Heteronuclear d-d and d-f Ru(II)/M complexes [M = Gd(III), Yb(III), Nd(III), Zn(II) or Mn(II)] of ligands combining phenanthroline and aminocarboxylate binding sites: combined relaxivity, cell imaging and photophysical studies

A ligand skeleton combining a 1,10-phenanthroline (phen) binding site and one or two heptadentate N3O4 aminocarboxylate binding sites, connected via alkyne spacers to the phen C3 or C3/C8 positions, has been used to prepare a range of heteronuclear Ru·M and Ru·M2 complexes which have been evaluated for their cell imaging, relaxivity, and photophysical properties. In all cases the phen unit is bound to a {Ru(bipy)2}2+ unit to give a phosphorescent {Ru(bipy)2(phen)}2+ luminophore, and the pendant aminocarboxylate sites are occupied by a secondary metal ion M which is either a lanthanide [Gd(III), Nd(III), Yb(III)] or another d-block ion [Zn(II), Mn(II)]. When M = Gd(III) or Mn(II) these ions provide the complexes with a high relaxivity for water; in the case of Ru·Gd and Ru·Gd2 the combination of high water relaxivity and 3MLCT phosphorescence from the Ru(II) unit provides the possibility of two different types of imaging modality in a single molecular probe. In the case of Ru·Mn and Ru·Mn2 the Ru(II)-based phosphorescence is substantially reduced compared to the control complexes Ru·Zn and Ru·Zn2 due to the quenching effect of the Mn(II) centres. Ultrafast transient absorption spectroscopy studies on Ru·Mn (and Ru·Zn as a non-quenched control) reveal the occurrence of fast (<1 ns) PET in Ru·Mn, from the Mn(II) ion to the Ru(II)-based 3MLCT state, i.e. MnII–(phen˙−)–RuIII → MnIII–(phen˙−)–RuII; the resulting MnIII–(phen˙−) state decays with τ ≈ 5 ns and is non-luminescent. This occurs in conformers when an ET pathway is facilitated by a planar, conjugated bridging ligand conformation connecting the two units across the alkyne bridge but does not occur in conformers where the two units are electronically decoupled by a twisted conformation of the bridging ligand. Computational studies (DFT) on Ru·Mn confirmed both the occurrence of the PET quenching pathway and its dependence on molecular conformation. In the complexes Ru·Ln and Ru·Ln2 (Ln = Nd, Yb), sensitised near-infrared luminescence from Nd(III) or Yb(III) is observed following photoinduced energy-transfer from the Ru(II) core, with Ru → Nd energy-transfer being faster than Ru → Yb energy-transfer due to the higher density of energy-accepting states on Nd(III)

Non-cubic layered structure of Ba(1-x)K(x)BiO3 superconductor

Bismuthate superconductor Ba(1-x)K(x)BiO3 (x=0.27-0.49, Tc=25-32K) grown by an electrolysis technique was studied by electron diffraction and high-resolution electron microscopy. The crystalline structure thereof has been found to be non-cubic, of the layered nature, and non-centrosymmetric, with the lattice parameters a ~ ap, c ~ 2ap (ap is a simple cubic perovskite cell parameter) containing an ordered arrangement of barium and potassium. The evidence for the layered nature of the bismuthate superconductor removes the principal crystallographic contradiction between bismuthate and cuprate high-Tc superconductors.Comment: 4 pages, 3 figures, to be published in Physical Review B as a Rapid Communicatio

A study on the response of single and double circular plates subjected to localised blast loading

The response of single and double layered steel plates to localised air-blast loading was examined. Two configurations, both comprising fully clamped circular plates with a 200 mm exposed diameter, were considered: 4mm thick single and (2+2) mm double layered plates. The localised air-blast loading was applied by centrally detonating discs of PE4 plastic explosive. Similar failure modes were evident in the single and double plate configurations, namely, Mode I (large inelastic deformation) and Mode II (capping failure along with deformation) responses. The double plates exhibited larger midpoint deflections than the single plates, and partial tearing of the front plate in the double plates was observed at a lower impulse than in the single plates. However, complete capping of both plates in the double plate configuration occurred at the same charge mass as for the single plates, implying that both configurations offer equivalent protection from capping failure as a result of this type of localised blast loading. A metallographic study of the deformed and torn plate regions did not reveal any phase transformation in the steel. It was also found that the 2 mm thick plates exhibited larger increases in grain size than the 4 mm thick plates

Quantum magnetism in two dimensions: From semi-classical N\'eel order to magnetic disorder

This is a review of ground-state features of the s=1/2 Heisenberg antiferromagnet on two-dimensional lattices. A central issue is the interplay of lattice topology (e.g. coordination number, non-equivalent nearest-neighbor bonds, geometric frustration) and quantum fluctuations and their impact on possible long-range order. This article presents a unified summary of all 11 two-dimensional uniform Archimedean lattices which include e.g. the square, triangular and kagome lattice. We find that the ground state of the spin-1/2 Heisenberg antiferromagnet is likely to be semi-classically ordered in most cases. However, the interplay of geometric frustration and quantum fluctuations gives rise to a quantum paramagnetic ground state without semi-classical long-range order on two lattices which are precisely those among the 11 uniform Archimedean lattices with a highly degenerate ground state in the classical limit. The first one is the famous kagome lattice where many low-lying singlet excitations are known to arise in the spin gap. The second lattice is called star lattice and has a clear gap to all excitations. Modification of certain bonds leads to quantum phase transitions which are also discussed briefly. Furthermore, we discuss the magnetization process of the Heisenberg antiferromagnet on the 11 Archimedean lattices, focusing on anomalies like plateaus and a magnetization jump just below the saturation field. As an illustration we discuss the two-dimensional Shastry-Sutherland model which is used to describe SrCu2(BO3)2.Comment: This is now the complete 72-page preprint version of the 2004 review article. This version corrects two further typographic errors (three total with respect to the published version), see page 2 for detail

Comprehensive analysis of epigenetic clocks reveals associations between disproportionate biological ageing and hippocampal volume

The concept of age acceleration, the difference between biological age and chronological age, is of growing interest, particularly with respect to age-related disorders, such as Alzheimer’s Disease (AD). Whilst studies have reported associations with AD risk and related phenotypes, there remains a lack of consensus on these associations. Here we aimed to comprehensively investigate the relationship between five recognised measures of age acceleration, based on DNA methylation patterns (DNAm age), and cross-sectional and longitudinal cognition and AD-related neuroimaging phenotypes (volumetric MRI and Amyloid-β PET) in the Australian Imaging, Biomarkers and Lifestyle (AIBL) and the Alzheimer’s Disease Neuroimaging Initiative (ADNI). Significant associations were observed between age acceleration using the Hannum epigenetic clock and cross-sectional hippocampal volume in AIBL and replicated in ADNI. In AIBL, several other findings were observed cross-sectionally, including a significant association between hippocampal volume and the Hannum and Phenoage epigenetic clocks. Further, significant associations were also observed between hippocampal volume and the Zhang and Phenoage epigenetic clocks within Amyloid-β positive individuals. However, these were not validated within the ADNI cohort. No associations between age acceleration and other Alzheimer’s disease-related phenotypes, including measures of cognition or brain Amyloid-β burden, were observed, and there was no association with longitudinal change in any phenotype. This study presents a link between age acceleration, as determined using DNA methylation, and hippocampal volume that was statistically significant across two highly characterised cohorts. The results presented in this study contribute to a growing literature that supports the role of epigenetic modifications in ageing and AD-related phenotypes