Preparation of metal-TCNQ charge-transfer complexes on conducting and insulating surfaces by photocrystallization

A generic method for the synthesis of metal-7,7,8,8-tetracyanoquinodimethane (TCNQ) charge-transfer complexes on both conducting and nonconducting substrates is achieved by photoexcitation of TCNQ in acetonitrile in the presence of a sacrificial electron donor and the relevant metal cation. The photochemical reaction leads to reduction of TCNQ to the TCNQ- monoanion. In the presence of Mx+(MeCN), reaction with TCNQ-(MeCN) leads to deposition of Mx+[TCNQ]x crystals onto a solid substrate with morphologies that are dependent on the metal cation. Thus, CuTCNQ phase I photocrystallizes as uniform microrods, KTCNQ as microrods with a random size distribution, AgTCNQ as very long nanowires up to 30 μm in length and with diameters of less than 180 nm, and Co[TCNQ]2(H2O)2 as nanorods and wires. The described charge-transfer complexes have been characterized by optical and scanning electron microscopy and IR and Raman spectroscopy. The CuTCNQ and AgTCNQ complexes are of particular interest for use in memory storage and switching devices. In principle, this simple technique can be employed to generate all classes of metal−TCNQ complexes and opens up the possibility to pattern them in a controlled manner on any type of substrate.

Characterisation of two distinctly different processes associated with the electrocrystallization of microcrystals of phase I CuTCNQ (TCNQ= 7, 7, 8, 8-tetracyanoquinodimethane)

Semi-conducting phase I CuTCNQ (TCNQ = 7,7,8,8-tetracyanoquinodimethane), which is of considerable interest as a switching device for memory storage materials, can be electrocrystallized from CH3CN via two distinctly different pathways when TCNQ is reduced to TCNQ˙− in the presence of [Cu(MeCN)4]+. The first pathway, identified in earlier studies, occurs at potentials where TCNQ is reduced to TCNQ˙− and involves a nucleation–growth mechanism at preferred sites on the electrode to produce arrays of well separated large branched needle-shaped phase I CuTCNQ crystals. The second pathway, now identified at more negative potentials, generates much smaller needle-shaped phase I CuTCNQ crystals. These electrocrystallize on parts of the surface not occupied in the initial process and give rise to film-like characteristics. This process is attributed to the reduction of Cu+[(TCNQ˙−)(TCNQ)] or a stabilised film of TCNQ via a solid–solid conversion process, which also involves ingress of Cu+via a nucleation–growth mechanism. The CuTCNQ surface area coverage is extensive since it occurs at all areas of the electrode and not just at defect sites that dominate the crystal formation sites for the first pathway. Infrared spectra, X-ray diffraction, surface plasmon resonance, quartz crystal microbalance, scanning electron microscopy and optical image data all confirm that two distinctly different pathways are available to produce the kinetically-favoured and more highly conducting phase I CuTCNQ solid, rather than the phase II material.

Engineering electrodeposited ZnO films and their memristive switching performance

We report the influence of zinc oxide (ZnO) seed layers on the performance of ZnO-based memristive devices fabricated using an electrodeposition approach. The memristive element is based on a sandwich structure using Ag and Pt electrodes. The ZnO seed layer is employed to tune the morphology of the electrodeposited ZnO films in order to increase the grain boundary density as well as construct highly ordered arrangements of grain boundaries. Additionally, the seed layer also assists in optimizing the concentration of oxygen vacancies in the films. The fabricated devices exhibit memristive switching behaviour with symmetrical and asymmetrical hysteresis loops in the absence and presence of ZnO seed layers, respectively. A modest concentration of oxygen vacancy in electrodeposited ZnO films as well as an increase in the ordered arrangement of grain boundaries leads to higher switching ratios in Ag/ZnO/Pt devices.

Collagen in the scarless fetal skin wound : detection with picrosirius-polarization

Our group has developed an ovine model of deep dermal, partial-thickness burn where the fetus heals scarlessly and the lamb heals with scar. The comparison of collagen structure between these two different mechanisms of healing may elucidate the process of scarless wound healing. Picrosirius staining followed by polarized light microscopy was used to visualize collagen fibers, with digital capture and analysis. Collagen deposition increased with fetal age and the fibers became thicker, changing from green (type III collagen) to yellow/red (type I collagen). The ratio of type III collagen to type I was high in the fetus (166), whereas the lamb had a much lower ratio (0.2). After burn, the ratios of type III to type I collagen did not differ from those in control skin for either fetus or lamb. The fetal tissue maintained normal tissue architecture after burn while the lamb tissue showed irregular collagen organization. In conclusion, the type or amount of collagen does not alter significantly after injury. Tissue architecture differed between fetal and lamb tissue, suggesting that scar development is related to collagen cross-linking or arrangement. This study indicates that healing in the scarless fetal wound is representative of the normal fetal growth pattern, rather than a "response" to burn injury.

Choroidal thickness in myopic and non-myopic children assessed with enhanced depth imaging optical coherence tomography

Purpose To examine choroidal thickness (ChT) and its topographical variation across the posterior pole in myopic and non-myopic children. Methods One hundred and four children aged 10-15 years of age (mean age 13.1 ± 1.4 years) had ChT measured using enhanced depth imaging optical coherence tomography (OCT). Forty one children were myopic (mean spherical equivalent -2.4 ± 1.5 D) and 63 non-myopic (mean +0.3 ± 0.3 D). Two series of 6 radial OCT line scans centred on the fovea were assessed for each child. Subfoveal ChT and ChT across a series of parafoveal zones over the central 6mm of the posterior pole were determined through manual image segmentation. Results Subfoveal ChT was significantly thinner in myopes (mean 303 ± 79 µm) compared to non-myopes (mean 359 ± 77 µm) (p<0.0001). Multiple regression analysis revealed both refractive error (r = 0.39, p<0.001) and age (r = 0.21, p = 0.02) were positively associated with subfoveal ChT. ChT also exhibited significant topographical variations, with the choroid being thicker in more central regions. The thinnest choroid was typically observed in nasal (mean 286 ± 77 µm) and inferior-nasal (306 ± 79 µm) locations, and the thickest in superior (346 ± 79 µm) and superior-temporal (341 ± 74 µm) locations. The difference in ChT between myopic and non-myopic children was significantly greater in central foveal regions compared to more peripheral regions (>3 mm diameter) (p<0.001). Conclusions Myopic children have significantly thinner choroids compared to non-myopic children of similar age, particularly in central foveal regions. The magnitude of difference in choroidal thickness associated with myopia appears greater than would be predicted by a simple passive choroidal thinning with axial elongation.

Estimation of vibration amplitude in Fourier domain optical coherence tomography interferometric signals from Doppler spectrum

In presented method combination of Fourier and Time domain detection enables to broaden the effective bandwidth for time dependent Doppler Signal that allows for using higher-order Bessel functions to calculate unambiguously the vibration amplitudes.

Voltage unbalance reduction in low voltage feeders by dynamic switching of residential customers among three phases

Low voltage distribution feeders with large numbers of single phase residential loads experience severe current unbalance that often causes voltage unbalance problems. The addition of intermittent generation and new loads in the form of roof top photovoltaic generation and electric vehicles makes these problems even more acute. In this paper, an intelligent dynamic residential load transfer scheme is proposed. Residential loads can be transferred from one phase to another phase to minimize the voltage unbalance along the feeder. Each house is supplied through a static transfer switch with three-phase input and single-phase output connection. The main controller, installed at the transformer will observe the power consumption in each load and determine which house(s) should be transferred from one phase to another in order to keep the voltage unbalance in the feeder at a minimum. The efficacy of the proposed load transfer scheme is verified through MATLAB and PSCAD/EMTDC simulations.

Smart Inter-Phase Switching of Residential Loads in Low Voltage Distribution Feeders

In order to dynamically reduce voltage unbalance along a low voltage distribution feeder, a smart residential load transfer system is discussed. In this scheme, residential loads can be transferred from one phase to another to minimize the voltage unbalance along the feeder. Each house is supplied through a static transfer switch and a controller. The master controller, installed at the transformer, observes the power consumption in each house and will determine which house(s) should be transferred from an initially connected phase to another in order to keep the voltage unbalance minimum. The performance of the smart load transfer scheme is demonstrated by simulations.

Switching radical stability by pH-induced orbital conversion

In most radicals the singly occupied molecular orbital (SOMO) is the highest-energy occupied molecular orbital (HOMO); however, in a small number of reported compounds this is not the case. In the present work we expand significantly the scope of this phenomenon, known as SOMO-HOMO energy-level conversion, by showing that it occurs in virtually any distonic radical anion that contains a sufficiently stabilized radical (aminoxyl, peroxyl, aminyl) non-pi-conjugated with a negative charge (carboxylate, phosphate, sulfate). Moreover, regular orbital order is restored on protonation of the anionic fragment, and hence the orbital configuration can be switched by pH. Most importantly, our theoretical and experimental results reveal a dramatically higher radical stability and proton acidity of such distonic radical anions. Changing radical stability by 3-4 orders of magnitude using pH-induced orbital conversion opens a variety of attractive industrial applications, including pH-switchable nitroxide-mediated polymerization, and it might be exploited in nature.

Orientation robust transmit polarization diversity techniques

Polarisation diversity is a technique to improve the quality of mobile communications, but its reliability is suboptimal because it depends on the mobile channel and the antenna orientations at both ends of the mobile link. A method to optimise the reliability is established by minimising the dependency on antenna orientations. While the mobile base station can have fixed antenna orientation, the mobile terminal is typically a handheld device with random orientations. This means orientation invariance needs to be established at the receiver in the downlink, and at the transmitter in the uplink. This research presents separate solutions for both cases, and is based on the transmission of an elliptically polarised signal synthesised from the channel statistics. Complete receiver orientation invariance is achieved in the downlink. Effects of the transmitter orientation are minimised in the uplink.

The relationship between BCOM1 gene variants and macular pigment optical density in persons with and without age-related macular degeneration

Background: Recent evidence indicates that gene variants related to carotenoid metabolism play a role in the uptake of macular pigments lutein (L) and zeaxanthine (Z). Moreover, these pigments are proposed to reduce the risk for advanced age-related macular degeneration (AMD). This study provides the initial examination of the relationship between the gene variants related to carotenoid metabolism, macular pigment optical density (MPOD) and their combined expression in healthy humans and patients with AMD. Participants and Methods: Forty-four participants were enrolled from a general population and a private practice including 20 healthy participants and 24 patients with advanced (neovascular) AMD. Participants were genotyped for the three single nucleotide polymorphisms (SNPs) upstream from BCMO1, rs11645428, rs6420424 and rs6564851 that have been shown to either up or down regulate beta-carotene conversion efficiency in the plasma. MPOD was determined by heterochromatic flicker photometry. Results: Healthy participants with the rs11645428 GG genotype, rs6420424 AA genotype and rs6564851 GG genotype all had on average significantly lower MPOD compared to those with the other genotypes (p < 0.01 for all three comparisons). When combining BCMO1 genotypes reported to have “high” (rs11645428 AA/rs6420424 GG/rs6564851 TT) and “low” (rs11645428 GG/rs6420424 AA/rs6564851 GG) beta-carotene conversion efficiency, we demonstrate clear differences in MPOD values (p<0.01). In patients with AMD there were no significant differences in MPOD for any of the three BCMO1 gene variants. Conclusion: In healthy participants MPOD levels can be related to high and low beta-carotene conversion BCMO1 genotypes. Such relationships were not found in patients with advanced neovascular AMD, indicative of additional processes influencing carotenoid uptake, possibly related to other AMD susceptibility genes. Our findings indicate that specific BCMO1 SNPs should be determined when assessing the effects of carotenoid supplementation on macular pigment and that their expression may be influenced by retinal disease.

Development of optical ray tracing model of a standard parabolic trough collector

Parabolic trough concentrator collector is the most matured, proven and widespread technology for the exploitation of the solar energy on a large scale for middle temperature applications. The assessment of the opportunities and the possibilities of the collector system are relied on its optical performance. A reliable Monte Carlo ray tracing model of a parabolic trough collector is developed by using Zemax software. The optical performance of an ideal collector depends on the solar spectral distribution and the sunshape, and the spectral selectivity of the associated components. Therefore, each step of the model, including the spectral distribution of the solar energy, trough reflectance, glazing anti-reflection coating and the absorber selective coating is explained and verified. Radiation flux distribution around the receiver, and the optical efficiency are two basic aspects of optical simulation are calculated using the model, and verified with widely accepted analytical profile and measured values respectively. Reasonably very good agreement is obtained. Further investigations are carried out to analyse the characteristics of radiation distribution around the receiver tube at different insolation, envelop conditions, and selective coating on the receiver; and the impact of scattered light from the receiver surface on the efficiency. However, the model has the capability to analyse the optical performance at variable sunshape, tracking error, collector imperfections including absorber misalignment with focal line and de-focal effect of the absorber, different rim angles, and geometric concentrations. The current optical model can play a significant role in understanding the optical aspects of a trough collector, and can be employed to extract useful information on the optical performance. In the long run, this optical model will pave the way for the construction of low cost standalone photovoltaic and thermal hybrid collector in Australia for small scale domestic hot water and electricity production.

Optical coupling of Au nanoparticles on vertical graphenes to maximize SERS response

Gold particle interaction with few-layer graphenes is of interest for the development of numerous optical nanodevices. The results of numerical studies of the coupling of gold nanoparticles with few-layer vertical graphene sheets are presented. The field strengths are computed and the optimum nanoparticle configurations for the formation of SERS hotpots are obtained. The nanoparticles are modeled as 8 nm diameter spheres atop 1.5 nm (5 layers) graphene sheet. The vertical orientation is of particular interest as it is possible to use both sides of the graphene structure and potentially double the number of particles in the system. Our results show that with the addition of an opposing particle a much stronger signal can be obtained as well as the particle separation can be controlled by the number of atomic carbon layers. These results provide further insights and contribute to the development of next-generation plasmonic devices based on nanostructures with hybrid dimensionality.

Universal codes from switching strategies

We discuss algorithms for combining sequential prediction strategies, a task which can be viewed as a natural generalisation of the concept of universal coding. We describe a graphical language based on Hidden Markov Models for defining prediction strategies, and we provide both existing and new models as examples. The models include efficient, parameterless models for switching between the input strategies over time, including a model for the case where switches tend to occur in clusters, and finally a new model for the scenario where the prediction strategies have a known relationship, and where jumps are typically between strongly related ones. This last model is relevant for coding time series data where parameter drift is expected. As theoretical contributions we introduce an interpolation construction that is useful in the development and analysis of new algorithms, and we establish a new sophisticated lemma for analysing the individual sequence regret of parameterised models.

Polarization of forecast densities : a new approach to time series classification

Time series classification has been extensively explored in many fields of study. Most methods are based on the historical or current information extracted from data. However, if interest is in a specific future time period, methods that directly relate to forecasts of time series are much more appropriate. An approach to time series classification is proposed based on a polarization measure of forecast densities of time series. By fitting autoregressive models, forecast replicates of each time series are obtained via the bias-corrected bootstrap, and a stationarity correction is considered when necessary. Kernel estimators are then employed to approximate forecast densities, and discrepancies of forecast densities of pairs of time series are estimated by a polarization measure, which evaluates the extent to which two densities overlap. Following the distributional properties of the polarization measure, a discriminant rule and a clustering method are proposed to conduct the supervised and unsupervised classification, respectively. The proposed methodology is applied to both simulated and real data sets, and the results show desirable properties.