = 17.062 Å), interleaved with amorphous carbon with a nominal thickness of 8 Å. The strong binding affinity between carboxylate anions and calcium cations in the formulation was used as a molecular template to guide CaCO3 crystallization. Computational modeling of the FTIR spectra showed good agreement with experimental data and confirmed that calcium ions are bridged between polymer chains, resulting in a net-like polymer structure. The process readily lends itself to explore the feasibility of creating molecular sheets of other important inorganic materials and potentially find applications in many fields such as super capacitors and "low k di-electric" systems.

Fabrication of hierarchically porous materials and nanowires through coffee ring effect.

We report a versatile method for the fabrication of nanowires and hierarchical porous materials from a wide variety of ceramic materials such as CaCO3, ZnO, CuO, Co3O4, Co-doped ZnO, and Ag2O. The method consists of evaporation of CO2-enriched water microdroplets (diameter ∼3 µm) deposited from an aerosol onto heated substrates (T = 120 °C). A variety of porous scaffolds with 1-3 µm sized pores can be generated by tuning the process conditions. Subsequent sintering of the scaffolds is shown to generate nanosized pores in the walls of the porous scaffold creating a dual hierarchy of pore sizes (∼50 nm and 1-3 µm). We propose a mechanism for the formation of scaffolds based on the coffee-ring effect during the evaporation of microdroplets. Ostwald-ripening of CaCO3 scaffolds prepared without sintering yields scaffold structures consisting of two-dimensional crystals of CaCO3 that are one unit cell thick. The favorable application of CaCO3 scaffolds for the enhancement of bone healing around titanium implants with improved biocompatibility is also demonstrated.

Covalent Coupling of Nanoparticles with Low-Density Functional Ligands to Surfaces via Click Chemistry.

We demonstrate the application of the 1,3-dipolar cycloaddition ("click" reaction) to couple gold nanoparticles (Au NPs) functionalized with low densities of functional ligands. The ligand coverage on the citrate-stabilized Au NPs was adjusted by the ligand:Au surface atom ratio, while maintaining the colloidal stability of the Au NPs in aqueous solution. A procedure was developed to determine the driving forces governing the selectivity and reactivity of citrate-stabilized and ligand-functionalized Au NPs on patterned self-assembled monolayers. We observed selective and remarkably stable chemical bonding of the Au NPs to the complimentarily functionalized substrate areas, even when estimating that only 1-2 chemical bonds are formed between the particles and the substrate.

Inkjet-printed thiol self-assembled monolayer structures on gold: quality control and microarray electrode fabrication.

Laterally structured, self-assembled monolayers (SAMs) of different thiols (HS-R-X, R = (CH 2) 3-16, X = -CH 3, -COOH, -NH 2) on gold have been prepared by inkjet printing. The printer is a modified, low-cost desktop printer (Epson Stylus Photo R200), the ink is a 1 mM solution of the thiol in ethanol/glycerol (6:1). The quality of inkjet-printed large area SAMs obtained in this study is between that of a layer self-assembled from a thiol solution and that obtained by soft lithography, according to cyclic voltammetry, electrochemical impedance spectroscopy, scanning electrochemical microscopy (SECM), and polarization-modulated Fourier transform infrared reflection-absorption spectroscopy (PM IRRAS). For the first time, simultaneous printing of two different thiols in a single print job as an alternative to sequential printing and backfilling is demonstrated. The smallest structures consisting of conductive disks of 40 microm diameter were analyzed as single spots by SECM and as random array electrodes with different average disk-disk distance. Conductive band electrodes with variable bandwidth (300 microm to 1 cm) are presented, as well as a pH switchable band structure. As compared to stamping, inkjet printing allows for simultaneous multiple thiol printing in a single print job with the resolution limited only by the droplet size and the precision of the translation stage.