Porphyrin Supramolecular Arrays Formed by Weakly Interacting Meso-Functional Groups on Au(111).

The formation of a binary porphyrinic self-assembled system between meso-tetrakis(4-carboxyphenyl) porphyrin (TCPP) and meso-tetrakis(4-dimethyl amino) porphyrin (TDAP) was easily designed through non-covalent interactions in solution and adsorbed on a gold substrate. It was found that non-covalent interactions and geometrical conformations between porphyrins allow their self-assembly into a well-defined arrangement, which was confirmed by UV-Vis spectroscopy, electrochemistry, atomic force microscopy and density functional theory (DFT) studies.

Structural, Physical, and Antifungal Characterization of Starch Edible Films Added with Nanocomposites and Mexican Oregano (Lippia berlandieri Schauer) Essential Oil.

The aim of this study was to evaluate the structural, physical, and antifungal characteristics of starch edible films added with nanocomposites and Mexican oregano (Lippia berlandieri Schauer) essential oil (EO). Starch edible films were formulated with Mexican oregano EO (0%, 1%, or 2% v/v) and bentonite or halloysite (2%). Physical properties such as L* (luminosity), hue, film thickness, and O2 and CO2 permeability were determined. Structural analysis was carried out via atomic force microscopy (AFM). Antifungal activity against Aspergillus niger, Fusarium spp., and Rhizopus spp. was evaluated. The addition of EO and nanocomposites reduced luminosity, providing color to the edible films. Film thickness increased through the addition of EO concentration. O2 and CO2 permeability was increased by bentonite/EO films, and for halloysite films, CO2 permeability decreased as EO concentration increased. The addition of EO with both nanocomposites shows an evident morphological change in film structure, decreasing pore density and increasing pore size. In general, Mexican oregano EO added to edible starch films has an adequate fungicidal effect. The most sensitive microorganism tested was A. niger. Edible films added with Mexican oregano EO and nanocomposites show better physical and antifungal properties due to an adequate structural change in the biopolymer matrix.

From self-assembly to charge transport with single molecules - an electrochemical approach.

Structure formation and self-assembly of physisorbed and chemisorbed organic monolayers will be describedon electrified solid-liquid interfaces employing in-situ scanning tunneling microscopy (STM) and surface-enhancedinfrared spectroscopy (SEIRAS) in combination with electrochemical techniques. We present first a casestudy on self-assembly by directional hydrogen bonding and its interplay with the electrode potential choosingaromatic carboxylic acids, with an emphasis on 1,3,5-benzene-tricarboxylic acid (TMA). Structure and electricalcharacteristics of chemisorbed organic monolayers involving the formation of covalent bonds with the substratesurface will be discussed for a series of 4-methyl-4'-(n-mercaptoalkyl)biphenylson Au(111) electrodes. In an attempt to explore single molecule properties, such as charge transport andredox-mediated tunneling, we subsequently introduce an STM-based technique to construct symmetric and asymmetricmetal/(single) molecule/metal junctions. Employing α,ω-alkanedithiols and redox-active derivatives of viologens we demonstratenovel transport and single molecule electrochemical studies, which bear unique novel perspectives for fundamentalas well as applied investigations.

Scanning tunneling microscopy and spectroscopy studies of 4-methyl- 4'-(n-mercaptoalkyl)biphenyls on Au(111)-(1x1).

4-methyl-4'-(n-mercaptoalkyl)biphenyl (CH3-C6H4-C6H4-(CH2)n-SH, n=3-6, BPn) monolayers assembled on Au(111)-(1x1) in 1,3,5,-trimethylbenzene (TMB) at various temperatures are studied by scanning tunneling microscopy (STM) and scanning tunneling spectroscopy (STS). High resolution STM images reveal that BP3 and BP5 form a (sqrt 3x2sqrt 3) repeating motif superimposed on a temperature-dependent Moire pattern. BP4 and BP6 adlayers are characterized by a coexisting (2sqrt 3x5sqrt 3) majority phase and a temperature-dependent (3xpsqrt 3) minority phase. Assembly at 60 degrees C or 90 degrees C leads to p=5. Compression of the adlayer was found at higher temperatures. Combined with high-resolution structure experiments, the electronic characteristics of BP3 and BP4 self-assembled monolayers (SAMs) were studied by monitoring current-distance (iT-Deltaz) and current-voltage (iT-Ebias) characteristics in TMB employing a gold STM tip|BPn|Au(111)-(1x1) configuration. The semilogarithmic (iT-Deltaz) plots yielded three linear regions in the range 10 pA