Volumetric Study of the Mixtures <i>n</i>‑Hexane + Isomeric Chlorobutane: Experimental Characterization and Volume Translated Peng–Robinson Predictions

The <i>pρTx</i> behavior of the binary mixtures <i>n</i>-hexane + isomeric chlorobutane has been studied over the whole composition range at temperatures between 283.15 and 323.15 K and pressures from 0.1 to 65.0 MPa. Experimental densities have been used to obtain different excess properties: excess molar volume, excess isobaric expansibility, excess isothermal compressibility, and excess internal pressure. These excess properties have been analyzed in terms of molecular interactions and structural effects. Finally, experimental densities of the binary mixtures have been compared with the predictions of the volume translated Peng–Robinson (VTPR) model. The overall average deviation between experimental and calculated densities is 0.00427 g·cm^–3, which can be considered reasonably good predictions

Reversible Monolayer–Bilayer Transition in Supported Phospholipid LB Films under the Presence of Water: Morphological and Nanomechanical Behavior

Mixed monolayer Langmuir–Blodgett (LB) films of 1,2-dipalmitoyl-<i>sn</i>-glycero-3-phosphocholine (DPPC) and cholesterol (Chol) in the 1:1 ratio have been prepared onto solid mica substrates. Upon immersion in water or in an aqueous HEPES solution (pH 7.4) the monolayer LB films were spontaneously converted into well-organized bilayers leaving free mica areas. The process has been demonstrated to be reversible upon removal of the aqueous solution, resulting in remarkably free of defects monolayers that are homogeneously distributed onto the mica. In addition, the nanomechanical properties exhibited by the as-formed bilayers have been determined by means of AFM breakthrough force studies. The bilayers formed by immersion of the monolayer in an aqueous media exhibit nanomechanical properties and stability under compression analogous to those of DPPC:Chol supported bilayers obtained by other methods previously described in the literature. Consequently, the hydration of a monolayer LB film has been revealed as an easy method to produce well-ordered bilayers that mimic the cell membrane and that could be used as model cell membranes

Acetylene Used as a New Linker for Molecular Junctions in Phenylene–Ethynylene Oligomer Langmuir–Blodgett Films

Langmuir and Langmuir–Blodgett films have been fabricated from an acetylene-terminated phenylene–ethynylene oligomer, namely 4-((4-((4-ethynylphenyl)­ethynyl)­phenyl)­ethynyl)­benzoic acid (HOPEA). Characterization of the Langmuir film by surface pressure vs area per molecule isotherms and Brewster angle microscopy reveals the formation of a high quality monolayer at the air–water interface. One layer Langmuir–Blodgett (LB) films were readily fabricated by the transfer of HOPEA Langmuir films onto solid substrates by the withdrawal of the substrate. The deposition mode was Z-type. Quartz crystal microbalance (QCM) experiments confirm the formation of directionally oriented, monolayer LB films, in which the HOPEA molecules are linked to the gold substrate by attachment through the acid group. The morphology of these films was analyzed by atomic force microscopy (AFM), which revealed an optimum transference surface pressure of 18 mN m^–1 for the formation of homogeneous films. Cyclic voltammetry also showed a significant blockage of gold electrodes covered by HOPEA monolayers. Electrical properties of HOPEA monolayers sandwiched between a bottom gold electrode and a gold STM (scanning tunneling microscope) tip have been recorded, revealing that the acetylene group is an efficient linker for electron transport. In addition, the STM experiments indicate a nonresonant tunneling mechanism of charge transport through these metal–molecule–metal junctions

Gas-Phase Synthesis of Iron Silicide Nanostructures Using a Single-Source Precursor: Comparing Direct-Write Processing and Thermal Conversion

The investigation of precursor classes for the fabrication of nanostructures is of specific interest for maskless fabrication and direct nanoprinting. In this study, the differences in material composition depending on the employed process are illustrated for focused-ion-beam- and focused-electron-beam-induced deposition (FIBID/FEBID) and compared to the thermal decomposition in chemical vapor deposition (CVD). This article reports on specific differences in the deposit composition and microstructure when the (H3Si)2Fe(CO)4 precursor is converted into an inorganic material. Maximum metal/metalloid contents of up to 90 at. % are obtained in FIBID deposits and higher than 90 at. % in CVD films, while FEBID with the same precursor provides material containing less than 45 at. % total metal/metalloid content. Moreover, the Fe:Si ratio is retained well in FEBID and CVD processes, but FIBID using Ga+ ions liberates more than 50% of the initial Si provided by the precursor. This suggests that precursors for FIBID processes targeting binary materials should include multiple bonding such as bridging positions for nonmetals. In addition, an in situ method for investigations of supporting thermal effects of precursor fragmentation during the direct-writing processes is presented, and the applicability of the precursor for nanoscale 3D FEBID writing is demonstrated

Single-Molecule Conductance Behavior of Molecular Bundles

Controlling the orientation of complex molecules in molecular junctions is crucial to their development into functional devices. To date, this has been achieved through the use of multipodal compounds (i.e., containing more than two anchoring groups), resulting in the formation of tri/tetrapodal compounds. While such compounds have greatly improved orientation control, this comes at the cost of lower surface coverage. In this study, we examine an alternative approach for generating multimodal compounds by binding multiple independent molecular wires together through metal coordination to form a molecular bundle. This was achieved by coordinating iron(II) and cobalt(II) to 5,5′-bis(methylthio)-2,2′-bipyridine (L1) and (methylenebis(4,1-phenylene))bis(1-(5-(methylthio)pyridin-2-yl)methanimine) (L2) to give two monometallic complexes, Fe-1 and Co-1, and two bimetallic helicates, Fe-2 and Co-2. Using XPS, all of the complexes were shown to bind to a gold surface in a fac fashion through three thiomethyl groups. Using single-molecule conductance and DFT calculations, each of the ligands was shown to conduct as an independent wire with no impact from the rest of the complex. These results suggest that this is a useful approach for controlling the geometry of junction formation without altering the conductance behavior of the individual molecular wires