The significance of Kekulé structures for the stability of aromatic systems—II

Dihydroheptazethrene (V) and 1:14,11:12-dibenzo-5,7-dihydro-pentacene (VI) were synthesized. The former gave heptazethrene (VII) on dehydrogenation, whilst the latter polymerized immediately. This difference is explained by the fact that heptazethrene (VII) can be formulated with a Kekulé structure and the dehydrogenation product of VI cannot. Heptazethrene is a basis hydrocarbon and is closely related to dibenzoheptazethrene (VIII). Heptazethrenequinone (II) is a true quinone giving a blue vat, whilst the isomer (IV) is a diketone and does not give a vat.     

Molecular ordering and 2D conductivity in ultrathin poly(3-hexylthiophene)/gold nanoparticle composite films

This paper reports the first comparison of the structure and electrical conductivity properties of spin cast (SC) and Langmuir-Schaeffer (LS) films of regioregular poly(3-hexylthiophene) (P3HT). In addition, the effect of incorporating highly monodisperse Au nanoparticles (NPs), with a core diameter of approximately 5 nm, into SC and LS P3HT films is described. A detailed picture of molecular organization in the films has been obtained using ultraviolet-visible absorption spectroscopy, atomic force microscopy, field-emission scanning electron microscopy, X-ray diffraction, and X-ray reflectivity. Film morphology was correlated with pseudo-two-dimensional conductivity measured using scanning electrochemical microscopy, with P3HT in the semiconducting regime. It was found that SC films, which were slightly thicker than those formed with the LS technique, exhibited greater organization. This resulted in an order of magnitude higher lateral conductivity for the SC films. Inclusion of Au NPs (50 wt %) into both SC and LS films resulted in the formation of uniform and relatively flat (rms roughness approximately 1 nm) composite films. Surprisingly, the addition of NPs did not disrupt the characteristic crystal structure found for the native P3HT films. The effect of Au NPs on film lateral conductivity was found to be determined by the distribution of Au NPs within the polymer, which varied significantly between SC and LS films. Whereas Au NPs aggregated into hexagonally packed clusters in SC films, NPs in LS films were predominantly uniformly distributed between the lamella bilayer. It was found that, while the inclusion of Au NPs caused the lateral conductivity to decrease in SC films, in LS films, the lateral conductivity increased by a factor of 2.     

Macrocycles in the construction of acyclic stereochemistry

The conformations of macrocyclic intermediates provide a useful medium through which distant chiral centers may control chemical reactions. In this paper, we show that macrocycles made by cyclization of simple acyclic starting materials with an auxiliary spacer may be used to prepare stereochemically complex acyclic products.     

Measurement of PCDDs, PCDFs, and non-ortho-PCBs by comprehensive two-dimensional gas chromatography-isotope dilution time-of-flight mass spectrometry (GC x GC-IDTOFMS)

Comprehensive two-dimensional gas chromatography with isotope-dilution time-of-flight mass spectrometry (GC × GC-IDTOFMS) was used to measure polychlorinated dibenzo-p-dioxin (PCDD), polychlorinated dibenzofuran (PCDF), and coplanar polychlorinated biphenyl (cPCB) concentrations in ash, sediment, vegetation, and fish samples. The GC × GC capability was achieved by using a quad jet, dual stage, thermal modulator. Zone compression of the GC peaks from modulation resulted in a significant increase of the signal intensity over classical GC-IDTOFMS. The GC × GC column set used an Rtx-Dioxin 2 phase as the first dimension (¹D) and an Rtx-500 as the second dimension (²D). The chromatographic separation of the 17 PCDD/Fs and the 4 cPCBs was attained in ¹D except for 2,3,7,8-TCDD and CB126 for which deconvoluted ion currents (DIC) were required to be reported separately. The Rtx-500 phase separated the bulk matrix interfering compounds from the target analytes in ²D. The instrumental limit of detection (iLODs) was 0.5 pg for 2,3,7,8-TCDD. The calibration curves showed good correlation coefficients for all the compounds investigated in the concentration range of 0.5–200 pg. GC × GC-IDTOFMS results compared favorably to those from conventional isotope-dilution one-dimensional gas chromatography-high resolution mass spectrometry (GC-IDHRMS). The comprehensive mass analysis of the TOFMS further permitted the identification of other contaminants of concern in the samples.     

Electrochemical templating of metal nanoparticles and nanowires on single-walled carbon nanotube networks

The use of single-walled carbon nanotube (SWNT) networks as templates for the electrodeposition of metal (Ag and Pt) nanostructures is described. Pristine SWNTs, grown on insulating SiO2 surfaces using catalyzed chemical vapor deposition, served as the working electrode. In the simplest case, electrical contact was made by depositing a gold strip on the SWNT substrate (device 1). Deposition of Ag and Pt over extensive periods (30 s) resulted in a high density of particles on the SWNTs, with almost contiguous nanowire formation from the Au/SWNT boundary moving to isolated nanoparticles at further distances from the contact. For direct electrochemical studies of Ag and Pt nucleation, the assembly was coated in a resist layer and a small window opened up to expose only the electrically connected SWNTs to solution (device 2). In this case, the electrochemical signature in voltammetric and amperometric studies of metal deposition was due solely to processes at the SWNTs. Coupled with high-resolution microscopy measurements (atomic force microscopy and field emission scanning electron microscopy), this approach provided detail on the nucleation and growth mechanisms of Ag and Pt on SWNTs under electrochemical control. In particular, Ag growth was found to be rapid and progressive with an increasing nanoparticle density with time, whereas Pt deposition was characterized by lower nucleation densities and slower growth rates with a tendency for larger particles to be produced over long times.     

Scanning electrochemical microscopy as a probe of Ag+ binding kinetics at Langmuir phospholipid monolayers

A new method has been developed for measuring local adsorption rates of metal ions at interfaces based on scanning electrochemical microscopy (SECM). The technique is illustrated with the example of Ag+ binding at Langmuir phospholipid monolayers formed at the water/air interface. Specifically, an inverted 25 microm diameter silver disc ultramicroelectrode (UME) was positioned in the subphase of a Langmuir trough, close to a dipalmitoyl phosphatidic acid (DPPA) monolayer, and used to generate Ag+ via Ag electro-oxidation. The method involved measuring the transient current-time response at the UME when the electrode was switched to a potential to electrogenerate Ag+. Since the Ag+/Ag couple is reversible, the response is highly sensitive to local mass transfer of Ag+ away from the electrode, which, in turn, is governed by the interaction of Ag+ with the monolayer. The methodology has been used to determine the influence of surface pressure on the adsorption of Ag+ ions at a phospholipid (dipalmitoyl phosphatidic acid) Langmuir monolayer. It is shown that the capacity for metal ion adsorption at the monolayer increased as the density of surface adsorption sites increased (by increasing the surface pressure). A model for mass transport and adsorption in this geometry has been developed to explain and characterise the adsorption process.     

The Rate Problem of a Thermally Regenerable Ion-Exchange System

Earlier equilibrium studies have established the thermal dependence of the equilibrium between salt solution and a mixed bed of weakly basic and weakly acidic ion-exchange resins. High resin utilization can be achieved if the resin properties and equilibrium conditions are optimized; the equilibrium characteristics of polyacrylic acid and polyvinylbenzyldiethylamine resins are quite suited for the practical desalination of brackish waters.

However, the adsorption rates exhibited by normal-sized resin beads of this type are much too slow for satisfactory operation of the process because of the low concentration of protons available for transfer between the resins. It is shown that increasing the porosity of the resins improves amine resin kinetics 10-fold and carboxylic acid resin kinetics 6-fold. Nevertheless such improvements are still inadequate for practical purposes, and it is concluded that for satisfactory rates to be achieved systems having much shorter diffusion paths are necessary.

Two further approaches to the rate problem are discussed, both involving the synthesis of novel resin systems. A mixed bed of microbeads (10-20 p) reacts at acceptable rates but presents mechanical problems; the magnetic flocculation of finely divided magnetic resins is reported as one possible solution to this problem. Another avenue is the synthesis of normal-sized beads of the amphoteric and snake-cage variety. Resins of this type that exchange at suitable rates are described.     

Minimality conditions on circularly ordered structures

We explore analogues of o‐minimality and weak o‐minimality for circularly ordered sets. Much of the theory goes through almost unchanged, since over a parameter the circular order yields a definable linear order. Working over ?? there are differences. Our main result is a structure theory (with infinitely many doubly transitive examples related to Jordan permutation groups) for ?₀‐categorical weakly circularly minimal structures. There is a 5‐homogeneous (or ‘5‐indiscernible’) example which is not 6‐homogeneous, but any example which is k‐homogeneous for some k ≥ 6 is k‐homogeneous for all k. (© 2005 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)     

Binaural weighting of monaural spectral cues for sound localization

For human listeners, cues for vertical-plane localization are provided by direction-dependent pinna filtering. This study quantified listeners' weighting of the spectral cues from each ear as a function of stimulus lateral angle, interaural time difference (ITD), and interaural level difference (ILD). Subjects indicated the apparent position of headphone-presented noise bursts synthesized in virtual auditory space. The synthesis filters for the two ears either corresponded to the same location or to two different locations separated vertically by 20 deg. Weighting of each ear's spectral information was determined by a multiple regression between the elevations to which each ear's spectrum corresponded and the vertical component of listeners' responses. The apparent horizontal source location was controlled either by choosing synthesis filters corresponding to locations on or 30 deg left or right of the median plane or by attenuating or delaying the signal at one ear. For broadband stimuli, spectral weighting and apparent lateral angle were determined primarily by ITD. Only for high-pass stimuli were weighting and lateral angle determined primarily by ILD. The results suggest that the weighting of monaural spectral cues and the perceived lateral angle of a sound source depend similarly on ITD, ILD, and stimulus spectral range.