Permethylation Introduces Destructive Quantum Interference in Saturated Silanes.

The single-molecule conductance of silanes is suppressed due to destructive quantum interference in conformations with cisoid dihedral angles along the molecular backbone. Yet, despite the structural similarity, σ-interference effects have not been observed in alkanes. Here we report that the methyl substituents used in silanes are a prerequisite for σ-interference in these systems. Through density functional theory calculations, we find that the destructive interference is not evident to the same extent in nonmethylated silanes. We find the same is true in alkanes as the transmission is significantly suppressed in permethylated cyclic and bicyclic alkanes. Using scanning tunneling microscope break-junction method we determine the single-molecule conductance of functionalized cyclohexane and bicyclo[2.2.2]octane that are found to be higher than that of equivalent permethylated silanes. Rather than the difference between carbon and silicon atoms in the molecular backbones, our calculations reveal that it is primarily the difference between hydrogen and methyl substituents that result in the different electron transport properties of nonmethylated alkanes and permethylated silanes. Chemical substituents play an important role in determining the single-molecule conductance of saturated molecules, and this must be considered when we improve and expand the chemical design of insulating organic molecules.

Large Variations in the Single-Molecule Conductance of Cyclic and Bicyclic Silanes.

Linear silanes are efficient molecular wires due to strong σ-conjugation in the transoid conformation; however, the structure-function relationship for the conformational dependence of the single-molecule conductance of silanes remains untested. Here we report the syntheses, electrical measurements, and theoretical characterization of four series of functionalized cyclic and bicyclic silanes including a cyclotetrasilane, a cyclopentasilane, a bicyclo[2.2.1]heptasilane, and a bicyclo[2.2.2]octasilane, which are all extended by linear silicon linkers of varying length. We find an unusual variation of the single-molecule conductance among the four series at each linker length. We determine the relative conductance of the (bi)cyclic silicon structures by using the common length dependence of the four series rather than comparing the conductance at a single length. In contrast with the cyclic π-conjugated molecules, the conductance of σ-conjugated (bi)cyclic silanes is dominated by a single path through the molecule and is controlled by the dihedral angles along this path. This strong sensitivity to molecular conformation dictates the single-molecule conductance of σ-conjugated silanes and allows for systematic control of the conductance through molecular design.

Silane and Germane Molecular Electronics.

This Account provides an overview of our recent efforts to uncover the fundamental charge transport properties of Si-Si and Ge-Ge single bonds and introduce useful functions into group 14 molecular wires. We utilize the tools of chemical synthesis and a scanning tunneling microscopy-based break-junction technique to study the mechanism of charge transport in these molecular systems. We evaluated the fundamental ability of silicon, germanium, and carbon molecular wires to transport charge by comparing conductances within families of well-defined structures, the members of which differ only in the number of Si (or Ge or C) atoms in the wire. For each family, this procedure yielded a length-dependent conductance decay parameter, ß. Comparison of the different ß values demonstrates that Si-Si and Ge-Ge σ bonds are more conductive than the analogous C-C σ bonds. These molecular trends mirror what is seen in the bulk. The conductance decay of Si and Ge-based wires is similar in magnitude to those from π-based molecular wires such as paraphenylenes However, the chemistry of the linkers that attach the molecular wires to the electrodes has a large influence on the resulting ß value. For example, Si- and Ge-based wires of many different lengths connected with a methyl-thiomethyl linker give ß values of 0.36-0.39 Å-1, whereas Si- and Ge-based wires connected with aryl-thiomethyl groups give drastically different ß values for short and long wires. This observation inspired us to study molecular wires that are composed of both π- and σ-orbitals. The sequence and composition of group 14 atoms in the σ chain modulates the electronic coupling between the π end-groups and dictates the molecular conductance. The conductance behavior originates from the coupling between the subunits, which can be understood by considering periodic trends such as bond length, polarizability, and bond polarity. We found that the same periodic trends determine the electric field-induced breakdown properties of individual Si-Si, Ge-Ge, Si-O, Si-C, and C-C bonds. Building from these studies, we have prepared a system that has two different, alternative conductance pathways. In this wire, we can intentionally break a labile, strained silicon-silicon bond and thereby shunt the current through the secondary conduction pathway. This type of in situ bond-rupture provides a new tool to study single molecule reactions that are induced by electric fields. Moreover, these studies provide guidance for designing dielectric materials as well as molecular devices that require stability under high voltage bias. The fundamental studies on the structure/function relationships of the molecular wires have guided the design of new functional systems based on the Si- and Ge-based wires. For example, we exploited the principle of strain-induced Lewis acidity from reaction chemistry to design a single molecule switch that can be controllably switched between two conductive states by varying the distance between the tip and substrate electrodes. We found that the strain intrinsic to the disilaacenaphthene scaffold also creates two state conductance switching. Finally, we demonstrate the first example of a stereoelectronic conductance switch, and we demonstrate that the switching relies crucially on the electronic delocalization in Si-Si and Ge-Ge wire backbones. These studies illustrate the untapped potential in using Si- and Ge-based wires to design and control charge transport at the nanoscale and to allow quantum mechanics to be used as a tool to design ultraminiaturized switches.

High-performance glucose biosensor based on chitosan-glucose oxidase immobilized polypyrrole/Nafion/functionalized multi-walled carbon nanotubes bio-nanohybrid film.

A highly electroactive bio-nanohybrid film of polypyrrole (PPy)-Nafion (Nf)-functionalized multi-walled carbon nanotubes (fMWCNTs) nanocomposite was prepared on the glassy carbon electrode (GCE) by a facile one-step electrochemical polymerization technique followed by chitosan-glucose oxidase (CH-GOx) immobilization on its surface to achieve a high-performance glucose biosensor. The as-fabricated nanohybrid composite provides high surface area for GOx immobilization and thus enhances the enzyme-loading efficiency. The structural characterization revealed that the PPy-Nf-fMWCNTs nanocomposite films were uniformly formed on GCE and after GOx immobilization, the surface porosities of the film were decreased due to enzyme encapsulation inside the bio-nanohybrid composite materials. The electrochemical behavior of the fabricated biosensor was investigated by cyclic voltammetry (CV), electrochemical impedance spectroscopy (EIS), and amperometry measurements. The results indicated an excellent catalytic property of bio-nanohybrid film for glucose detection with improved sensitivity of 2860.3µAmM(-1)cm(-2), the linear range up to 4.7mM (R(2)=0.9992), and a low detection limit of 5µM under a signal/noise (S/N) ratio of 3. Furthermore, the resulting biosensor presented reliable selectivity, better long-term stability, good repeatability, reproducibility, and acceptable measurement of glucose concentration in real serum samples. Thus, this fabricated biosensor provides an efficient and highly sensitive platform for glucose sensing and can open up new avenues for clinical applications.

Conformations of cyclopentasilane stereoisomers control molecular junction conductance.

Here we examine the impact of ring conformation on the charge transport characteristics of cyclic pentasilane structures bound to gold electrodes in single molecule junctions. We investigate the conductance properties of alkylated cyclopentasilane cis and trans stereoisomers substituted in the 1,3-position with methylthiomethyl electrode binding groups using both the scanning tunneling microscope-based break junction technique and density functional theory based ab initio calculations. In contrast with the linear ones, these cyclic silanes yield lower conductance values; calculations reveal that the constrained dihedral geometries occurring within the ring are suboptimal for σ-orbital delocalization, and therefore, conductance. Theoretical calculations reproduce the measured conductance trends for both cis and trans isomers and find several distinct conformations that are likely to form stable molecular junctions at room temperature. Due to the weakened σ-conjugation in the molecule, through-space interactions are found to contribute significantly to the conductance. This manuscript details the vast conformational flexibility in cyclopentasilanes and the tremendous impact it has on controlling conductance.

Single-molecule conductance in atomically precise germanium wires.

While the electrical conductivity of bulk-scale group 14 materials such as diamond carbon, silicon, and germanium is well understood, there is a gap in knowledge regarding the conductivity of these materials at the nano and molecular scales. Filling this gap is important because integrated circuits have shrunk so far that their active regions, which rely so heavily on silicon and germanium, begin to resemble ornate molecules rather than extended solids. Here we unveil a new approach for synthesizing atomically discrete wires of germanium and present the first conductance measurements of molecular germanium using a scanning tunneling microscope-based break-junction (STM-BJ) technique. Our findings show that germanium and silicon wires are nearly identical in conductivity at the molecular scale, and that both are much more conductive than aliphatic carbon. We demonstrate that the strong donor ability of C-Ge σ-bonds can be used to raise the energy of the anchor lone pair and increase conductance. Furthermore, the oligogermane wires behave as conductance switches that function through stereoelectronic logic. These devices can be trained to operate with a higher switching factor by repeatedly compressing and elongating the molecular junction.

Fabrication of highly porous poly (ɛ-caprolactone) fibers for novel tissue scaffold via water-bath electrospinning.

Highly porous fibers were prepared by water-bath electrospinning from pure poly(ɛ-caprolactone) (PCL), and its blends with methoxy poly(ethylene glycol) (MPEG). These fibers were further analyzed by scanning electron microscopy (SEM), differential scanning calorimetry (DSC), X-ray diffraction (XRD), and gravimetric as well as contact angle measurement. SEM images showed that the fibers diameters as well as pores diameter on the fibers were affected by the weight ratio of MPEG/PCL. DSC and XRD not only revealed suppression of crystallinity of PCL but also indicated the presence of trace amount of MPEG in PCL water-bath collected fibers. The potential use of these hydrophilic porous electrospun fibrous mats as scaffolding materials was evaluated in vitro using mouse osteoblasts (MC3T3-E1) as reference cell lines. Cytotoxicity assessment of the fiber mats indicated that the porous electrospun mat containing trace amount of MPEG was nontoxic to the cell. Cell culture results showed that porous fibrous mats were good in promoting the cell attachment and proliferation. This novel electrospun matrix could be used as potential tissue scaffold material.

Influence of heat treatment on morphological changes of nano-structured titanium oxide formed by anodic oxidation of titanium in acidic fluoride solution.

TiO(2) nanotube array (TN) on titanium plate was fabricated by using an electrochemical method. The crystal structure and surface morphology of TN array was examined by X-ray diffraction (XRD) and Field Emission Scanning Electronic Microscopy (FE-SEM), respectively. The stability of the nanotube structure and crystal phase transition was studied at different temperatures in dry oxygen ambient. The as-deposited films were found to be amorphous. The tubes crystallized in the anatase phase at a temperature of 450 degrees C. Anatase crystallites formed inside the tubes walls was transformed completely to rutile at 500 degrees C in dry environment. With the heating temperature increased the intensity of rutile peak increased with decrease in reflection from titanium. Intense rutile peak was observed at 600 degrees C. The average pore diameter as calculated from FE-SEM images was 50-100 nm. At higher temperature tubular structure completely collapsed leaving dense rutile crystallites. A model was proposed to explain the formation mechanism of TN fabricated on titanium plate in HF/H(2)SO(4) electrolyte.