Distribution of esterase activity in porcine ear skin, and the effects of freezing and heat separation

Porcine ear skin is widely used to study skin permeation and absorption of ester compounds, whose permeation and absorption profiles may be directly influenced by in situ skin esterase activity. Importantly, esterase distribution and activity in porcine ear skin following common protocols of skin handling and storage have not been characterised. Thus, we have compared the distribution and hydrolytic activity of esterases in freshly excised, frozen, heated and explanted porcine ear skin. Using an esterase staining kit, esterase activity was found to be localised in the stratum corneum and viable epidermis. Under frozen storage and a common heating protocol of epidermal sheet separation, esterase staining in the skin visibly diminished. This was confirmed by a quantitative assay using HPLC to monitor the hydrolysis of aspirin, in freshly excised, frozen or heated porcine ear skin. Compared to vehicle-only control, the rate of aspirin hydrolysis was approximately three-fold higher in the presence of freshly excised skin, but no different in the presence of frozen or heated skin. Therefore, frozen and heat-separated porcine ear skin should not be used to study the permeation of ester-containing permeants, in particular co-drugs and pro-drugs, whose hydrolysis or degradation can be modulated by skin esterases.

Complexation of lanthanides, actinides and transition metal cations with a 6-(1,2,4-triazin-3-yl)-2,2′:6′,2′′-terpyridine ligand: implications for actinide(III)/lanthanide(III) partitioning

The quadridentate N-heterocyclic ligand 6-(5,5,8,8-tetramethyl-5,6,7,8-tetrahydro-1,2,4-benzotriazin- 3-yl)-2,2′ : 6′,2′′-terpyridine (CyMe4-hemi-BTBP) has been synthesized and its interactions with Am(III),U(VI), Ln(III) and some transition metal cations have been evaluated by X-ray crystallographic analysis, Am(III)/Eu(III) solvent extraction experiments, UVabsorption spectrophotometry, NMR studies and ESI-MS. Structures of 1 : 1 complexes with Eu(III), Ce(III) and the linear uranyl (UO2 2+) ion were obtained by X-ray crystallographic analysis, and they showed similar coordination behavior to related BTBP complexes. In methanol, the stability constants of the Ln(III) complexes are slightly lower than those of the analogous quadridentate bis-triazine BTBP ligands, while the stability constant for the Yb(III)complex is higher. 1H NMR titrations and ESI-MS with lanthanide nitrates showed that the ligand forms only 1 : 1 complexes with Eu(III), Ce(III) and Yb(III), while both 1 : 1 and 1 : 2 complexes were formed with La(III) and Y(III) in acetonitrile. A mixture of isomeric chiral 2 : 2 helical complexes was formed with Cu(I), with a slight preference (1.4 : 1) for a single directional isomer. In contrast, a 1 : 1 complex was observed with the larger Ag(I) ion. The ligand was unable to extract Am(III) or Eu(III) from nitric acid solutions into 1-octanol, except in the presence of a synergist at low acidity. The results show that the presence of two outer 1,2,4-triazine rings is required for the efficient extraction and separation of An(III)from Ln(III) by quadridentate N-donor ligands.

Lanthanide speciation in potential SANEX and GANEX actinide/ 2 lanthanide separations using Tetra-N-Donor extractants

Lanthanide(III) complexes with N-donor ex-tractants, which exhibit the potential for the separation of minor actinides from lanthanides in the management of spent nuclear fuel, have been directly synthesized and characterized in both solution and solid states. Crystal structures of the Pr3+, Eu3+, Tb3+, and Yb3+ complexes of 6,6′-bis(5,5,8,8-tetramethyl-5,6,7,8-tetrahydro-1,2,4-benzotriazin3-yl)-1,10-phenanthroline(CyMe4-BTPhen) and the Pr3+, Eu3+, and Tb3+ complexes of 2,9-bis(5,5,8,8-tetramethyl-5,6,7,8-tetrahydro-1,2,4-benzotria-zin-3-yl)-2,2′-bypyridine (CyMe4-BTBP) were obtained. The majority of these structures displayed coordination of two ofthe tetra-N-donor ligands to each Ln3+ ion, even when in some cases the complexations were performed with equimolar amounts of lanthanide and N-donor ligand. The structures showed that generally the lighter lanthanides had their coordination spheres completed by a bidentate nitrate ion, giving a 2+ charged complex cation, whereas the structures of the heavier lanthanides displayed tricationic complex species with a single water molecule completing their coordination environments. Electronic absorption spectroscopic titrations showed formation of the 1:2 Ln3+/LN4‑donor species (Ln = Pr3+, Eu3+, Tb3+) in methanol when the N-donor ligand was in excess. When the Ln3+ ion was in excess, evidence for formation of a 1:1 Ln3+/LN4‑donor complex species was observed. Luminescent lifetime studies of mixtures of Eu3+ with excess CyMe4-BTBP and CyMe4-BTPhen in methanol indicated that the nitrate-coordinated species is dominant in solution. X-ray absorption spectra of Eu3+ and Tb3+ species, formed by extraction from an acidic aqueous phase into an organic solution consisting of excess N-donor extractant in pure cyclohexanone or 30% tri-n-butyl phosphate (TBP) in cyclohexanone, were obtained. The presence of TBP in the organic phase did not alter lanthanide speciation. Extended X-ray absorption fine structure data from these spectra were fitted using chemical models established by crystallography and solution spectroscopy and showed the dominant lanthanide species in the bulk organic phase was a 1:2 Ln3+/LN‑donor species.

Modelling of urban sensible heat flux at multiple spatial scales : a demonstration using airborne hyperspectral imagery of Shanghai and a temperature–emissivity separation approach

Urbanization related alterations to the surface energy balance impact urban warming (‘heat islands’), the growth of the boundary layer, and many other biophysical processes. Traditionally, in situ heat flux measures have been used to quantify such processes, but these typically represent only a small local-scale area within the heterogeneous urban environment. For this reason, remote sensing approaches are very attractive for elucidating more spatially representative information. Here we use hyperspectral imagery from a new airborne sensor, the Operative Modular Imaging Spectrometer (OMIS), along with a survey map and meteorological data, to derive the land cover information and surface parameters required to map spatial variations in turbulent sensible heat flux (QH). The results from two spatially-explicit flux retrieval methods which use contrasting approaches and, to a large degree, different input data are compared for a central urban area of Shanghai, China: (1) the Local-scale Urban Meteorological Parameterization Scheme (LUMPS) and (2) an Aerodynamic Resistance Method (ARM). Sensible heat fluxes are determined at the full 6 m spatial resolution of the OMIS sensor, and at lower resolutions via pixel aggregation and spatial averaging. At the 6 m spatial resolution, the sensible heat flux of rooftop dominated pixels exceeds that of roads, water and vegetated areas, with values peaking at ∼ 350 W m− 2, whilst the storage heat flux is greatest for road dominated pixels (peaking at around 420 W m− 2). We investigate the use of both OMIS-derived land surface temperatures made using a Temperature–Emissivity Separation (TES) approach, and land surface temperatures estimated from air temperature measures. Sensible heat flux differences from the two approaches over the entire 2 × 2 km study area are less than 30 W m− 2, suggesting that methods employing either strategy maybe practica1 when operated using low spatial resolution (e.g. 1 km) data. Due to the differing methodologies, direct comparisons between results obtained with the LUMPS and ARM methods are most sensibly made at reduced spatial scales. At 30 m spatial resolution, both approaches produce similar results, with the smallest difference being less than 15 W m− 2 in mean QH averaged over the entire study area. This is encouraging given the differing architecture and data requirements of the LUMPS and ARM methods. Furthermore, in terms of mean study QH, the results obtained by averaging the original 6 m spatial resolution LUMPS-derived QH values to 30 and 90 m spatial resolution are within ∼ 5 W m− 2 of those derived from averaging the original surface parameter maps prior to input into LUMPS, suggesting that that use of much lower spatial resolution spaceborne imagery data, for example from Advanced Spaceborne Thermal Emission and Reflection Radiometer (ASTER) is likely to be a practical solution for heat flux determination in urban areas.

Separation of performance-approach and performance-avoidance achievement goals: A broader analysis

In the literature on achievement goals, performance-approach goals (striving to do better than others) and performance-avoidance goals (striving to avoid doing worse than others) tend to exhibit a moderate to high correlation, raising questions about whether the 2 goals represent distinct constructs. In the current article, we sought to examine the separability of these 2 goals using a broad factor-analytic approach that attended to issues that have been overlooked or underexamined in prior research. Five studies provided strong evidence for the separation of these 2 goal constructs: Separation was observed not only with exploratory factor analysis across different age groups and countries (Studies 1a and 1b) but also with change analysis (Study 2), ipsative factor analysis (Study 3), within-person analysis (Study 4), and behavioral genetics analysis (Study 5). We conclude by discussing the implications of the present research for the achievement goal literature, as well as the psychological literature in general.

Stylised worlds: Colour Separation Overlay in BBC television plays of the 1970s

This essay aims to understand and interrogate the use of Colour Separation Overlay (CSO) as a mode of experimental production and aesthetic innovation in television drama in the 1970s. It sets out to do this by describing, accounting for and evaluating CSO as a production technique, considering the role of key production personnel, and analysing four specific BBC productions. Deploying methodologies of archival research, practitioner interview, and close textual analysis, the essay also delivers a significant reassessment of the role of the producer and designer in the conceptualisation and realisation of small-screen dramatic fiction.

Phase separation and surface segregation in ceria-zirconia solid solutions

Using a combination of density functional theory calculations and statistical mechanics, we show that a wide range of intermediate compositions of ceria – zirconia solid solutions are thermodynamically metastable with respect to phase separation into Ce-rich and Zr-rich oxides. We estimate that the maximum equilibrium concentration of Zr in CeO2 at 1373 K is ~2%, and therefore equilibrated samples with higher Zr content are expected to exhibit heterogeneity at the atomic scale. We also demonstrate that in the vicinity of the (111) surface, cation redistribution at high temperatures will occur with significant Ce enrichment of the surface, which we attribute to the more covalent character of Zr-O bonds compared to Ce-O bonds. Although the kinetic barriers for cation diffusion normally prevent the decomposition/segregation of ceria-zirconia solid solutions in typical catalytic applications, the separation behaviour described here can be expected to occur in modern three-way catalytic converters, where very high temperatures are reached.

Estimation of magnet separation for magnetic suspension applications

This thesis describes a form of non-contact measurement using two dimensional hall effect sensing to resolve the location of a moving magnet which is part of a ‘magnetic spring’ type suspension system. This work was inspired by the field of Space Robotics, which currently relies on solid link suspension techniques for rover stability. This thesis details the design, development and testing of a novel magnetic suspension system with a possible application in space and terrestrial based robotics, especially when the robot needs to traverse rough terrain. A number of algorithms were developed, to utilize experimental data from testing, that can approximate the separation between magnets in the suspension module through observation of the magnetic fields. Experimental hardware was also developed to demonstrate how two dimensional hall effect sensor arrays could provide accurate feedback, with respects to the magnetic suspension modules operation, so that future work can include the sensor array in a real-time control system to produce dynamic ride control for space robots. The research performed has proven that two dimensional hall effect sensing with respects to magnetic suspension is accurate, effective and suitable for future testing.

Effective separation of Am(III) and Eu(III) from HNO3 Q1 Q2 solutions using CyMe4-BTPhen-functionalized silica-coated magnetic nanoparticles

It has been shown that CyMe4-BTPhen-functionalized silica-coated maghemite (c-Fe2O3) magnetic nanoparticles (MNPs) are capable of quantitative separation of Am(III) from Eu(III) from HNO3 solutions. These MNPs also show a small but significant selectivity for Am(III) over Cm(III) with a separation factor of around 2 in 4 M HNO3. The water molecule in the cavity of the BTPhen may also play an important part in the selectivity.

Effective separation of Am(III) and Eu(III) from HNO3 solutions using CyMe4-BTPhen-functionalized silica-coated magnetic nanoparticles

It has been shown that CyMe4-BTPhen-functionalized silica-coated maghemite (c-Fe2O3) magnetic nanoparticles (MNPs) are capable of quantitative separation of Am(III) from Eu(III) from HNO3 solutions. These MNPs also show a small but significant selectivity for Am(III) over Cm(III) with a separation factor of around 2 in 4 M HNO3. The water molecule in the cavity of the BTPhen may also play an important part in the selectivity.

Evaluating perceptual separation in a pilot system for affective composition

Research evaluating perceptual responses to music has identified many structural features as correlates that might be incorporated in computer music systems for affectively charged algorithmic composition and/or expressive music performance. In order to investigate the possible integration of isolated musical features to such a system, a discrete feature known to correlate some with emotional responses – rhythmic density – was selected from a literature review and incorporated into a prototype system. This system produces variation in rhythm density via a transformative process. A stimulus set created using this system was then subjected to a perceptual evaluation. Pairwise comparisons were used to scale differences between 48 stimuli. Listener responses were analysed with Multidimensional scaling (MDS). The 2-Dimensional solution was then rotated to place the stimuli with the largest range of variation across the horizontal plane. Stimuli with variation in rhythmic density were placed further from the source material than stimuli that were generated by random permutation. This, combined with the striking similarity between the MDS scaling and that of the 2-dimensional emotional model used by some affective algorithmic composition systems, suggests that isolated musical feature manipulation can now be used to parametrically control affectively charged automated composition in a larger system.

GPVI and CLEC-2

The glycoprotein VI (GPVI)-FcR gamma-chain complex initiates powerful activation of platelets by the subendothelial matrix proteins collagen and laminin, which are exposed following vessel damage. Initiation of platelet activation is through an immunoreceptor tyrosine-based activation motif (ITAM). C-type lectin receptor 2 (CLEC-2), following engagement by its endogenous ligand, podoplanin, also mediates powerful platelet activation through Src and Syk kinases, but regulates Syk through a novel dimerization mechanism via a single YxxL motif known as a hemITAM. This chapter compares the signaling pathways of both receptors and their role in hemostasis and thrombosis. Platelets are also increasingly implicated in processes beyond hemostasis and thrombosis. One such process is the efficient separation of the lymphatic and blood vasculatures, which is dependent on CLEC-2-mediated platelet activation.