The first isolated examples of intermolecular oxidative addition of alkenyl and alkynyl iodides to Au
are reported. Using a 5,5'-difluoro-2,2'-bipyridyl ligated complex, oxidative addition of ...geometrically defined alkenyl iodides occurs readily, reversibly and stereospecifically to give alkenyl-Au
complexes. Conversely, reversible alkynyl iodide oxidative addition generates bimetallic complexes containing both Au
and Au
centers. Stoichiometric studies show that both new initiation modes can form the basis for the development of C-C bond forming cross-couplings.
Peroxisomes participate in many important functions in plants, including seed reserve mobilization, photorespiration, defense against oxidative stress, and auxin and jasmonate signaling. In mammals, ...defects in peroxisome biogenesis result in multiple system abnormalities, severe developmental delay, and death, whereas in unicellular yeasts, peroxisomes are dispensable unless required for growth of specific substrates. PEX10 encodes an integral membrane protein required for peroxisome biogenesis in mammals and yeast. To investigate the importance of PEX10 in plants, we characterized a Ds insertion mutant in the PEX10 gene of Arabidopsis (AtPEX10). Heterozygous AtPEX10::dissociation element mutants show normal vegetative phenotypes under optimal growth conditions, but produce about 20% abnormal seeds. The embryos in the abnormal seeds are predominantly homozygous for the disruption allele. They show retarded development and some morphological abnormalities. No viable homozygous mutant plants were obtained. AtPEX10 fused to yellow fluorescent protein colocalized with green fluorescent protein-serine-lysine-leucine, a well-documented peroxisomal marker, suggesting that AtPEX10 encodes a peroxisomal protein that is essential for normal embryo development and viability.
The aims of this study were to evaluate six portable blood glucose meters for use in cats in a clinical setting and to identify potential sources of inaccuracy such as the effect of glucose ...concentration and haematocrit. Excess fluorinated whole-blood samples were obtained and were tested using the six meters and a reference laboratory method. Bland-Altman plots were constructed and an error grid analysis was performed, using a grid adapted in this study for diabetic cats. Error grids are a clinically oriented non-parametric approach to blood glucose data, and are designed to determine whether differences between glucometer and laboratory readings are clinically significant. All the meters studied had the potential to under- or overestimate blood glucose levels to varying degrees throughout the glycaemic range. This variation was not consistent enough to be predictable and correctable. The study failed to demonstrate any link between haematocrit and difference between laboratory and glucometer readings.
In the current discourse on the transition from school to work, career decision-making has a pivotal but paradoxical position. Sociological literature emphasises the dominance of socially-structured ...pathways, whilst policy-making operates on assumptions of individual freedom to choose. In this paper we draw on the work of Pierre Bourdieu to present a new model of career decision-making, given the shorthand title of 'careership'. There are three completely integrated dimensions to the model. These are (i) pragmatically rational decision-making, located in the habitus of the person making the decision; (ii) the interactions with others in the (youth training) field, related to the unequal resources different 'players' possess; and (iii) the location of decisions within the partly unpredictable pattern of turning-points and routines that make up the life course. This model avoids the twin pitfalls of implicit social determinism or of seeing (young) people as completely free agents.
Compartmentation of proteins and processes is a defining feature of eukaryotic cells. The growth and development of organisms is critically dependent on the accurate sorting of proteins within cells. ...The mechanisms by which cytosol-synthesized proteins are delivered to the membranes and membrane compartments have been extensively characterized. However, the protein complement of any given compartment is not precisely fixed and some proteins can move between compartments in response to metabolic or environmental triggers. The mechanisms and processes that mediate such relocation events are largely uncharacterized. Many proteins can in addition perform multiple functions, catalysing alternative reactions or performing structural, non-enzymatic functions. These alternative functions can be equally important functions in each cellular compartment. Such proteins are generally not dual-targeted proteins in the classic sense of having targeting sequences that direct de novo synthesized proteins to specific cellular locations. We propose that redox post-translational modifications (PTMs) can control the compartmentation of many such proteins, including antioxidant and/or redox-associated enzymes.
Between 1997 and 1999, 280 dogs with mast cell tumours were identified, of which 59 (21 per cent) had multiple tumours. Follow-up data for survival analysis were available for 145 dogs with single ...tumours and 50 dogs with multiple tumours. There was no significant difference between the survival times of the two groups; the survival rates after 12 and 24 months were 88 per cent and 83 per cent, respectively, for the dogs with single tumours, and 86 per cent at both intervals for the dogs with multiple tumours. Eight of the dogs with single tumours had lymph node metastases (stage II disease) and these dogs had a median survival time of 431 days, whereas the 50 dogs with multiple tumours (classified as stage III disease) and the dogs with single tumours (classified as stage I disease) had not reached their median survival times. Golden retrievers appeared to be predisposed to developing multiple tumours in the population studied, with an odds ratio of 3.8. This study found no evidence that dogs with multiple tumours had different survival times than those with single tumours, although there was evidence that the presence of lymph node metastasis generally carried a poorer prognosis.
We report systematic temperature-dependent X-ray measurements on the most stable carbamazepine polymorph. This active pharmaceutical ingredient is used to demonstrate how the thermal expansion can ...probe certain intermolecular interactions resulting in anisotropic expansion behavior. We show that most structural features can be captured by electronic structure calculations at the quasi-harmonic approximation (QHA) provided a dispersion-corrected density functional based method is employed. The impact of thermal expansion on the phonon modes and hence free energy contributions is large enough to impact the relative stability of different polymorphs.
The structural characteristics and physical properties of the 3,5‐bis(2‐pyridyl)‐1,2,4‐triazolate (L1) bridged dinuclear iron(II) spin‐crossover complex {Fe(NCBH3)(py)}2(μ‐L1)2 (1) in both powder ...(1p) and single crystal (1c) forms have been investigated. Both forms of {Fe(NCBH3)(py)}2(μ‐L1)2 display a thermally induced spin transition; however, the transitions have different T1/2 values and different degrees of spin conversion. Both forms display the photomagnetic light‐induced excited spin‐state trapping (LIESST) effect as well as reverse LIESST and have been compared by Raman spectral and powder X‐ray diffraction methods, which indicate that they are polymorphs. The single crystal form 1c shows a “half” spin transition and has been further characterised at temperatures above and below the spin transition by low temperature crystallographic methods including single crystal LIESST experiments (at 40 K) and by Mössbauer spectroscopy; thus, the nature of the HS‐LS form and the different spin isomers were revealed. To complement the experimental results, compound 1 and several other related FeII dinuclear spin‐crossover compounds have been evaluated by quantum‐chemical DFT calculations. Additionally, the susceptibilities for the powder form 1p, which displays a complete two‐step spin‐crossover, were also fitted to a phenomenological model for dinuclear spin‐crossover complexes.
A detailed synthetic, crystallographic, magnetic, light‐induced excited spin‐state trapping (LIESST), Mössbauer effect and theoretical investigation of spin‐crossover transitions is described for two polymorphs (crystalline and powder forms) of a triazolate‐bridged dinuclear iron(II) complex.
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