Anionic migration in aromatic systems effected by collisional activation. Unusual fragmentations of deprotonated anilides containing methoxyl and ethoxyl substituents

Long-range cross-ring reactions occur when (M - H)(-) ions of methoxy- and ethoxy-C6H4-(-)NCOR (R = H, CH3, C6H5 and CH3O) are subjected to collisional activation, These reactions are generally minor processes: a particular example is the cross-ring elimination p-C2H5O-C6H4-(NCOCH3)-N-- --> [CH3-(p-C2H5O-C6H4-NCO)] --> p-(O--)-C6H4-NCO + C2H4 + CH4. Major processes of these (M - H)(-) ions involve (i) losses of radicals to form stabilised radical anions, e.g. (a) loss of a ring H-. or (b) CH3. (or C2H5.) from the alkoxy group, and (ii) proximity effects when the two substituents are ortho, e.g. loss of CH3OH from o-CH3O-C6H4-(NCHO)-N-- yields deprotonated benzoxazole. Another fragmentation of an arylmethoxyl anion involves loss of CH2O. It is proposed that losses of CH2O are initiated by anionic centres but the actual mechanisms in the cases studied depend upon the substitution pattern of the methoxyanilide: o- and p-methoxyanilides may undergo ipso proton transfer/elimination reactions, whereas the in-analogues undergo proton transfer reactions to yield an o-CH3O substituted aryl carbanion followed by proton transfer from CH3O to the carbanion site with concomitant loss of CH2O.

Supramolecular organization in fluorene/indenofluorene-oligothiophene alternating conjugated copolymers

A series of conjugated copolymers containing fluorene or indenofluorene units alternating with oligothiophene segments, with potential interest for use as the active layer in field-effect transistors, is investigated. Atomic force microscopy analysis of the morphology of thin deposits shows either the formation of fibrillar structures, which are the signature of long-range π stacking, or the presence of untextured aggregates, resulting from disordered assembly. These morphologies are interpreted in terms of the supramolecular organization of the conjugated chains. Molecular modeling simulations indicate that the commensurability between the lengths of the monomer units and the presence of alkyl side groups are the two key structural factors governing the chain organization into highly ordered assemblies. The most favorable structures are those combining fluorene (indenofluorene) units with unsubstituted bithiophene (terthiophene) segments.

Price linkages in the copper futures, primary, and scrap markets

This study investigates how markets for different levels of copper purity are interrelated by testing the long-run price linkage and causalities among the copper futures, primary, copper scrap, and brass scrap markets. It is expected that copper markets that deal with high purity levels, such as the futures, primary, and copper scrap markets, have a long-run relationship. However, brass scrap markets where copper with a lower purity is traded may not have a price linkage with other copper markets. The results reveal that a long-run relationship holds between the futures, primary, and copper scrap markets but the brass scrap market does not have a long-run relationship with the other markets. From the short-run and long-run causality tests, we determine that the futures market plays an important role in transmitting price information to other copper markets while such information flow is not found for the brass scrap market.

Levels and trends of PBDEs and HBCDs in the global environment : status at the end of 2012

In this paper, we have compiled and reviewed the most recent literature, published from January2010 to December 2012, relating to the human exposure, environmental distribution, behaviour, fate and concentration time trends of polybrominated diphenyl ether (PBDE) and hexabromocyclododecane (HBCD) flame retardants, in order to establish their current trends and priorities for future study. Due to the large volume of literature included, we have provided full detail of the reviewed studies as Electronic Supplementary Information and here summarise the most relevant findings. Decreasing time trends for penta-mix PBDE congeners were seen for soils in northern Europe, sewage sludge in Sweden and the USA, carp from a US river, trout from three of the Great Lakes and in Arctic and UK marine mammals and many birds, but increasing time trends continue in Arctic polar bears and some birds at high trophic levels in northern Europe. This is a result of the time delay inherent in long-range atmospheric transport processes. In general, concentrations of BDE209 (the major component of the deca-mix PBDE product) are continuing to increase. Of major concern is the possible/likely debromination of the large reservoir of BDE209 in soils and sediments worldwide, to yield lower brominated congeners which are both more mobile and more toxic, and we have compiled the most recent evidence for the occurrence of this degradation process. Numerous studies reported here reinforce the importance o f this future concern. Time trends for HBCDs are mixed, with both increases and decreases evident in different matrices and locations and, notably, with increasing occurrence in birds of prey.

Vocalizations of the North Island Brown Kiwi (Apteryx mantelli)

Few studies have investigated the vocal communication of ratites, and none has investigated the spectral and temporal structure of vocalizations of Apteryx, the only extant ratite genus in New Zealand. We describe the long-range vocalization (whistle call) and vocal behavior of male and female North Island Brown Kiwi (Apteryx mantelli). Spontaneous calling by seven pairs was recorded in the field over a one-year period. Call notes produced by males were tonal in nature; the fundamental frequency was ~1.5 kHz, with overtones reaching up to ~13.0 kHz. Call notes produced by females contained a series of tightly packed, poorly defined harmonics and consisted of a fundamental frequency of ~0.1 kHz, with overtones reaching ~7.0 kHz. The amplitude within notes of females was concentrated into two prominent formants. Some individuals of pairs exhibited duetting behavior that resulted in alteration of the inter-note interval after the onset of the call of their mate. Our findings draw attention to the uniqueness of the North Island Brown Kiwi's vocalizations, and we uncovered some unexpected structural features that call for further investigation.

Is the sun too bright in Queensland? An approach to robust outdoor colour beacon detection

Using cameras onboard a robot for detecting a coloured stationary target outdoors is a difficult task. Apart from the complexity of separating the target from the background scenery over different ranges, there are also the inconsistencies with direct and reflected illumination from the sun,clouds, moving and stationary objects. They can vary both the illumination on the target and its colour as perceived by the camera. In this paper, we analyse the effect of environment conditions, range to target, camera settings and image processing on the reported colours of various targets. The analysis indicates the colour space and camera configuration that provide the most consistent colour values over varying environment conditions and ranges. This information is used to develop a detection system that provides range and bearing to detected targets. The system is evaluated over various lighting conditions from bright sunlight, shadows and overcast days and demonstrates robust performance. The accuracy of the system is compared against a laser beacon detector with preliminary results indicating it to be a valuable asset for long-range coloured target detection.

Tailoring surface properties and structure of layered double hydroxides using silanes with different number of functional groups

Four silanes, trimethylchlorosilane (TMCS), dimethyldiethoxylsilane (DMDES), 3-aminopropyltriethoxysilane (APTES) and tetraethoxysilane (TEOS), were adopted to graft layered double hydroxides (LDH) via an induced hydrolysis silylation method (IHS). Fourier transform infrared spectra (FTIR) and 29Si MAS nuclear magnetic resonance spectra (29Si MAS NMR) indicated that APTES and TEOS can be grafted onto LDH surfaces via condensation with hydroxyl groups of LDH, while TMCS and DMDES could only be adsorbed on the LDH surface with a small quantity. A combination of X-ray diffraction patterns (XRD) and 29Si MAS NMR spectra showed that silanes were exclusively present in the external surface and had little influence on the long range order of LDH. The surfactant intercalation experiment indicated that the adsorbed and/or grafted silane could not fix the interlamellar spacing of the LDH. However, they will form crosslink between the particles and affect the further surfactant intercalation in the silylated samples. The replacement of water by ethanol in the tactoids and/or aggregations and the polysiloxane oligomers formed during silylation procedure can dramatically increase the value of BET surface area (SBET) and total pore volumes (Vp) of the products.

Excitation of bound plasmons along nanoscale stripe waveguides: A comparison of end and grating coupling techniques

In this paper we excite bound long range stripe plasmon modes with a highly focused laser beam. We demonstrate highly confined plasmons propagating along a 50 μm long silver stripe 750 nm wide and 30 nm thick. Two excitation techniques were studied: focusing the laser spot onto the waveguide end and focusing the laser spot onto a silver grating. By comparing the intensity of the out-coupling photons at the end of the stripe for both grating and end excitation we are able to show that gratings provide an increase of a factor of two in the output intensity and thus out-coupling of plasmons excited by this technique are easier to detect. Authors expect that the outcome of this paper will prove beneficial for the development of passive nano-optical devices based on stripe waveguides, by providing insight into the different excitation techniques available and the advantages of each technique.

Experimental evaluation of the performance of 2×2 MIMO-OFDM for vehicle-to-infrastructure communications

In this paper, a novel 2×2 multiple-input multiple-output orthogonal frequency division multiplexing (MIMO-OFDM) testbed based on an Analog Devices AD9361 highly integrated radio frequency (RF) agile transceiver was specifically implemented for the purpose of estimating and analyzing MIMO-OFDM channel capacity in vehicle-to-infrastructure (V2I) environments using the 920 MHz industrial, scientific, and medical (ISM) band. We implemented two-dimensional discrete cosine transform-based filtering to reduce the channel estimation errors and show its effectiveness on our measurement results. We have also analyzed the effects of channel estimation error on the MIMO channel capacity by simulation. Three different scenarios of subcarrier spacing were investigated which correspond to IEEE 802.11p, Long-Term Evolution (LTE), and Digital Video Broadcasting Terrestrial (DVB-T)(2k) standards. An extensive MIMO-OFDM V2I channel measurement campaign was performed in a suburban environment. Analysis of the measured MIMO channel capacity results as a function of the transmitter-to-receiver (TX-RX) separation distance up to 250 m shows that the variance of the MIMO channel capacity is larger for the near-range line-of-sight (LOS) scenarios than for the long-range non-LOS cases, using a fixed receiver signal-to-noise ratio (SNR) criterion. We observed that the largest capacity values were achieved at LOS propagation despite the common assumption of a degenerated MIMO channel in LOS. We consider that this is due to the large angular spacing between MIMO subchannels which occurs when the receiver vehicle rooftop antennas pass by the fixed transmitter antennas at close range, causing MIMO subchannels to be orthogonal. In addition, analysis on the effects of different subcarrier spacings on MIMO-OFDM channel capacity showed negligible differences in mean channel capacity for the subcarrier spacing range investigated. Measured channels described in this paper are available on request.

Mapping bound plasmon propagation on a nanoscale stripe waveguide using quantum dots: Influence of spacer layer thickness

In this paper we image the highly confined long range plasmons of a nanoscale metal stripe waveguide using quantum emitters. Plasmons were excited using a highly focused 633 nm laser beam and a specially designed grating structure to provide stronger incoupling to the desired mode. A homogeneous thin layer of quantum dots was used to image the near field intensity of the propagating plasmons on the waveguide. We observed that the photoluminescence is quenched when the QD to metal surface distance is less than 10 nm. The optimised spacer layer thickness for the stripe waveguides was found to be around 20 nm. Authors believe that the findings of this paper prove beneficial for the development of plasmonic devices utilising stripe waveguides.

Some limit theorems for regenerative queues

We consider a single server queue with the interarrival times and the service times forming a regenerative sequence. This traffic class includes the standard models: lid, periodic, Markov modulated (e.g., BMAP model of Lucantoni [18]) and their superpositions. This class also includes the recently proposed traffic models in high speed networks, exhibiting long range dependence. Under minimal conditions we obtain the rates of convergence to stationary distributions, finiteness of stationary moments, various functional limit theorems and the continuity of stationary distributions and moments. We use the continuity results to obtain approximations for stationary distributions and moments of an MMPP/GI/1 queue where the modulating chain has a countable state space. We extend all our results to feedforward networks where the external arrivals to each queue can be regenerative. In the end we show that the output process of a leaky bucket is regenerative if the input process is and hence our results extend to a queue with arrivals controlled by a leaky bucket.

Supramolecular ordering in oligothiophene−fullerene monolayers

Scanning tunneling microscopy (STM) of monolayers comprising oligothiophene and fullerene molecular semiconductors reveals details of their molecular-scale phase separation and ordering with potential implications for the design of organic electronic devices, in particular future bulk heterojunction solar cells. Prochiral terthienobenzenetricarboxylic acid (TTBTA) self-assembles at the solution/graphite interface into either a porous chicken wire network linked by dimeric hydrogen bonding associations of COOH groups (R22(8)) or a close-packed network linked in a novel hexameric hydrogen bonding motif (R66(24)). Analysis of high-resolution STM images shows that the chicken wire phase is racemically mixed, whereas the close-packed phase is enantiomerically pure. The cavities of the chicken wire structure can efficiently host C60 molecules, which form ordered domains with either one, two, or three fullerenes per cavity. The observed monodisperse filling and long-range co-alignment of fullerenes is described in terms of a combination of an electrostatic effect and the commensurability between the graphite and molecular network, which leads to differentiation of otherwise identical adsorption sites in the pores.

Structure of the noncubic phase in the ferroelectric state of Pr-substituted SrTiO3

Sr1−xPrxTiO3 has recently been shown to exhibit ferroelectricity at room temperature. In this paper powder x-ray and neutron-diffraction patterns of this system at room temperature have been analyzed to show that the system exhibits cubic (Pm-3m) structure for x<=0.05 and tetragonal (I4/mcm) for x>0.05. The redundancy of the noncentrosymmetric structural model (I4cm) in the ferroelectric state suggests the absence of long-range ordered ferroelectric domains and supports the relaxor ferroelectric model for this system.

Ultrasonic attenuation in strongly disordered electronic systems

The attenuation of long-wavelength phonons due to their interaction with electronic excitations in disordered systems is investigated here. Lattice strain couples to electronic stress, and thus ultrasonic attenuation measures electronic viscosity. The enhancement and critical divergence of electronic viscosity due to localization effects is calculated for the first time. Experimental consequences for the anomalous increase of ultrasonic attenuation in disordered metals close to the metal-insulator transition are discussed. In the localized regime, the appropriate model is one of electronic two-level systems (TLS’s) coupled to phonons. The TLS consists of a pair of states with one localized state occupied and the other unoccupied. The density of such low-excitation-energy TLS’s is nonzero due to long-range Coulomb interactions. The question of whether these could be significant low-energy excitations in glasses is touched upon.

Magnetic superconductors: Model theories and experimental properties of rare-earth compounds

Superconducting and magnetically long-range ordered states were believed to be mutually exclusive phenomena. The discovery of rare-earth compounds in recent years, which exhibit both superconductivity and magnetic ordering (ferromagnetic, antiferromagnetic or sinusoidal), has led to considerable theoretical and experimental work on such systems. In the present article, we give a review of various theoretical models and important experimental results. In the theoretical sections, we start with the Abrikosov-Gorkov pair breaking theory for dilute alloys and discuss its improvement in the work of Müller-Hartmann and Zittartz. Then, in the context of magnetic superconductors, various microscopic theories that have been advanced are presented. These predict re-entrant behaviour in some systems (ferromagnetic superconductors) and coexistence regions in others (particularly antiferromagnetic superconductors). Following this, phenomenological generalized Ginzburg-Landau theories for two kinds of orders (superconducting and magnetic) are presented. A section dealing with renormalization group analysis of phase diagrams in magnetic superconductors is given. In experimental sections, the properties of each rare-earth compounds (ternary as well as some tetranery) are reviewed. These involve susceptibility, heat capacity, resistivity, upper critical field, neutron scattering and magnetic resonance measurements. The anomalous behaviour of the upper critical field of antiferromagnetic superconductors near the Néel temperature is discussed both in theory sections and experimental section for various systems.