Selecting Room-Temperature Ionic Liquids to Optimize Voltammetric Responses: The Oxidation of NADH

The electrochemistry of nicotinamide adenine dinucleotide (NADH) in its reduced form was examined in two room-temperature ionic liquids (RTILs): 1-ethyl-3-methylimidazolium bis-(trifluoromethylsulfonyl)imide ([C(2)mim][NTf2]) and 1-butyl-3-methylimidazolium hexafluorophos-phate ([C(4)mim][PF6]). NADH oxidation has previously been studied in aqueous solution where it follows the pathway: one-electron oxidation to the NADH(center dot+) radical cation, deprotonation to produce the neutral NAD(center dot) radical, then oxidation to the NAD(+) cation. The electrochemistry of NADH was examined in [C(2)mim][NTf2] and [C(4)mim][PF6] at the bare Pt electrode (10 mu m diameter): In [C(2)mim][NTf2], no oxidation was observed; in [C(4)mim][PF6], an oxidative signal was observed, which likely followed the pathway described above, where upon formation of the NADH(center dot+) radical cation, the [PF6](-) anion (unlike the [NTf2](-) anion) reacts with the proton to form HPF6, which decomposes. This demonstrates the tunability of RTILs, whereby the choice of one anion in an RTIL over another can promote a reaction. Poly(vinylferrocene) (PVF) was studied as a mediator for the NADH detection in both RTILs to attempt to lower the potential of NADH detection. The Pt electrode was modified with PVF, and the oxidation of PVF to PVF+ was observed in [C(2)mim][NTf2] and [C(4)mim][PF6], but no mediation of the NADH oxidation was observed.

Liquid Structure and Dynamics of Aqueous Isopropanol over gamma-Alumina

The liquid structures of thin films of aqueous solutions of 0, 7, 19, 50, and 100 mol % isopropanol above O/Al-terminated gamma-alumina surfaces have been investigated by means of classical molecular dynamics simulations. The structuring effect of the oxide oil the liquid mixtures is strong and heavily dependent on the local structure of the oxide. Two distinct re-ions are found oil the oxide Surface characterized by the degree of coordination of Al atoms. Above octahedral Al atoms, water and isopropanol molecules adsorb via the oxygen atoms to maximize the electrostatic interaction, whereas above tetrahedral Al sites the solvent molecules adsorb via hydrogen atoms with the oxygen atoms away front the surface. More mobility is found in the second layer compared with the first; however, its structure is still influenced significantly by the orientation of molecules in the first adsorbed layer. Qualitatively, the displacement of water from the surface by the adsorption of isopropanol occurs with 2.6 Water molecules lost for every alcohol molecule present based on the effective surface areas of the two species calculated from the pure simulations.

Raman microscopy in the diagnosis and prognosis of surgically resected nonsmall cell lung cancer

The main curative therapy for patients with nonsmall cell lung cancer is surgery. Despite this, the survival rate is only 50%, therefore it is important to more efficiently diagnose and predict prognosis for lung cancer patients. Raman spectroscopy is useful in the diagnosis of malignant and premalignant lesions. The aim of this study is to investigate the ability of Raman microscopy to diagnose lung cancer from surgically resected tissue sections, and predict the prognosis of these patients. Tumor tissue sections from curative resections are mapped by Raman microscopy and the spectra analzsed using multivariate techniques. Spectra from the tumor samples are also compared with their outcome data to define their prognostic significance. Using principal component analysis and random forest classification, Raman microscopy differentiates malignant from normal lung tissue. Principal component analysis of 34 tumor spectra predicts early postoperative cancer recurrence with a sensitivity of 73% and specificity of 74%. Spectral analysis reveals elevated porphyrin levels in the normal samples and more DNA in the tumor samples. Raman microscopy can be a useful technique for the diagnosis and prognosis of lung cancer patients receiving surgery, and for elucidating the biochemical properties of lung tumors. (C) 2010 Society of Photo-Optical Instrumentation Engineers. [DOI: 10.1117/1.3323088]

USE OF RETRODIRECTIVE ARRAY PHASE CONJUGATION CIRCUITRY FOR NEAR- AND FAR-FIELD POSITION ANGLE OF ARRIVAL DETECTION

In this article, we present position indication functionality as obtained by using a retrodirective array, thereby allowing location information extraction of the position of the remote transmitter with which the retrodirective array is cooperating. This is carried out using straightforward circuitry with no requirement for complex angle of arrival algorithms, thereby giving a result in real time enabling tracking of fast moving transmitters. We show using a 10 x element retrodirective array, operating at 2.4 GHz that accuracies of far-field angle of arrival of within +/- 1 degrees over the arrays +/- 30 degrees azimuth field of view are possible. While in the near-field for angles of arrival of +/- 10 degrees it is possible to extract the position of a dipole source down to a resolution of 032 lambda. (C) 2010 Wiley Periodicals, Inc. Microwave Opt Technol Lett 52: 1031-1034, 2010; Published online in Wiley InterScience (www.interscience.wiley.com). DOI 10.1002/mop.25097

RCS CONTROL USING CASCADED CIRCULARLY POLARIZED FREQUENCY SELECTIVE SURFACES AND AN AMC STRUCTURE AS A SWITCHABLE TWIST POLARIZER

This article presents a cascaded arrangement comprising a double-layer frequency selective surface circularly polarizing (CPFSS) and a second screen that can be switched between artificial magnetic conduction (AMC) or perfect electric conducting. (PEC) states. The CPFSS consists of two stacked aluminium sheets patterned with periodic split ring structures While the AMC is a PCB sheet patterned with metallic squares interconnected by links By either open or short circuiting these links it is shown that the cascade of screens can be made to twist, or not to twist, an incident 45 degrees linearly polirized signal through 90 degrees upon reflection from the assembly The system was designed and optimized using CST software and predictions were validated experimentally and measured monostatic reflection loss results (C) 2010 Wiley Periodicals, Inc Microwave Opt Technol Lett 52 577-580, 2010. Published online in Wiley InterScience (www.interscience.wiley.com) DOI 10.1002/mop.24979

Anionic N,O-ligated Pd(II) complexes: highly active catalysts for alcohol oxidation.

There is a need to develop effective catalytic methods for alcohol oxidation. Pd(II) complexes have shown great promise as catalysts, however a comparatively small number of ligands have been reported so far. Herein we report the use of commercially available anionic N,O-ligands to produce highly active catalysts.

Total synthesis of (+)-A83586C, (+)-kettapeptin and (+)-azinothricin: powerful new inhibitors of beta-catenin/TCF4-and E2F-mediated gene transcription

Herein we describe our asymmetric total syntheses of (+)-A83586C, (+)-kettapeptin and (+)-azinothricin. We also demonstrate that molecules of this class powerfully inhibit beta-catenin/TCF4- and E2F-mediated gene transcription within malignant human colon cancer cells at low drug concentrations.

On the dissolution of non-metallic solid elements (sulfur, selenium, tellurium and phosphorus) in ionic liquids

Ionic liquids are shown to be good solvents for elemental sulfur, selenium, phosphorus and tellurium, and can be designed to maximise the solubility of these elements. The presence of the [S-3](center dot-) radical anion in diluted solutions of sulfur in some ionic liquids has been confirmed, and is the origin of their intense blue colour (cf. lapis lazuli).

Fast, copper-free click chemistry: a convenient solid-phase approach to oligonucleotide conjugation

Solid-phase oligonucleotide conjugation by nitrile oxide-alkyne click cycloaddition chemistry has been successfully demonstrated; the reaction, compatible with all nucleobases, requires no metal catalyst and proceeds under physiological conditions.

Electromagnetic interaction between a metallic nanoparticle and surface in tunnelling proximity-modelling and experiment

We simulate the localized surface plasmon resonances of an Au nanoparticle within tunnelling proximity of an Au substrate. The results demonstrate that the calculated resonance energies can be identified with those experimentally detected for light emission from the tip-sample junction of a scanning tunnelling microscope. Relative to the modes of an isolated nanoparticle these modes show significant red-shifting, extending further into the infrared with increasing radius, primarily due to a proximity-induced lowering of the effective bulk plasmon frequency. Spatial mapping of the field enhancement factor shows an oscillatory variation of the field, absent in the case of a dielectric substrate; also the degree of localization of the modes, and thus the resolution achievable electromagnetically, is shown to depend primarily on the nanoparticle radius, which is only weakly dependent on wavelength.

Barrier height variations and interface properties of PtSi/Si structures

To study some of the interfacial properties of PtSi/Si diodes, Schottky structures were fabricated on (100) crystalline silicon substrates by conventional thermal evaporation of Pt on Si followed by annealing at different temperatures (from 400 degrees C to 700 degrees C) to form PtSi. The PtSi/n-Si diodes, all yielded Schottky barrier (SB) heights that are remarkably temperature dependent. The temperature range (20-290 K) over which the I-V characteristics were measured in the present study is broader with a much lower limit (20 K), than what is usually reported in literature. These variations in the barrier height are adequately interpreted by introducing spatial inhomogeneity into the barrier potential with a Gaussian distribution having a mean barrier of 0.76 eV and a standard deviation of 30 meV. Multi-frequency capacitance-voltage measurements suggest that the barrier is primarily controlled by the properties of the silicide-silicon interface. The forward C-V characteristics, in particular, show small peaks at low frequencies that can be ascribed to interface states rather than to a series resistance effect.

Quantum efficiency in GaAs Schottky photodetectors with enhancement due to surface plasmon excitations

The overall quantum efficiency in surface plasmon (SP) enhanced Schottky barrier photodetectors is examined by considering both the external and internal yield. The external yield is considered through calculations of absorption and transmission of light in a configuration that allows reflectance minimization due to SP excitation. Following a Monte Carlo method, a procedure is presented to estimate the internal yield while taking into account the effect of elastic and inelastic scattering processes on excited carriers subsequent to photon absorption. The relative importance of internal photoemission and band-to-band contributions to the internal yield is highlighted along with the variation of the yield as a function of wavelength, metal thickness and other salient parameters of the detector. (C) 2002 Elsevier Science Ltd. All rights reserved.