Synthesis and reactivity of tantalum corrole complexes Ziegler, Jessica A; Buckley, Heather L; Arnold, John
Dalton transactions : an international journal of inorganic chemistry,
2017, Letnik:
46, Številka:
3
Journal Article
Recenzirano
Reaction of the free base corrole (Mes
(p-OMePh)corrole)H
with tantalum trialkyl precursors TaMe
Cl
and TaBn
N
Bu resulted in the formation of the tantalum dichloride (1) and tantalum imido (4) ...corrole complexes via alkane elimination. The X-ray crystal structures of these two compounds have been determined and the structural parameters are discussed. The Ta centre of 1 was found to sit out of the plane of the corrole ring by 0.903 Å and is cis-ligated, similarly to what has been reported for group 4 porphyrin complexes. From complex 1 we synthesized the dimethyl derivative (2), the reactivity of which is compared to an analogous tantalum dimethyl porphyrin cation. The imido complex 4 reacted with triphenylmethanol and 4-methylbenzyl alcohol, resulting in different extents of protonation of the imido group.
The blazar Mrk 501 (z = 0.034) was observed at very-high-energy (VHE, E 100 GeV) gamma-ray wavelengths during a bright flare on the night of 2014 June 23-24 (MJD 56832) with the H.E.S.S. phase-II ...array of Cherenkov telescopes. Data taken that night by H.E.S.S. at large zenith angle reveal an exceptional number of gamma-ray photons at multi-TeV energies, with rapid flux variability and an energy coverage extending significantly up to 20 TeV. This data set is used to constrain Lorentz invariance violation (LIV) using two independent channels: a temporal approach considers the possibility of an energy dependence in the arrival time of gamma-rays, whereas a spectral approach considers the possibility of modifications to the interaction of VHE gamma-rays with extragalactic background light (EBL) photons. The non-detection of energy-dependent time delays and the non-observation of deviations between the measured spectrum and that of a supposed power-law intrinsic spectrum with standard EBL attenuation are used independently to derive strong constraints on the energy scale of LIV (EQG) in the subluminal scenario for linear and quadratic perturbations in the dispersion relation of photons. For the case of linear perturbations, the 95% confidence level limits obtained are EQG,1 > 3.6 × 1017 GeV using the temporal approach and EQG,1 > 2.6 × 1019 GeV using the spectral approach. For the case of quadratic perturbations, the limits obtained are EQG,2 > 8.5 × 1010 GeV using the temporal approach and EQG,2 > 7.8 × 1011 GeV using the spectral approach.
We previously reported low rates of pump thrombosis and hemorrhagic stroke, but increased bleeding, under our original antithrombosis protocol (P1) in HeartWare recipients. We designed and ...implemented a revised protocol (P2) to reduce complexity and bleeding. Thrombelastography and PFA‐100 guide antiplatelet titration. Goals for P2 were altered to decrease antiplatelet use and anticoagulation intensity. We compared the incidence and rates of gastrointestinal bleeding (GIB), embolic (eCVA) and hemorrhagic (hCVA) stroke, pump thrombosis (PT), and total bleeding (GIB+hCVA), total thrombosis (eCVA+PT), and total events between P1 and P2. Laboratory and medication data were assessed. Patients with and without hemocompatibility‐related adverse events (HRAEs) were compared. The study included 123 patients (P1: 65; P2: 58). GIB rate decreased (P1: 0.66; P2 0.30 EPPY, P = .003). CVA rates and incidence were statistically similar, although hCVA incidence increased (P1: 3%; P2: 12%, P = .06). Incidence (P1: 3%; P2: 16%, P = .02) and rate (P1: 0.03; P2: 0.12 EPPY, P = .08) of PT increased. Incidence and rate of overall HRAEs and thrombotic events were similar, while bleeding rate decreased (P1: 0.69; P2: 0.40 EPPY, P = .02). Twelve‐month medication burden decreased. Compared to non‐HRAE patients, patients with bleeding HRAEs had more antiplatelet and pentoxifylline use, but less statin use; and lower PFAs. Patients with thrombotic HRAEs had less dual antiplatelet use, lower INRs, R‐times, and PFA‐ADP values. A revised antithrombotic protocol decreased GIB and overall hemorrhagic HRAE rate and medication burden. Unfortunately, PT increased. Non‐HRAE and HRAE patients differed in anticoagulation and antiplatelet intensity. These differences will guide the revision of P2.
Comparison of changes in GI bleeding and pump thrombosis under original (Protocol 1) and revised (Protocol 2) antithrombosis regimens.
Summary
Biological membranes are often poorly visible with the electron microscope after high‐pressure freezing and freeze‐substitution. The water content of the sample and of the substitution medium ...is one factor among others that strongly influences membrane visibility. In order to investigate this effect, high‐pressure frozen yeast cells, rat‐pancreas tissue and arthropod tissue were freeze‐substituted with and without adding water to the substitution medium. The visibility of the biological membranes was generally improved if the substitution medium contained 1–5% water. The effect was especially pronounced in yeast cells, where membrane visibility was poor after freeze‐substitution with water‐free medium but good after addition of 5% water to the substitution medium.
Increased brain volume in autism appears to be driven mainly by an unexplained white matter enlargement, and we have reported a similar phenomenon in developmental language disorder (DLD). ...Localization of this enlargement would strongly guide research into its cause, tissue basis, and functional implications. We utilized a white matter parcellation technique that divides cerebral white matter into an outer zone containing the radiate compartment and an inner zone containing sagittal and bridging system compartments. In both high‐functioning autism and DLD, enlargement localized to the radiate white matter (all lobes in autism, all but parietal in DLD), whereas inner zone white matter compartments showed no volume differences from controls. Furthermore, in both autism and DLD, later or longer‐myelinating regions showed greater volume increases over controls. Neither group showed cerebral cortex, corpus callosum, or internal capsule volume differences from control. Radiate white matter myelinates later than deep white matter; this pattern of enlargement thus is consistent with striking postnatal head circumference percentile increases reported in autism. These findings suggest an ongoing postnatal process in both autism and DLD that is probably intrinsic to white matter, that primarily affects intrahemispheric and corticocortical connections, and that places these two disorders on the same spectrum.
Abstract Volumetric magnetic resonance imaging (MRI) brain data provide a valuable tool for detecting structural differences associated with various neurological and psychiatric disorders. Analysis ...of such data, however, is not always straightforward, and complications can arise when trying to determine which brain structures are “smaller” or “larger” in light of the high degree of individual variability across the population. Several statistical methods for adjusting for individual differences in overall cranial or brain size have been used in the literature, but critical differences exist between them. Using agreement among those methods as an indication of stronger support of a hypothesis is dangerous given that each requires a different set of assumptions be met. Here we examine the theoretical underpinnings of three of these adjustment methods (proportion, residual, and analysis of covariance) and apply them to a volumetric MRI data set. These three methods used for adjusting for brain size are specific cases of a generalized approach which we propose as a recommended modeling strategy. We assess the level of agreement among methods and provide graphical tools to assist researchers in determining how they differ in the types of relationships they can unmask, and provide a useful method by which researchers may tease out important relationships in volumetric MRI data. We conclude with the recommended procedure involving the use of graphical analyses to help uncover potential relationships the ROI volumes may have with head size and give a generalized modeling strategy by which researchers can make such adjustments that include as special cases the three commonly employed methods mentioned above.
The filter media in biofiltration systems play an important role in removing potentially harmful pollutants from urban stormwater runoff. This study compares the heavy metal removal potential (Cu, ...Zn, Cd, Pb) of five materials (potting soil, compost, coconut coir, sludge and a commercial mix) using laboratory columns. Total/dissolved organic carbon (TOC/DOC) was also analysed because some of the test materials had high carbon content which affects heavy metal uptake/release. Potting soil and the commercial mix offered the best metal uptake when dosed with low (Cu: 44.78 μg/L, Zn: 436.4 μg/L, Cd, 1.82 μg/L, Pb: 51.32 μg/L) and high concentrations of heavy metals (Cu: 241 μg/L, Zn: 1127 μg/L, Cd: 4.57 μg/L, Pb: 90.25 μg/L). Compost and sludge also had high removal efficiencies (>90%). Heavy metal leaching from these materials was negligible. A one-month dry period between dosing experiments did not affect metal removal efficiencies. TOC concentrations from all materials increased after the dry period. Heavy metal removal was not affected by filter media depth (600 mm vs. 300 mm). Heavy metals tended to accumulate at the upper 5 cm of the filter media although potting soil showed bottom-enriched concentrations. We recommend using potting soil as the principal media mixed with compost or sludge since these materials perform well and are readily available. The use of renewable materials commonly found in Singapore supports a sustainable approach to urban water management.
•Heavy metal removal by soil, compost, coconut, sludge and commercial mix was tested.•The heavy metals included Cu, Zn, Cd and Pb.•Soil and commercial mix had the highest metal uptake out of the five materials.•The depth of the material did not affect heavy metal removal.•Most of the heavy metals accumulated in the top 5 cm of the materials tested.
Newborn and 14-day-old mice inoculated subcutaneously with chikungunya virus (CHIKV) developed lethargy, difficulty walking, dragging of hind limbs, and reduced weight gain within 7-10 days after ...infection (PI). During the initial 6-7 days PI, the animals had viremia; high levels (10(6)-10(8) PFU) of CHIKV were also present in leg muscle. The virus persisted in muscle for several days after viremia disappeared. The major histopathologic changes were in skeletal muscle, which were focal necrosis and inflammation, followed by fibrosis and dystrophic calcification. Some mice also showed dystrophic calcification in the joint cartilage, but there were few deaths, and most of the animals eventually recovered. CHIKV antigen was shown by immunohistochemistry in the muscle for several weeks after infection. Based on the clinical and pathologic similarities with CHIKV infection in humans, young ICR and CD-1 mice offer a useful and realistic model for further study of the pathogenesis and treatment of CHIKV infection.
High‐functioning autistic and normal school‐age boys were compared using a whole‐brain morphometric profile that includes both total brain volume and volumes of all major brain regions. We performed ...MRI‐based morphometric analysis on the brains of 17 autistic and 15 control subjects, all male with normal intelligence, aged 7–11 years. Clinical neuroradiologists judged the brains of all subjects to be clinically normal. The entire brain was segmented into cerebrum, cerebellum, brainstem and ventricles. The cerebrum was subdivided into cerebral cortex, cerebral white matter, hippocampus–amygdala, caudate nucleus, globus pallidus plus putamen, and diencephalon (thalamus plus ventral diencephalon). Volumes were derived for each region and compared between groups both before and after adjustment for variation in total brain volume. Factor analysis was then used to group brain regions based on their intercorrelations. Volumes were significantly different between groups overall; and diencephalon, cerebral white matter, cerebellum and globus pallidus–putamen were significantly larger in the autistic group. Brain volumes were not significantly different overall after adjustment for total brain size, but this analysis approached significance and effect sizes and univariate comparisons remained notable for three regions, although not all in the same direction: cerebral white matter showed a trend towards being disproportionately larger in autistic boys, while cerebral cortex and hippocampus–amygdala showed trends toward being disproportionately smaller. Factor analysis of all brain region volumes yielded three factors, with central white matter grouping alone, and with cerebral cortex and hippocampus–amygdala grouping separately from other grey matter regions. This morphometric profile of the autistic brain suggests that there is an overall increase in brain volumes compared with controls. Additionally, results suggest that there may be differential effects driving white matter to be larger and cerebral cortex and hippocampus–amygdala to be relatively smaller in the autistic than in the typically developing brain. The cause of this apparent dissociation of cerebral cortical regions from subcortical regions and of cortical white from grey matter is unknown, and merits further investigation.
Context: Zinc transporter 8 (ZnT8) is a newly discovered islet autoantigen in human type 1A diabetes (T1D).
Objective: The objective was to document changes in ZnT8 autoantibody (ZnT8A) titer and ...prevalence after onset of disease in relationship to 65 kDa glutamate decarboxylase antibody (GADA) and islet cell antigen antibody (IA2A).
Design/Patients: Autoantibody radioimmunoprecipitation assays were performed on sera from three groups: 21 individuals monitored every 3 months from diagnosis for 2.5 yr; 61 individuals monitored at six monthly intervals for 5–12 yr; and a cross-sectional study of 424 patients with T1D of 20–57 yr duration. Circulating C-peptide was determined as an index of residual β-cell function.
Results: ZnT8A titers declined exponentially from clinical onset of T1D with a t1/2 ranging from 26 to 530 wk, similar to C-peptide (23–300 wk). Life-table analysis of antibody prevalence to 12 yr indicated that ZnT8A measured with either Arg325 or Trp325 probes persisted for a shorter interval than IA2A. Although prevalence of ZnT8A, IA2A, and GADA were comparable at disease onset (70.4 vs. 73.4 vs. 64%), only 6.7% of individuals remained ZnT8A positive after 25 yr compared with 19.5% for IA2A and 25.9% for GADA. Titers of ZnT8A and IA2A in seropositive individuals decreased progressively, whereas GADA remained elevated consistent with periodic reactivation of GADA humoral autoimmunity.
Conclusions: ZnT8 humoral autoreactivity declines rapidly in the first years after disease onset and is less persistent than IA2A or GADA in the longer term. ZnT8A determination may be a useful measure of therapeutic efficacy in the context of immune-based clinical interventions.
ZnT8 autoantibody titer declines rapidly post-onset of type 1 diabetes, and its prevalence falls from 70% initially to less than 10% within 20 years.
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