Synthesis and structure of a chiral areno-bridged [2.4]metacyclophane

The reductive coupling reaction of 1,4-bis(3-acetyl-5-tert-butyl-2-methoxyphenyl)butane 3 was carried out using TiCl₄-Zn in pyridine followed by a McMurry coupling reaction to afford the compounds anti and syn 1,2-dimethyl[2.4]MCP-1-ene 4. Bromination of 4 with BTMA-Br₃ in dry CH₂Cl₂ afforded the interesting compound 1,2-bis-(bromomethyl)-5,15-di-tert-butyl-8,18-dimethoxy[2.4]MCP-1-ene 6 and consecutive debromination with Zn and AcOH in CH₂Cl₂ solution afforded the stable solid 5,15-di-tert-butyl-8,18-dimethoxy-1,2-dimethylene[2.4]MCP 7 in 89% yield. Compound 7 was conveniently employed in a Diels–Alder reaction with dimethyl acetylenedicarboxylate (DMAD) to provide 2-(3′,6′-dihydrobenzo)-5,15-di-tert-butyl-8,18-dimethoxy[2.4]MCP-4′,5′-dimethylcarboxylate 8 in good yield. Diels–Alder adduct 8 was converted into a novel and inherently chiral areno-bridged compound [2.4]MCP 9 by aromatization. The chirality of the two conformers was characterized by circular dichroism (CD) spectra of the separated enantiomer which are perfect mirror images of each other.     

High Performance (fT~500GHZ) In0.52Al0.48As/In0.53Ga0.47As/InP Quantum Wire MODFETs Employing Asymmetric Coupled-Well Channels

A coupled-well InAlAs/InGaAs quantum wire MODFET structure is proposed, for which simulations predict improved frequency performance (>500 GHz), over a wider range of V_g, as compared to well/wire devices with a standard MODFET heterointerface. A comparison of several transverse potential well profiles, obtained by varying the placement of a thin barrier within a 100 Å finite well, is presented. In all cases, the quantum wires consist of a 0.1 m long channel and a 150 Å finite-square-well lateral profile. It has been found that the peak of the electron distribution for the first confined state, as measured from the heterointerface, changes dramatically depending on the location of the thin barrier. For quantum wire structures, realized in the lattice matched system of In_0.52Al_0.48As/In_0.53Ga_0.47As/InP, a change in the barrier location of 25 Å is accompanied by a shift in the carrier peak of more than 40 Å (~20 Å closer to or farther from the spacer-well interface than in the standard MODFET profile). Implications of this are reflected in the current-voltage characteristics (I_d-V_d) and frequency responses (f_T-V_g) of the proposed structures.     

Characterization of Langmuir-Blodgett film using differential charging in X-ray photoelectron spectroscopy

Differential charging is often regarded as a problem in X-ray photoelectron spectroscopy (XPS) studies, especially for insulating or partially conducting samples. Neutralization techniques have been developed to circumvent this effect. Instead of neutralizing the positive charge, which is often the technique to obtain good quality data, it is possible to exploit this phenomenon to get useful information about the sample. An attempt is made here to use this differential charging to study the mono- and multilayer Langmuir-Blodgett (LB) films of cadmium arachidate on silicon substrate. The surface potential was probed by measuring XPS line shift with respect to their neutral position and was found to have correlation with the thickness of the films. No differential charging was observed in the monolayer LB film where there was only one layer of cadmium headgroup. Significant differential charging was observed for multilayer films, the total charging as well as the differential charging in these films increase with increasing number of layers. Angle-resolved XPS measurements were performed to obtain additional information about the structure of the films. Charging of the upper layer of the films close to the vacuum interface was found to be less compared to that of the interior. The discrete cadmium layers were found to be more differentially charged compared to the continuous hydrocarbon stacks in the multilayer LB films. Charging of the discrete cadmium layers has been utilized to obtain quantitative information of the multilayer LB films.     

Synthesis of polyhydroxy piperidines and their analogues: a novel approach towards selective inhibitors of alpha-glucosidase

Various polyhydroxy piperidine azasugars have been synthesized from precursors 18a and 18b, obtained in both enantiomeric forms from d-ribose. Out of these polyhydroxy piperidine azasugars, 22, 39 and 20 were found to be potent as well as selective inhibitors of alpha-glucosidase with K(i) values ranging as low as 1.07 microM, 16.4 microM, and 88.2 microM, respectively. Replacement of the hydroxy methylene moiety of (K(i) 33% at 1 mM) by an amino methylene moiety (32, K(i) 36.8 microM) showed a remarkable increase in the activity (almost 30 times). Furthermore, increasing the lipophilicity of by N-alkylation with a dodecyl group (36) showed a three-fold enhancement in the activity (K(i) 217 microM to K(i) 72.3 microM).     

Synthesis and characterization of silicalite-1/carbon-graphite membranes

Silicalite-1/carbon-graphite composite membranes have been prepared using a standard hydrothermal synthesis method and characterized by XRD, SEM, TGA, BET and permeation experiments. Single gas permeation fluxes and binary mixtures separation and selectivity data are reported for methane, ethane and propane using the composite membranes. Carbon-graphite oxidized for 4 h prior to membrane preparation had the most promising separation properties. The permeation fluxes for the binary mixtures reflect that of the single component flux ratios. At 20 degrees C the membranes show high separation selectivity toward lighter component in binary mixtures. Single gas permeances for methane and ethane were found to decrease with increasing temperatures while that of propane fluctuates.     

Amphiphilic block copolymer-stabilized gold nanoparticles for aerobic oxidation of alcohols in aqueous solution

Stable Au nanoparticles in P123 aqueous solution using a simple method have been developed and the colloidal Au nanoparticles were successfully applied for the effective oxidation of various alcohols using molecular O(2) as oxidant at 30 degrees C in aqueous solution.     

Two-Dimensional Supramolecular Polymerization of a Bis-Urea Macrocycle into a Brick-Like Hydrogen-Bonded Network

We report on a dendronized bis-urea macrocycle 1 self-assembling via a cooperative mechanism into two-dimensional (2D) nanosheets formed solely by alternated urea-urea hydrogen bonding interactions. The pure macrocycle self-assembles in bulk into one-dimensional liquid-crystalline columnar phases. In contrast, its self-assembly mode drastically changes in CHCl₃ or tetrachloroethane, leading to 2D hydrogen-bonded networks. Theoretical calculations, complemented by previously reported crystalline structures, indicate that the 2D assembly is formed by a brick-like hydrogen bonding pattern between bis-urea macrocycles. This assembly is promoted by the swelling of the trisdodecyloxyphenyl groups upon solvation, which frustrates, due to steric effects, the formation of the thermodynamically more stable columnar macrocycle stacks. This work proposes a new design strategy to access 2D supramolecular polymers by means of a single non-covalent interaction motif, which is of great interest for materials development.     

Through-bond excited energy transfer mediated by an amidinium-carboxylate salt bridge in Zn-porphyrin free-base porphyrin dyads

Excited energy-transfer processes were investigated for a supramolecular Zn-porphyrin free-base porphyrin dyad, ZnPA-2 x FbPC-2, in which beta-octaalkylated meso-diarylporphyrins are connected through an amidinium-carboxylate salt bridge. The rate of energy transfer in the dyad (1.3 x 10(9) s(-1)) is substantially slower than that in the previously reported dyad, ZnPA-1FbPC-1 (4.0 x 10(9) s(-1)), in which meso-tetraarylporphyrins are connected through the same amidinium-carboxylate salt bridge. The F?rster-type mechanism can explain only minor parts of these rates (3.3 x 10(8) and 5.1 x 10(8) s(-1), respectively). Thus, Dexter-type through-bond energy transfer may be invoked. Indeed, bridge-mediated electronic processes would be favored in ZnPA-1 x FbPC-1 over ZnPA-2 x FbPC-2 on the basis of steric and electronic factors. Sterically, the phenyl groups in ZnPA-2 and FbPC-2 are more closely perpendicular to the porphyrin planes than those in ZnPA-1 and FbPC-1. Electronically, the energy and symmetry of the occupied frontier orbitals should favor ZnPA-1 x FbPC-1 over ZnPA-2 x FbPC-2 in terms of electronic interactions through the bridge. Therefore, the observed trend (ZnPA-1 x FbPC-1>ZnPA-2 x FbPC-2), consistent with these considerations, lends further support to the through-bond mechanism. Thus, the amidinium-carboxylate salt bridge is effective in mediating through-bond energy transfer even though the bond is noncovalent.     

Organic/inorganic interfaced field-effect transistor properties with a novel organic semiconducting material

A novel 1,3,4-oxadiazole-substituted benzo[b]triphenylene was synthesized by three-step synthetic procedure and OFET device design was successfully designed after theoretical calculations made using Gaussian software. For investigating the field-effect properties of designed organic electronic device, a SiO₂ (300 nm) was thermally grown on p-Si wafer at 1000 °C as a dielectric layer and gate, source and drain contacts have been deposited using Au metal with physical vapour deposition. 1,3,4-Oxadiazole-substituted benzo[b]triphenylene was spin coated on the source and drain electrodes of our device, forming organic/inorganic interfaced field-effect transistors. Surface morphology and thin film properties were investigated using AFM. All electrical measurements were done in air ambient. The device showed a typical p-type channel behaviour with increasing negative gate bias voltage values. Our results have surprisingly shown that the saturation regime of this device has high mobility (μ_FET), excellent on/off ratio (I_on/I_off), high transconductance (g_m) and a small threshold voltage (V_Th). The values of μ_FET, I_on/I_off, g_m and V_Th were found as 5.02 cm²/Vs, 0.7 × 10³, 5.64 μS/mm and 1.37 V, respectively. These values show that our novel organic material could be a potential candidate for organic electronic device applications in the future.