Substitution of Ti3+ and Ti4+ in hibonite (CaAl12O19)

The structures of eight synthetic samples of hibonite, with variable Ti oxidation state and Ti concentration (2.4–15.9 wt% TiO2) that span the range reported for natural hibonite found in meteorites, were determined by Rietveld refinements of neutron powder diffraction data. Ti3+ was found to exclusively occupy the octahedral face-sharing M4 site irrespective of the presence or absence of Ti4+. Ti4+ partitions between the trigonal bipyramidal M2 site and the M4 site. The ratio (Ti4+ on M2):(Ti4+ on M4) appears to be constant for all the samples, with an average of 0.18(2) irrespective of the concentrations of Ti3+ and Ti4+. These substitutional sites were shown to be the most stable configurations for Ti in hibonite from calculations using density functional theory, although the predicted preference of Ti4+ for M4 over M2 is not as strong as is observed. This is attributed to the different Ti contents of the experimental and calculated structures and suggests that the Ti site occupancies might change between these concentrations. Furthermore, it is shown that Ti has a preference to occupy neighboring M4 sites such that Ti-Ti interactions occur with stabilization energies of 83 kJ/mol for Ti3+-Ti3+ and at least 15 kJ/mol for Ti4+-Ti4+. Features in optical spectroscopy and electron spin resonance data from meteoritic and synthetic hibonites that have been used to infer Ti3+/Ti4+ are shown to actually derive from these Ti-Ti interactions. The amount of Ti4+ in hibonite can be determined from the unit-cell parameters if ∑Ti is determined independently. Ti3+/Ti4+ in hibonite may record the oxygen fugacity (fO2) of the early solar nebula, however, the existence of Ti3+-Ti3+ and Ti4+-Ti4+ interactions and the potential for Ti4+-Ti3+ interactions need to be considered when interpreting spectroscopic data in terms of Ti valence state and fO2. Hibonite as a single-mineral oxybarometer must be used with caution due to the potential role of crystal chemistry (including Ti-Ti interactions) to stabilize Ti oxidation states independently of fO2

Brain MRI in a patient with classical galactosemia: acute event of unilateral hemispheric cerebral edema

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Caspase-2 is upregulated after sciatic nerve transection and its inhibition protects dorsal root ganglion neurons from Apoptosis after serum withdrawal

Sciatic nerve (SN) transection-induced apoptosis of dorsal root ganglion neurons (DRGN) is one factor determining the efficacy of peripheral axonal regeneration and the return of sensation. Here, we tested the hypothesis that caspase-2(CASP2) orchestrates apoptosis of axotomised DRGN both in vivo and in vitro by disrupting the local neurotrophic supply to DRGN. We observed significantly elevated levels of cleaved CASP2 (C-CASP2), compared to cleaved caspase-3 (C-CASP3), within TUNEL+DRGN and DRG glia (satellite and Schwann cells) after SN transection. A serum withdrawal cell culture model, which induced 40% apoptotic death in DRGN and 60% in glia, was used to model DRGN loss after neurotrophic factor withdrawal. Elevated C-CASP2 and TUNEL were observed in both DRGN and DRG glia, with C-CASP2 localisation shifting from the cytosol to the nucleus, a required step for induction of direct CASP2-mediated apoptosis. Furthermore, siRNAmediated downregulation of CASP2 protected 50% of DRGN from apoptosis after serum withdrawal, while downregulation of CASP3 had no effect on DRGN or DRG glia survival. We conclude that CASP2 orchestrates the death of SN-axotomised DRGN directly and also indirectly through loss of DRG glia and their local neurotrophic factor support. Accordingly, inhibiting CASP2 expression is a potential therapy for improving both the SN regeneration response and peripheral sensory recovery

Territorialising brand experience and consumption: negotiating a role for pop-up retailing

The evolving consumption landscape creates challenges for retailers in accommodating their modus operandi to negotiate changing consumer needs, arguably requiring a ‘new’ type of retailing to hopefully facilitate future success. We suggest that an important aspect of such negotiation will be the use of ‘pop-up’ activity, and we critically evaluate the potential of these ephemeral consumption spaces to constitute and shape consumers’ brand-oriented relations and experiences into the future. Informed by the work of Deleuze and Guattari, we take a territorological perspective. Drawing on data from eight UK-based pop-up cases, we analyse: (1) how these temporary ‘territories’ of brand experience are developed and implemented; (2) what differentiates them from other, traditionally conceived, territories of brand experience; and (3) critically evaluate pop-up’s neglected characterisation in terms of a more ‘fluid’ spatial-temporal retail territory, to better understand its role in contemporary consumer culture. We posit that the development of pop-up activities occurs through the coordination of actions of a variety of stakeholders, constituting a spatial-temporal confluence of both material and processual elements to create a ‘refrain’, through the compression and compaction of interior, intermediary, exterior and annexed milieus. In doing so, we offer a new lens through which to view the creation of retail consumption spaces

Once more on the Witten index of 3d supersymmetric YM-CS theory

The problem of counting the vacuum states in the supersymmetric 3d Yang-Mills-Chern-Simons theory is reconsidered. We resolve the controversy between its original calculation by Witten at large volumes and the calculation based on the evaluation of the effective Lagrangian in the small volume limit. We show that the latter calculation suffers from uncertainties associated with the singularities in the moduli space of classical vacua where the Born-Oppenheimer approximation breaks down. We also show that these singularities can be accurately treated in the Hamiltonian Born-Oppenheimer method, where one has to match carefully the effective wave functions on the Abelian valley and the wave functions of reduced non-Abelian QM theory near the singularities. This gives the same result as original Witten's calculation.Comment: 27 page

Psychosocial developmental milestones in men with classic galactosemia

Patients with classic galactosemia suffer from several long term effects of their disease. Research in a group of mainly female patients has shown that these patients may also have a developmental delay with regard to their social aptitude. To study if male galactosemia patients achieve psychosocial developmental milestones more slowly than male peers from the general Dutch population, we assessed their development with the Course of Life Questionnaire (CoLQ). A total of 18 male galactosemia patients participated in this study (response rate 69%): 11 Dutch patients and seven American patients. We found severe delays in the social and psychosexual scales of this questionnaire, but not on the autonomy axis. These results are comparable to an earlier study with a limited number of male patients. The observed delays could be secondary to less developed social skills, cognitive dysfunction, or disrupted language development. We strongly recommend screening of galactosemia patients for developmental delays, to ensure early intervention through social skills training