Ruthenium(II) bis(terpyridine) electron transfer complexes with alkynyl-ferrocenyl bridges: synthesis, structures, and electrochemical and spectroscopic studies

Two novel alkynyl-bridged symmetric bis-tridentate ligands 1,2-bis(1'-[4'-(2,2':6', 2 ''-terpyridinyl)]-ferrocenyl)ethyne (3a; tpy-Fc-C C-Fc-tpy; Fc = ferrocenyl; tpy = terpyridyl) and 1,4-bis(1'-[4'-(2,2':6', 2 ''-terpyridinyl)]ferrocenyl)-1,3-butadiyne (3b; tpy-Fc-C C-C C-Fc-tpy) and their Ru2+ complexes 6a and 6b have been synthesized and characterized by cyclic voltammetry, UV-vis and luminescence spectroscopy, and in the case of 3b by single-crystal X-ray diffraction. Cyclic voltammograms of both compounds, 3a and 3b, display two severely overlapping ferrocene-based oxidative peaks with only one reductive peak. The redox behavior of 6a and 6b is dominated by the Ru2+/Ru3+ redox couple (E-1/2 from 1.33 to 1.34 V), the Fe2+/Fe3+ redox couples (E-1/2 from 0.46 to 0.80 V), and the tpy/tpy(-)/tpy(2-)redox couples (E-1/2 from -1.19 to -1.48 V). The UV-vis spectra of 6a and 6b show absorption bands assigned to the (1)[(d(pi)(Fe))(6)] -> (1)[(d(pi)(Fe))(5)(pi*(Ru)(tpy))(1)] MMLCT transition at similar to 555 nm. Complexes 6a and 6b are luminescent in H2O-CH3CN (4 : 1, v/v) solution at room temperature, and 6b exhibits the strongest luminescence intensity (lambda(em)(max): 710 nm, Phi(em): 2.28 x 10(-4), tau: 358 ns) relative to analogous ferrocene-based bis(terpyridine) Ru(II) complexes reported so far.

Structural damage diagnosis of steel truss bridges by outlier detection

This study discusses structural damage diagnosis of real steel truss bridges by measuring trafficinduced vibration of bridges and utilizing a damage indicator derived from linear system parameters of a time series model. On-site damage experiments were carried out on real steel truss bridges. Artificial damage was applied to the bridge by severing a truss member with a cutting machine.Vehicle-induced vibrations of the bridges before and after applying damagewere measured and used in structural damage diagnosis of the bridges. Changes in the damage indicator are detected by Mahalanobis-Taguchi system (MTS) which is one of multivariate outlier analyses. The damage indicator and outlier detection was successfully applied to detect anomalies in the steel truss bridges utilizing vehicle-induced vibrations. Observations through this study demonstrate feasibility of the proposed approach for real world applications.

Experimentally validated partial least squares model for dynamic line rating

This study presents a model based on partial least squares (PLS) regression for dynamic line rating (DLR). The model has been verified using data from field measurements, lab tests and outdoor experiments. Outdoor experimentation has been conducted both to verify the model predicted DLR and also to provide training data not available from field measurements, mainly heavily loaded conditions. The proposed model, unlike the direct measurement based DLR techniques, enables prediction of line rating for periods ahead of time whenever a reliable weather forecast is available. The PLS approach yields a very simple statistical model that accurately captures the physical performance of the conductor within a given environment without requiring a predetermination of parameters as required by many physical modelling techniques. Accuracy of the PLS model has been tested by predicting the conductor temperature for measurement sets other than those used for training. Being a linear model, it is straightforward to estimate the conductor ampacity for a set of predicted weather parameters. The PLS estimated ampacity has proven its accuracy through an outdoor experiment on a piece of the line conductor in real weather conditions.

Partial least squares model for dynamic rating of overhead line in wind intensive areas based on field measurements

This paper presents a statistical model for the thermal behaviour of the line model based on lab tests and field measurements. This model is based on Partial Least Squares (PLS) multi regression and is used for the Dynamic Line Rating (DLR) in a wind intensive area. DLR provides extra capacity to the line, over the traditional seasonal static rating, which makes it possible to defer the need for reinforcement the existing network or building new lines. The proposed PLS model has a number of appealing features; the model is linear, so it is straightforward to use for predicting the line rating for future periods using the available weather forecast. Unlike the available physical models, the proposed model does not require any physical parameters of the line, which avoids the inaccuracies resulting from the errors and/or variations in these parameters. The developed model is compared with physical model, the Cigre model, and has shown very good accuracy in predicting the conductor temperature as well as in determining the line rating for future time periods. 

The hydraulics and resulting bed scour within the vicinity of Submerged Single Span Arch Bridges

As a consequence of climate change there is now a more frequent occurrence of extreme rainfall events where, with higher rates of urbanisation, the built environment has become increasingly affected by flooding.. This is of particular importance in relation to the stability of bridge structures that span rivers and canals etc. In November 2009, the UK and Ireland were subjected to extraordinarily severe weather conditions for several days. The rainfall was logged as the highest level of rainfall ever recorded within the UK, and as a direct consequence, unprecedented flooding occurred in Cumbria. This flooding led to the collapse of three road bridges which were generally 19th century masonry arch bridges, with relatively shallow foundations. In the UK, knowledge of the combined effect of bridge scouring and inundation has been not been particularly widely studied. Research carried out by Hamill et al [1] considered the hydraulic analysis of single arch bridges under flood conditions, but no consideration was given towards the likely damage to these structures due to scouring. Prior to this, Bierry and Delleur [2] produced a classic paper in predicting the discharge downstream of an inundated arch, focussing on predicting afflux as opposed to bridge scour. Further work on backwater effects was carried out by Martin-Vide & Prio [3] in semi-circular arch bridges. Both pressurized and free-surface flows at the bridge were investigated. Flows on a mobile bed in clear-water conditions were compared to those with a rigid bed, but no predictive equation for scour under pressurised conditions was considered. This paper will present initial findings from an experimental investigation into the effects of surcharged flow and subsequent scour within the vicinity of single span arch bridges. Velocities profiles will be shown within the vicinity of the arch, in addition to the depth of clear water scour, for a series of flows and model spans. The data will be presented, where results will be correlated to the most recent predictive equations that are proposed.

Dimensionality, Reliability and Validity of the InterRAI Depression Rating Scale in a Canadian Palliative Care Population

A reliable and valid instrument is needed to screen for depression in palliative patients. The interRAI Depression Rating Scale (DRS) is based on seven items in the interRAI Palliative Care instrument. This study is the first to explore the dimensionality, reliability and validity of the DRS in a palliative population. Palliative home care patients (n = 5,175) residing in Ontario (Canada) were assessed with the interRAI Palliative Care instrument. Exploratory factor analysis and Mokken scale analysis were used to identify candidate conceptual models and evaluate scale homogeneity/performance. Confirmatory factor analysis compared models using standard goodness-of-fit indices. Convergent and divergent validity were investigated by examining polychoric correlations between the DRS and other items. The “known groups” test determined if the DRS meaningfully distinguished among client subgroups. The non-hierarchical two factor model showed acceptable fit with the data, and ordinal alpha coefficients of 0.83 and 0.82 were observed for the two DRS subscales. Omega hierarchical (ωh) was 0.78 for the bifactor model, with the general factor explaining three quarters of the common variance. Despite the multidimensionality evident in the factor analyses, bifactor modelling and the Mokken homogeneity coefficient (0.34) suggest that the DRS is a coherent scale that captures important information on sub-constructs of depression (e.g., somatic symptoms). Higher correlations were seen between the DRS and mood and psychosocial well-being items, and lower correlations with functional status and demographic variables. The DRS distinguished in the expected manner for known risk factors (e.g., social support, pain). The results suggest that the DRS is primarily unidimensional and reliable for use in screening for depression in palliative care patients.