2,112 research outputs found

    Synthesis and coordination chemistry of 2-(di-2-pyridylamino)pyrimidine; structural aspects of spin crossover in an Fe(II) complex

    Get PDF
    This paper was accepted on February 26 20122-(Di-2-pyridylamino)pyrimidine (L), a potentially ditopic tetradentate ligand, was synthesized from commercially available di-2-pyridylamine and 2-chloropyrimidine. Despite being capable of bridging two metal atoms with bidentate chelation of both metal centres, L prefers to chelate or bridge through the more basic pyridyl donors of the di-2-pyridylamine moiety. Mononuclear trans-[Fe(NCS)2(L)2] and [Cu(L)2(H2O)](BF4)2ā€¢H2O complexes, and a discrete [Ag2(L)4](PF6)2 metallomacrocycle were isolated and structurally characterized by X-ray crystallography. A mononuclear palladium complex [PdCl2(L)]ā€¢(solvate), where solvate = Ā½H2O or CH2Cl2, was also readily obtained in 71% yield. One example of the ligand acting as a bis(bidentate) bridging ligand was observed in a dinuclear [(PdCl2)2(L)]ā€¢Ā¾H2O complex that was obtained only in very low yield (ca. 3%) from the reaction that produced [PdCl2(L)]ā€¢Ā½H2O. trans-[Fe(NCS)2(L)2] undergoes a temperature dependent HS-LS (HS = high spin; LS = low spin) crossover at ca. 205 K that was 2 observed by X-ray crystallography and magnetic measurements and attempts were made to understand the structural basis of this process. Despite efforts to isolate examples of L bridging two iron(II) centres, only the mononuclear trans-[Fe(NCS)2(L)2] species could be obtained.Rachel S. Crees, Boujemma Moubaraki, Keith S. Murray, and Christopher J. Sumb

    An endogenous inhibitor of angiogenesis downregulated by hypoxia in human aortic valve stenosis promotes disease pathogenesis

    Get PDF
    Acknowledgements The authors would like to acknowledge the NHS Grampian Biorepository for their support and assistance with all immunohistochemistry. Sources of funding This work was generously funded by the British Heart Foundation, UK (FS/17/28/32807) and Grampian NHS Endowments.Peer reviewedPublisher PD

    Hysteretic thermal spin-crossover in heteroleptic Fe(II) complexes using alkyl chain substituted 2,2ā€™-dipyridylamine ligands

    Get PDF
    The alkyl chain carrying ligands N,N-di(pyridin-2-yl)butanamide (LC4) and N,N-di(pyridin-2-yl)decanamide (LC10) were combined with NCSāˆ’ co-ligands to form the neutral heteroleptic Fe(II) complexes trans-[FeII(LC4)2(NCS)2] (1C4) and trans-[FeII(LC10)2(NCS)2] (1C10). Variable temperature crystallographic studies revealed that 1C4 is in the orthorhombic space group Pna21 between 85ā€“200 K whereas 1C10 is in the monoclinic space group P21/c between 85ā€“140 K. The average Feā€“N bond lengths suggest that at 85 K 1C4 contains LS Fe(II) centres; however, the ca. 0.18 ƅ increase in the average Feā€“N bond lengths between 85 and 120 K suggests a spin-transition to the HS state occurs within this temperature interval. 1C10 contains LS Fe(II) centres between 85 and 105 K. Upon warming from 105 to 140 K the average Feā€“N bond lengths increase by ca. 0.19 ƅ, which suggests a spin-transition to the HS state. Solid-state magnetic susceptibility measurements showed that 1C4 undergoes semi-abrupt spin-crossover with T1/2 = 127.5 K and a thermal hysteresis of ca. 13 K whereas, 1C10 undergoes an abrupt spin-crossover with T1/2 = 119.0 K, and is also accompanied by thermal hysteresis of ca. 4 K. The crystallographic and magnetic data show that the length of the complex's alkyl chain substituents can have a large impact on the structure of the crystal lattice as well as a subtle effect on the T1/2 value for thermal spin-crossover

    Interactive digital interventions to promote self-management in adults with asthma : systematic review and meta-analysis

    Get PDF
    This paper presents independent research funded by the National Institute for Health Research (NIHR) under its Programme Grants for Applied Research Programme (Grant Reference Number (RP-PG- 1211ā€“20001).Background: To identify, summarise and synthesise the evidence for using interactive digital interventions to support patient self-management of asthma, and determine their impact. Methods: Systematic review with meta-analysis. We searched MEDLINE, EMBASE, CINAHL, PsycINFO, ERIC, Cochrane Library, DoPHER, TROPHI, Social Science Citation Index and Science Citation Index. The selection criteria requirement was studies of adults (16 years and over) with asthma, interventions that were interactive digital interventions and the comparator was usual care. Outcomes were change in clinical outcomes, cost effectiveness and patient-reported measures of wellbeing or quality of life. Only Randomised Controlled Trials published in peer-reviewed journals in English were eligible. Potential studies were screened and study characteristics and outcomes were extracted from eligible papers independently by two researchers. Where data allowed, meta-analysis was performed using a random effects model. Results: Eight papers describing 5 trials with 593 participants were included, but only three studies were eligible for inclusion for meta-analysis. Of these, two aimed to improve asthma control and the third aimed to reduce the total dose of oral prednisolone without worsening control. Analyses with data from all three studies showed no significant differences and extremely high heterogeneity for both Asthma Quality of Life (AQLQ) (Standardised Mean Difference (SMD) 0.05; 95 % Confidence Interval (CI) 0.32 to -0.22: I2 96.8) and asthma control (SMD 0.21; 95 % CI -0.05 to .42; I2 = 87.4). The removal of the third study reduced heterogeneity and indicated significant improvement for both AQLQ (SMD 0.45; 95 % CI 0.13 to 0.77: I2 = 0.34) and asthma control (SMD 0.54; 95 % CI 0.22 to 0.86: I2 = 0.11). No evidence of harm was identified. Conclusion: Digital self-management interventions for adults with asthma show promise, with some evidence of small beneficial effects on asthma control. Overall, the evidence base remains weak due to the lack of large, robust trials.Publisher PDFPeer reviewe

    Hexahalorhenate (iv) salts of metal oxazolidine nitroxides

    Get PDF
    Eight coordination compounds of formulae [FeII(Lā€¢)2][ReIVCl6] (1a), [FeII(Lā€¢)2][ReIVBr6] (1b), [CoII(Lā€¢)2][ReIVCl6]Ā·CH3CN (2a), [CoII(Lā€¢)2][ReIVBr6] (2b), [NiII(Lā€¢)(CH3CN)3][ReIVCl6]Ā·CH3CN (3a), [NiII(Lā€¢)(CH3CN)3][ReIVBr6]Ā·3CH3CN (3b), [CuII(Lā€¢)2][ReIVCl6] (4a)and [CuII(Lā€¢)2][ReIVBr6] (4b), where Lā€¢ is the aminoxyl radical chelating ligand, 4,4-dimethyl-2,2-di(2-pyridyl)oxazolidine-N- oxide, have been synthesised. Structural and magnetic studies reveal metal-radical intramolecular antiferromagnetic interactions in the [MII(Lā€¢)2]2+ cations in the iron, cobalt and copper based compounds (1a, 1b, 2a, 2b, 4a and 4b) with the central metal ion low-spin in the case of Fe (1a and 1b) and a gradual, cobalt based, spin-crossover transition present in 2a and 2b. The nickel based compounds, 3a and 3b, were analysed in the dried form (3a(dried) and 3b(dried)) and directly in acetonitrile (3a(solvated) and 3b(solvated)). Microanalysis and IR spectroscopy on 3a(dried) and 3b(dried) suggests the dried samples are best formulated as [NiII(Lā€¢)(H2O)3][ReIVX6], where X = Cl (3a(dried)) and Br (3b(dried)). All forms for 3a and 3b exhibit cationic metal-radical ferromagnetic interactions resulting in S = 3/2 ground states. In addition, 3a(dried) exhibits spin-canting behaviour with an ordering temperature of 2.7 K, an open hysteresis loop with a coercive field Hc, = 580 Oe, and a remanent magnetisation Mr = 0.21 Ī¼B, resulting in a canting angle of ~1.8Ā°. In contrast 3b(dried) shows no spin-canting behaviour; a maximum in Ļ‡M vs. T at T = 3 K suggesting long-range antiferromagnetic order. 3a(solvated) and 3b(solvated) show no indication of long-range magnetic ordering, unlike 4a and 4b where anomalies are evident in the low-temperature magnetic susceptibility measurements

    California Extremely Large Telescope: Conceptual Design for a Thirty-Meter Telescope

    Get PDF
    Following great success in the creation of the Keck Observatory, scientists at the California Institute of Technology and the University of California have begun to explore the scientific and technical prospects for a much larger telescope. The Keck telescopes will remain the largest telescopes in the world for a number of years, with many decades of forefront research ahead after that. Though these telescopes have produced dramatic discoveries, it is already clear that even larger telescopes must be built if we are to address some of the most profound questions about our universe. The time required to build a larger telescope is approximately ten years, and the California community is presently well-positioned to begin its design and construction. The same scientists who conceived, led the design, and guided the construction of the Keck Observatory have been intensely engaged in a study of the prospects for an extremely large telescope. Building on our experience with the Keck Observatory, we have concluded that the large telescope is feasible and is within the bounds set by present-day technology. Our reference telescope has a diameter of 30 meters, the largest size we believe can be built with acceptable risk. The project is currently designated the California Extremely Large Telescope (CELT)

    Cerebellar c9RAN proteins associate with clinical and neuropathological characteristics of C9ORF72 repeat expansion carriers.

    Get PDF
    Clinical and neuropathological characteristics associated with G4C2 repeat expansions in chromosome 9 open reading frame 72 (C9ORF72), the most common genetic cause of amyotrophic lateral sclerosis (ALS) and frontotemporal dementia, are highly variable. To gain insight on the molecular basis for the heterogeneity among C9ORF72 mutation carriers, we evaluated associations between features of disease and levels of two abundantly expressed "c9RAN proteins" produced by repeat-associated non-ATG (RAN) translation of the expanded repeat. For these studies, we took a departure from traditional immunohistochemical approaches and instead employed immunoassays to quantitatively measure poly(GP) and poly(GA) levels in cerebellum, frontal cortex, motor cortex, and/or hippocampus from 55 C9ORF72 mutation carriers [12 patients with ALS, 24 with frontotemporal lobar degeneration (FTLD) and 19 with FTLD with motor neuron disease (FTLD-MND)]. We additionally investigated associations between levels of poly(GP) or poly(GA) and cognitive impairment in 15 C9ORF72 ALS patients for whom neuropsychological data were available. Among the neuroanatomical regions investigated, poly(GP) levels were highest in the cerebellum. In this same region, associations between poly(GP) and both neuropathological and clinical features were detected. Specifically, cerebellar poly(GP) levels were significantly lower in patients with ALS compared to patients with FTLD or FTLD-MND. Furthermore, cerebellar poly(GP) associated with cognitive score in our cohort of 15 patients. In the cerebellum, poly(GA) levels similarly trended lower in the ALS subgroup compared to FTLD or FTLD-MND subgroups, but no association between cerebellar poly(GA) and cognitive score was detected. Both cerebellar poly(GP) and poly(GA) associated with C9ORF72 variant 3 mRNA expression, but not variant 1 expression, repeat size, disease onset, or survival after onset. Overall, these data indicate that cerebellar abnormalities, as evidenced by poly(GP) accumulation, associate with neuropathological and clinical phenotypes, in particular cognitive impairment, of C9ORF72 mutation carriers
    • ā€¦
    corecore