Simultaneous control of spectroscopic and electrochemical properties in functionalised electrochemiluminescent tris(2,2'-bipyridine)ruthenium(II) complexes

Using a combination of electrochemical, spectroscopic and computational techniques, we have explored the fundamental properties of a series of ruthenium diimine complexes designed for coupling with other molecules or surfaces for electrochemiluminescence (ECL) sensing applications. With appropriate choice of ligand functionality, it is possible to manipulate emission wavelengths while keeping the redox ability of the complex relatively constant. DFT calculations show that in the case of electron withdrawing substituents such as ester or amide, the excited state is located on the substituted bipyridine ligand whereas in the case of alkyl functionality it is localised on a bipyridine. The factors that dictate annihilation ECL efficiency are interrelated. For example, the same factors that determine ΔG for the annihilation reaction (i.e. the relative energies of the HOMO and LUMO) have a corresponding effect on the energy of the excited state product. As a result, most of the complexes populate the excited state with an efficiency (Φex) of close to 80% despite the relatively wide range of emission maxima. The quantum yield of emission (Φp) and the possibility of competing side reactions are found to be the main determinants of ECL intensity.

Detection of curved edges at subpixel accuracy using deformable models

One approach to the detection of curves at subpixel accuracy involves the reconstruction of such features from subpixel edge data points. A new technique is presented for reconstructing and segmenting curves with subpixel accuracy using deformable models. A curve is represented as a set of interconnected Hermite splines forming a snake generated from the subpixel edge information that minimizes the global energy functional integral over the set. While previous work on the minimization was mostly based on the Euler-Lagrange transformation, the authors use the finite element method to solve the energy minimization equation. The advantages of this approach over the Euler-Lagrange transformation approach are that the method is straightforward, leads to positive m-diagonal symmetric matrices, and has the ability to cope with irregular geometries such as junctions and corners. The energy functional integral solved using this method can also be used to segment the features by searching for the location of the maxima of the first derivative of the energy over the elementary curve set.

Local energy and pre-envelope

We observe that the local energy is the pre-envelope for analytic function. The maxima and phase of this function can be used to compute and classify visual features such as motion and stereo disparity, texture, etc. We examine the construction of new filters for computing Local Energy, and compare these filters with the Gabor filters and the three-point-filter of Venkatesh and Owens.

Exploiting monge structures in optimum subwindow search

Optimum subwindow search for object detection aims to find a subwindow so that the contained subimage is most similar to the query object. This problem can be formulated as a four dimensional (4D) maximum entry search problem wherein each entry corresponds to the quality score of the subimage contained in a subwindow. For n x n images, a naive exhaustive search requires O(n⁴) sequential computations of the quality scores for all subwindows. To reduce the time complexity, we prove that, for some typical similarity functions like Euclidian metric, χ² metric on image histograms, the associated 4D array carries some Monge structures and we utilise these properties to speed up the optimum subwindow search and the time complexity is reduced to O(n³). Furthermore, we propose a locally optimal alternating column and row search method with typical quadratic time complexity O(n²). Experiments on PASCAL VOC 2006 demonstrate that the alternating method is significantly faster than the well known efficient subwindow search (ESS) method whilst the performance loss due to local maxima problem is negligible.

The Bassian Isthmus and the major ocean currents of southeast Australia influence the phylogeography and population structure of a southern Australian intertidal barnacle Catomerus polymerus (Darwin)

Southern Australia is currently divided into three marine biogeographical provinces based on faunal distributions and physical parameters. These regions indicate eastern and western distributions, with an overlap occurring in the Bass Strait in Victoria. However, studies indicate that the boundaries of these provinces vary depending on the species being examined, and in particular on the mode of development employed by that species, be they direct developers or planktonic larvae dispersers. Mitochondrial DNA sequence analysis of the surf barnacle Catomerus polymerus in southern Australia revealed an east–west phylogeographical split involving two highly divergent clades (cytochrome oxidase I 3.5 ± 0.76%, control region 6.7 ± 0.65%), with almost no geographical overlap. Spatial genetic structure was not detected within either clade, indicative of a relatively long-lived planktonic larval phase. Five microsatellite loci indicated that C. polymerus populations exhibit relatively high levels of genetic divergence, and fall into four subregions: eastern Australia, central Victoria, western Victoria and Tasmania, and South Australia. F_ST values between eastern Australia (from the eastern mitochondrial DNA clade) and the remaining three subregions ranged from 0.038 to 0.159, with other analyses indicating isolation by distance between the subregions of western mitochondrial origin. We suggest that the east–west division is indicative of allopatric divergence resulting from the emergence of the Bassian land-bridge during glacial maxima, preventing gene flow between these two lineages. Subsequently, contemporary ecological conditions, namely the East Australian, Leeuwin, and Zeehan currents and the geographical disjunctions at the Coorong and Ninety Mile Beach are most likely responsible for the four subregions indicated by the microsatellite data.

In vitro strain measurements in cerebral aneurysm models for cyber-physical diagnosis

Background: The development of new diagnostic technologies for cerebrovascular diseases requires an understanding of the mechanism behind the growth and rupture of cerebral aneurysms. To provide a comprehensive diagnosis and prognosis of this disease, it is desirable to evaluate wall shear stress, pressure, deformation and strain in the aneurysm region, based on information provided by medical imaging technologies. Methods: In this research, we propose a new cyber-physical system composed of in vitro dynamic strain experimental measurements and computational fluid dynamics (CFD) simulation for the diagnosis of cerebral aneurysms. A CFD simulation and a scaled-up membranous silicone model of a cerebral aneurysm were completed, based on patient-specific data recorded in August 2008. In vitro blood flow simulation was realized with the use of a specialized pump. A vision system was also developed to measure the strain at different regions on the model by way of pulsating blood flow circulating inside the model. Results: Experimental results show that distance and area strain maxima were larger near the aneurysm neck (0.042 and 0.052), followed by the aneurysm dome (0.023 and 0.04) and finally the main blood vessel section (0.01 and 0.014). These results were complemented by a CFD simulation for the addition of wall shear stress, oscillatory shear index and aneurysm formation index. Diagnosis results using imaging obtained in August 2008 are consistent with the monitored aneurysm growth in 2011. Conclusion: The presented study demonstrates a new experimental platform for measuring dynamic strain within cerebral aneurysms. This platform is also complemented by a CFD simulation for advanced diagnosis and prediction of the growth tendency of an aneurysm in endovascular surgery.

A potential-controlled switch on/off mechanism for selective excitation in mixed electrochemiluminescent systems

We demonstrate the complete, rapid, and reversible switching between the emissions from two electrogenerated chemiluminescence (ECL) systems contained within the same solution, controlled by simple modification of the applied potential. The fundamental bases of the approach are the ability to selectively 'switch on' luminophores at distinct oxidation potentials, and an intriguing observation that the emission from the well-known electrochemiluminescent complex, fac-Ir(ppy)3, (where ppy is 2-phenylpyridinato), can be selectively 'switched-off' at high overpotentials. The dependence of this phenomenon on high concentrations of the co-reactant implicates quenching of the excited [Ir(ppy)3]* state by electron transfer. Rapid spectral scanning during modulation of the applied potential reveals well resolved maxima for mixtures comprising either green and red or green and blue luminophores, illustrating the vast potential of this approach for multiplexed ECL detection.

Mixing Matrix Estimation From Sparse Mixtures With Unknown Number of Sources

In blind source separation, many methods have been proposed to estimate the mixing matrix by exploiting sparsity. However, they often need to know the source number a priori, which is very inconvenient in practice. In this paper, a new method, namely nonlinear projection and column masking (NPCM), is proposed to estimate the mixing matrix. A major advantage of NPCM is that it does not need any knowledge of the source number. In NPCM, the objective function is based on a nonlinear projection and its maxima just correspond to the columns of the mixing matrix. Thus a column can be estimated first by locating a maximum and then deflated by a masking operation. This procedure is repeated until the evaluation of the objective function decreases to zero dramatically. Thus the mixing matrix and the number of sources are estimated simultaneously. Because the masking procedure may result in some small and useless local maxima, particle swarm optimization (PSO) is introduced to optimize the objective function. Feasibility and efficiency of PSO are also discussed. Comparative experimental results show the efficiency of NPCM, especially in the cases where the number of sources is unknown and the sources are relatively less sparse.

Feeding ecology of wintering terns in Guinea-Bissau

We studied the feeding ecology of Little Terns Sterna albifrons, Sandwich Terns S. sandvicensis and Royal Terns S. maxima in the Archipélago dos Bijagós (11°40′N, 15°45′W) in Guinea-Bissau (West Africa) during the winter of 1992/1993. More than 95% of all prey taken by these terns were roundfish, ranging in weight from 0.3 to 40 g. Birds usually fed alone, but sometimes they were observed feeding in mixed-species flocks consisting of 15-200 individuals. Capture rate (n fish per hour foraging) in these flocks was higher than that of solitary birds. However, smaller fish were caught by birds foraging in flocks, so food intake rate (g/h) did not differ between solitary and flock-feeding birds. The relationships between foraging behaviour of the three tern species and abiotic factors, such as time, tide and water clarity, have been investigated. Capture rate of Royal Terns increased with water clarity. For Little Terns and Sandwich Terns, food intake rate was lower in the most turbid waters compared to clearer waters. There was very little foraging activity during high tide. For Little Terns and Royal Terns, food intake rate was about twice as high during receding and low tides as during an incoming tide. Food intake rate averaged 8 g/h in Little Terns, 60 g/h in Sandwich Terns and 45 g/h in Royal Terns. With a rough model, we estimate the maximum rate of daily energy expenditure of terns wintering in the tropics at 3 x BMR (defined as energy expenditure of inactive bird at thermoneutrality in a post-absorptive state during the resting phase of the daily cycle). From an energetic viewpoint, wintering Sandwich Terns in Guinea-Bissau seem to have an easy living.