Metalloporphyrin anion sensors: the effect of the metal centre on the anion binding properties of amide-functionalised and tetraphenyl metalloporphyrins

This article describes the synthesis and anion binding properties of a series of ‘picket fence’ metalloporphyrin complexes, within which the metal centre is systematically varied. The porphyrin structure contains four amide bonds and is the same for each metal. The anion binding properties of these receptors are further contrasted with those of their tetraphenylporphyrin congeners to elucidate both the effect of the metal centre and the influence of the amide groups on the anion recognition process. Anion binding was demonstrated using UV/visible and 1H NMR spectroscopies, electrochemistry and luminescence. The metal centre was found to be highly influential in the strength and selectivity of binding; for example, the cadmium and mercury complexes exhibited far greater affinities for anions than the zinc complexes in competitive solvents such as DMSO. The amide functionalities were found to enhance the anion binding process.

Invisible and visible language planning: ideological factors in the family language policy of Chinese immigrant families in Quebec

This ethnographic inquiry examines how family languages policies are planned and developed in ten Chinese immigrant families in Quebec, Canada, with regard to their children’s language and literacy education in three languages, Chinese, English, and French. The focus is on how multilingualism is perceived and valued, and how these three languages are linked to particular linguistic markets. The parental ideology that underpins the family language policy, the invisible language planning, is the central focus of analysis. The results suggest that family language policies are strongly influenced by socio-political and economical factors. In addition, the study confirms that the parents’ educational background, their immigration experiences and their cultural disposition, in this case pervaded by Confucian thinking, contribute significantly to parental expectations and aspirations and thus to the family language policies.

Extended optimal estimation techniques for sea surface temperature from the Spinning Enhanced Visible and Infra-Red Imager (SEVIRI)

Sea surface temperature (SST) can be estimated from day and night observations of the Spinning Enhanced Visible and Infra-Red Imager (SEVIRI) by optimal estimation (OE). We show that exploiting the 8.7 μm channel, in addition to the “traditional” wavelengths of 10.8 and 12.0 μm, improves OE SST retrieval statistics in validation. However, the main benefit is an improvement in the sensitivity of the SST estimate to variability in true SST. In a fair, single-pixel comparison, the 3-channel OE gives better results than the SST estimation technique presently operational within the Ocean and Sea Ice Satellite Application Facility. This operational technique is to use SST retrieval coefficients, followed by a bias-correction step informed by radiative transfer simulation. However, the operational technique has an additional “atmospheric correction smoothing”, which improves its noise performance, and hitherto had no analogue within the OE framework. Here, we propose an analogue to atmospheric correction smoothing, based on the expectation that atmospheric total column water vapour has a longer spatial correlation length scale than SST features. The approach extends the observations input to the OE to include the averaged brightness temperatures (BTs) of nearby clear-sky pixels, in addition to the BTs of the pixel for which SST is being retrieved. The retrieved quantities are then the single-pixel SST and the clear-sky total column water vapour averaged over the vicinity of the pixel. This reduces the noise in the retrieved SST significantly. The robust standard deviation of the new OE SST compared to matched drifting buoys becomes 0.39 K for all data. The smoothed OE gives SST sensitivity of 98% on average. This means that diurnal temperature variability and ocean frontal gradients are more faithfully estimated, and that the influence of the prior SST used is minimal (2%). This benefit is not available using traditional atmospheric correction smoothing.

Estimation of sea surface temperature from the Spinning Enhanced Visible and Infra Red Imager, improved using numerical weather prediction

Most of the operational Sea Surface Temperature (SST) products derived from satellite infrared radiometry use multi-spectral algorithms. They show, in general, reasonable performances with root mean square (RMS) residuals around 0.5 K when validated against buoy measurements, but have limitations, particularly a component of the retrieval error that relates to such algorithms' limited ability to cope with the full variability of atmospheric absorption and emission. We propose to use forecast atmospheric profiles and a radiative transfer model to simulate the algorithmic errors of multi-spectral algorithms. In the practical case of SST derived from the Spinning Enhanced Visible and Infrared Imager (SEVIRI) onboard Meteosat Second Generation (MSG), we demonstrate that simulated algorithmic errors do explain a significant component of the actual errors observed for the non linear (NL) split window algorithm in operational use at the Centre de Météorologie Spatiale (CMS). The simulated errors, used as correction terms, reduce significantly the regional biases of the NL algorithm as well as the standard deviation of the differences with drifting buoy measurements. The availability of atmospheric profiles associated with observed satellite-buoy differences allows us to analyze the origins of the main algorithmic errors observed in the SEVIRI field of view: a negative bias in the inter-tropical zone, and a mid-latitude positive bias. We demonstrate how these errors are explained by the sensitivity of observed brightness temperatures to the vertical distribution of water vapour, propagated through the SST retrieval algorithm.

Component-resolved bleaching spectra of quartz optically stimulated luminescence: preliminary results and implications for dating

Bleaching spectra of the ‘fast’ and ‘medium’ optically stimulated luminescence (OSL) components of quartz are reported. A dependence of photoionization cross-section, σ, on wavelength was observed for the fast and medium components and a significant difference in their responses to stimulation wavelength was found. The ratio of the fast and medium photoionization cross-sections, σfast/σmedium, varied from 30.6 when stimulated with View the MathML source light to 1.4 at View the MathML source. At View the MathML source the fast and medium photoionization cross-sections were found to be sufficiently different that infrared bleaching at raised temperatures allowed the selective removal of the fast component with negligible depletion of the medium. A method for optically separating the OSL components of quartz is suggested, based on the wavelength dependence of photoionization cross-sections.

Further investigations of the quartz optically stimulated luminescence components using linear modulation

The optically stimulated luminescence (OSL) from quartz is known to be the sum of several components with different rates of charge loss, originating from different trap types. The OSL components are clearly distinguished using the linear modulation (LM OSL) technique. A variety of pre-treatment and measurement conditions have been used on sedimentary samples in conjunction with linearly modulated optical stimulation to study in detail the behaviour of the OSL components of quartz. Single aliquots of different quartz samples have been found to contain typically five or six common LM OSL components when stimulated at View the MathML source. The components have been parameterised in terms of thermal stability (i.e. E and s), photoionisation cross-section energy dependence and dose response. The results of studies concerning applications of component-resolved LM OSL measurements on quartz are also presented. These include the detection of partial bleaching in young samples, use of ‘stepped wavelength’ stimulation to observe OSL from single components and attempts to extend the age range of quartz OSL dating.

Global radiative and climate effect of the water vapour continuum at visible and near-infrared wavelengths

Recent laboratory measurements show that absorption by the water vapour continuum in near-infrared windows may be about an order of magnitude higher than assumed in many radiation codes. The radiative impact of the continuum at visible and near-infrared wavelengths is examined for the present day and for a possible future warmer climate (with a global-mean total column water increase of 33%). The calculations use a continuum model frequently used in climate models (‘CKD’) and a continuum model where absorption is enhanced at wavelengths greater than 1 µm based on recent measurements (‘CAVIAR’). The continuum predominantly changes the partitioning between solar radiation absorbed by the surface and the atmosphere; changes in top-of-atmosphere net irradiances are smaller. The global-mean clear-sky atmospheric absorption is enhanced by 1.5 W m−2 (about 2%) and 2.8 W m−2 (about 3.5%) for CKD and CAVIAR respectively, relative to a hypothetical no-continuum case, with all-sky enhancements about 80% of these values. The continuum is, in relative terms, more important for radiation budget changes between the present day and a possible future climate. Relative to the no-continuum case, the increase in global-mean clear-sky absorption is 8% higher using CKD and almost 20% higher using CAVIAR; all-sky enhancements are about half these values. The effect of the continuum is estimated for the solar component of the water vapour feedback, the reduction in downward surface irradiance and precipitation change in a warmer world. For CKD and CAVIAR respectively, and relative to the no-continuum case, the solar component of the water vapour feedback is enhanced by about 4 and 9%, the change in clear-sky downward surface irradiance is 7 and 18% more negative, and the global-mean precipitation response decreases by 1 and 4%. There is a continued need for improved continuum measurements, especially at atmospheric temperatures and at wavelengths below 2 µm.

A critical evaluation of the ability of the Spinning Enhanced Visible and Infrared Imager (SEVIRI) thermal infrared red-green-blue rendering to identify dust events: theoretical analysis

Using a combination of idealized radiative transfer simulations and a case study from the first field campaign of the Saharan Mineral Dust Experiment (SAMUM) in southern Morocco, this paper provides a systematic assessment of the limitations of the widely used Spinning Enhanced Visible and Infrared Imager (SEVIRI) red-green-blue (RGB) thermal infrared dust product. Both analyses indicate that the ability of the product to identify dust, via its characteristic pink coloring, is strongly dependent on the column water vapor, the lower tropospheric lapse rate, and dust altitude. In particular, when column water vapor exceeds ∼20–25 mm, dust presence, even for visible optical depths of the order 0.8, is effectively masked. Variability in dust optical properties also has a marked impact on the imagery, primarily as a result of variability in dust composition. There is a moderate sensitivity to the satellite viewing geometry, particularly in moist conditions. The underlying surface can act to confound the signal seen through variations in spectral emissivity, which are predominantly manifested in the 8.7μm SEVIRI channel. In addition, if a temperature inversion is present, typical of early morning conditions over the Sahara and Sahel, an increased dust loading can actually reduce the pink coloring of the RGB image compared to pristine conditions. Attempts to match specific SEVIRI observations to simulations using SAMUM measurements are challenging because of high uncertainties in surface skin temperature and emissivity. Recommendations concerning the use and interpretation of the SEVIRI RGB imagery are provided on the basis of these findings.

Temporally stable feature clusters for maritime object tracking in visible and thermal imagery

This paper describes a new approach to detect and track maritime objects in real time. The approach particularly addresses the highly dynamic maritime environment, panning cameras, target scale changes, and operates on both visible and thermal imagery. Object detection is based on agglomerative clustering of temporally stable features. Object extents are first determined based on persistence of detected features and their relative separation and motion attributes. An explicit cluster merging and splitting process handles object creation and separation. Stable object clus- ters are tracked frame-to-frame. The effectiveness of the approach is demonstrated on four challenging real-world public datasets.

Making: the invisible visible

In this book essay I argue that modern and contemporary works of art (i.e. paintings, photographs, films, and videos) really ought to retrieve something of their auratic-character, which turns the physical toward the metaphysical, the material toward the immaterial, the visible toward the invisible - making artworks, ‘things among things, something other than [a] thing’ (Theodor W. Adorno, Aesthetic Theory, 86). There is, perhaps, an aura to art or art is a medium or a conduit or a technology for rediscovering and reproducing aura, which makes it something other than a mere thing. Such works of art are constitutively enigmatic, a certain form of magic making: they (re-)distribute the visible and the invisible, they (re-)configure appearance and disappearance. Such works of art may become visual events, which begin an education in and through (dis-)appearances. To achieve this end, I detail Theodor W. Adorno’s and Walter Benjamin’s respective theories of (art’s) aura in the age of technological reproducibility, which I relate to Jacques Rancière’s more recent discussion of the ‘pensive image,’ and I focus my reading on a number of works by Susan Hiller (photographs), John Constable (paintings), Alfred Stieglitz (photographs), and Tacita Dean (photograph and 16mm film).

Tibouchina pulchra (Cham.) Cogn., a native Atlantic Forest species, as a bio-indicator of ozone: Visible injury

Tibouchina pulchra saplings were exposed to carbon filtered air (CF), ambient non-filtered air (NF) and ambient non-filtered air + 40 ppb ozone (NF + O-3) 8 h per day during two months. The AOT40 values at the end of the experiment were 48, 910 and 12,895 ppb h(-1), respectively, for the three treatments. After 25 days of exposure (AOT40=3871 ppb h(-1)), interveinal red stippling appeared in plants in the NF + O-3 chamber. In the NF chamber, symptoms were observed only after 60 days of exposure (AOT40 = 910 ppb h(-1)). After 60 days, injured leaves per plant corresponded to 19% in NF + O-3 and 1% in the NF treatment; and the average leaf area injured was 7% within the NF + O-3 and 0.2% within the NF treatment. The extent of leaf area injured (leaf injury index) was mostly explained by the accumulated exposure of ozone (r(2) = 0.89; p < 0.05). (C) 2007 Elsevier Ltd. All rights reserved.

Luminescence studies on nitride quaternary alloys double quantum wells

We present theoretical photoluminescence (PL) spectra of undoped and p-doped Al(x)In(1-xy)Ga(y)N/Al(X)In(1) (X) (Y)Ga(Y)N double quantum wells (DQWs). The calculations were performed within the k.p method by means of solving a full eight-band Kane Hamiltonian together with the Poisson equation in a plane wave representation, including exchange-correlation effects within the local density approximation. Strain effects due to the lattice mismatch are also taken into account. We show the calculated PL spectra, analyzing the blue and red-shifts in energy as one varies the spike and the well widths, as well as the acceptor doping concentration. We found a transition between a regime of isolated quantum wells and that of interacting DQWs. Since there are few studies of optical properties of quantum wells based on nitride quaternary alloys, the results reported here will provide guidelines for the interpretation of forthcoming experiments. (C) 2008 Elsevier B.V. All rights reserved.