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Copper(I) (±)-N,N'-bis(2,4,6-trimethylbenzylidene)-1,2-diaminocyclohexane reacts with either ethene or butadiene to give the corresponding alkene complexes. In each case crystallographic studies show that the alkene coordinates in an η2 fashion. In the butadiene complex a dimer is formed where the butadiene bridges two copper complexes. Variable temperature NMR spectroscopy of the ethene adduct demonstrates fluxional behaviour, which is attributed to the rotation of the coordinated ethene relative to the complex, ΔG‡ 255 = 50 ± 2 kJ mol-1. [ABSTRACT FROM AUTHOR]

Copper(i) (±)-N,N′-bis(2,4,6-trimethylbenzylidene)-1,2-diaminocyclohexane reacts with either ethene or butadiene to give the corresponding alkene complexes. In each case crystallographic studies show that the alkene coordinates in an η2fashion. In the butadiene complex a dimer is formed where the butadiene bridges two copper complexes. Variable temperature NMR spectroscopy of the ethene adduct demonstrates fluxional behaviour, which is attributed to the rotation of the coordinated ethene relative to the complex, ΔG‡255= 50 ± 2 kJ mol−1. [ABSTRACT FROM AUTHOR]

AbstractHistorically people with intellectual disabilities have not been offered or received cognitive behavioural interventions that have been shown to be effective for mental health and emotional problems experienced by those without such disabilities. This is despite many people with intellectual disabilities having life experiences that potentially result in them having an increased risk to such problems. This paper discusses whether such therapeutic disdain is justified based on the evidence that is available and emerging concerning the application of cognitive behavioural interventions for this population. Issues concerning access to services, the ability of people with intellectual disabilities to engage in and benefit from the cognitive components of CBT, and the effect of cognitive abilities and IQ level on treatment effectiveness are explored in relation to this question. [ABSTRACT FROM AUTHOR]

For image-guided radiotherapy (IGRT) systems based on cone beam CT (CBCT) integrated into a linear accelerator, the reproducible alignment of imager to x-ray source is critical to the registration of both the x-ray-volumetric image with the megavoltage (MV) beam isocentre and image sharpness. An enhanced method of determining the CBCT to MV isocentre alignment using the QUASAR Penta-Guide phantom was developed which improved both precision and accuracy. This was benchmarked against our existing method which used software and a ball-bearing (BB) phantom provided by Elekta. Additionally, a method of measuring an image sharpness metric (MTF50) from the edge response function of a spherical air cavity within the Penta-Guide phantom was developed and its sensitivity was tested by simulating misalignments of the kV imager. Reproducibility testing of the enhanced Penta-Guide method demonstrated a systematic error of <0.2 mm when compared to the BB method with near equivalent random error (s = 0.15 mm). The mean MTF50 for five measurements was 0.278 ± 0.004 lp mm[?]1 with no applied misalignment. Simulated misalignments exhibited a clear peak in the MTF50 enabling misalignments greater than 0.4 mm to be detected. The Penta-Guide phantom can be used to precisely measure CBCT-MV coincidence and image sharpness on CBCT-IGRT systems. [ABSTRACT FROM AUTHOR]

The synthesis is reported of a series of metalloporphyrins (and the corresponding free-base porphyrin), mono-meso-substituted with a bipyridyl group via an amide link at the 4-position of one phenyl group: [Re(CO)3(Pic)Bpy-MTPP][OTf], where M = Mg, Zn, Pd or 2H, Pic = 3-picoline, Bpy = 2,2′-bipyridine, TPP = tetraphenylporphyrin. The photochemical reactions of the assemblies with the sacrificial electron donor triethylamine have been investigated by IR spectroscopy and compared to the behaviour of analogues of the type Bpy-MTPP without rhenium. Selective long-wavelength irradiation of the metalloporphyrin unit in the presence of excess picoline leads to reduction at the rhenium bipyridine centre. In the absence of 3-picoline, the latter is not reduced, but substituted by added halide or by the THF solvent. Mechanistic analysis highlights the differences between the zinc and magnesium chelate on the one hand and the palladium porphyrin on the other. The free-base assembly, [Re(CO)3(Pic)Bpy-H2TPP][OTf] is unreactive. The zinc and magnesium porphyrin assemblies initially coordinate Et3N before undergoing photo-induced inner-sphere electron transfer from the triethylamine to form a charge-shifted excited state of the assembly. In contrast, the palladium-based dyad reacts via outer-sphere reductive quenching of a porphyrin-based excited state. The substitution products are postulated to form by a mechanism involving an electron-transfer chain. [ABSTRACT FROM AUTHOR]

Abstract: A mechanistic study of organosulfide oxidation by H2O2, using a dinuclear manganese complex as the catalyst, has revealed an unusual switch in the philicity of the oxidant for the first and the second oxygen transfer steps; this switch has been exploited to tune selectivity for each of the products. [Copyright &y& Elsevier]

Abstract: Resonance Raman and UV–visible diffuse reflectance spectra were recorded from samples of cotton, viscose, polyester, nylon, and acrylic textile swatches dyed black with one of seven single dyes, a mixture of two dyes, or one of seven mixtures of three dyes. The samples generally gave characteristic Raman spectra of the dyes, demonstrating that the technique is applicable for the forensic analysis of dyed black textiles. Survey studies of the widely used dye Reactive Black 5 show that essentially the same Raman spectrum is obtained on bulk sampling from the dye in solution, on viscose, on cotton at different uptakes, and on microscope sampling from the dye in cotton threads and single fibres. The effects of laser irradiation on the Raman bands and emission backgrounds from textile samples with and without dye are also reported. [Copyright &y& Elsevier]

Abstract: Ultrafast time-resolved UV–visible absorption spectroscopy has been used to study four model azo dyes and five commercial azo dyes. All of the dyes have been found to show strong bleaching of their ground-state absorption bands on photoexcitation, with recovery lifetimes of 1–5ps in aqueous solution that are attributed to rapid and efficient non-radiative decay; two commercial azo dyes deposited in cellophane have been found to show an additional longer-lived component with a lifetime of >50ps that is attributed to the effects of intermolecular interactions with the cellulosic environment. [Copyright &y& Elsevier]

Fitness of tick-borne pathogens may be determined by the degree to which their infection dynamics in vertebrate hosts permits transmission cycles if infective and uninfected tick stages are active at different times of the year. To investigate this hypothesis we developed a simulation model that integrates the transmission pattern imposed by seasonally asynchronous nymphal and larval Ixodes scapularis ticks in northeastern North America, with a model of infection in white-footed mice (Peromyscus leucopus) reservoir hosts, using the bacteria Borrelia burgdorferi and Anaplasma phagocytophilum as examples. In simulations, survival of microparasites, their sensitivity to reduced rodent and tick abundance, and to ‘dilution’ by a reservoir-incompetent host depended on traits that allowed (i) highly efficient transmission from acutely-infected hosts, (ii) long-lived acute or ‘carrier’ host infections, and/or (iii) transmission amongst co-feeding ticks. Minimum values for transmission efficiency to ticks, and duration of host infectivity, necessary for microparasite persistence, were always higher when nymphal and larval ticks were seasonally asynchronous than when these instars were synchronous. Thus, traits influencing duration of host infectivity, transmission efficiency to ticks and co-feeding transmission are likely to be dominant determinants of fitness in I. scapularis-borne microparasites in northeastern North America due to abiotic forcings influencing I. scapularis seasonality. [ABSTRACT FROM AUTHOR]

Abstract: This paper reports an HPLC–MS/MS investigation of praziquantel (anthelmintic agent) oxidation by iodosylbenzene in an organic medium, using iron(III) tetraarylporphyrins (where aryl=phenyl, pentafluorophenyl, 2-nitrophenyl, 2-trifluoromethylphenyl and mesityl) and manganese(III) tetraphenylporphyrin as catalysts. The majority of the oxidation products have been identified by sequential MS and NMR analyses. The selectivities of the oxidations by these cytochrome P-450 models are studied and compared. Time dependent reaction profiles suggest that with all the catalysts, the initial oxidation occurs predominantly at the 7-position. With Fe(T2TFMPP)Cl the yield and selectivity (64%) for 7-hydroxypraziquantel remain high even after 24h reaction, whereas with the other catalysts this initial product is further oxidized to di- and trihydroxypraziquantel. The Fe(TFPP)Cl system results in the higher yield (11%) of cis- and trans-4′-hydroxypraziquantel, the major metabolites from in vivo and in vitro metabolism of praziquantel by cytochrome P-450 monooxygenases. [Copyright &y& Elsevier]