First-principles extrapolation method for accurate CO adsorption energies on metal surfaces

We show that a simple first-principles correction based on the difference between the singlet-triplet CO excitation energy values obtained by DFT and high-level quantum chemistry methods yields accurate CO adsorption properties on a variety of metal surfaces. We demonstrate a linear relationship between the CO adsorption energy and the CO singlet-triplet splitting, similar to the linear dependence of CO adsorption energy on the energy of the CO 2$\pi$* orbital found recently {[Kresse {\em et al.}, Physical Review B {\bf 68}, 073401 (2003)]}. Converged DFT calculations underestimate the CO singlet-triplet excitation energy $\Delta E_{\rm S-T}$, whereas coupled-cluster and CI calculations reproduce the experimental $\Delta E_{\rm S-T}$. The dependence of $E_{\rm chem}$ on $\Delta E_{\rm S-T}$ is used to extrapolate $E_{\rm chem}$ for the top, bridge and hollow sites for the (100) and (111) surfaces of Pt, Rh, Pd and Cu to the values that correspond to the coupled-cluster and CI $\Delta E_{\rm S-T}$ value. The correction reproduces experimental adsorption site preference for all cases and obtains $E_{\rm chem}$ in excellent agreement with experimental results.Comment: Table sent as table1.eps. 3 figure

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

Uncovering the heterogeneity and temporal complexity of neurodegenerative diseases with Subtype and Stage Inference

The heterogeneity of neurodegenerative diseases is a key confound to disease understanding and treatment development, as study cohorts typically include multiple phenotypes on distinct disease trajectories. Here we introduce a machine-learning technique\u2014Subtype and Stage Inference (SuStaIn)\u2014able to uncover data-driven disease phenotypes with distinct temporal progression patterns, from widely available cross-sectional patient studies. Results from imaging studies in two neurodegenerative diseases reveal subgroups and their distinct trajectories of regional neurodegeneration. In genetic frontotemporal dementia, SuStaIn identifies genotypes from imaging alone, validating its ability to identify subtypes; further the technique reveals within-genotype heterogeneity. In Alzheimer\u2019s disease, SuStaIn uncovers three subtypes, uniquely characterising their temporal complexity. SuStaIn provides fine-grained patient stratification, which substantially enhances the ability to predict conversion between diagnostic categories over standard models that ignore subtype (p = 7.18 7 10 124 ) or temporal stage (p = 3.96 7 10 125 ). SuStaIn offers new promise for enabling disease subtype discovery and precision medicine

Pre-release evaluation of the efficacy of the leaf-sucking bug Carvalhotingis visenda (Heteroptera: Tingidae) as a biological control agent for cat's claw creeper Macfadyena unguis-cati (Bignoniaceae)

In classical weed biological control, assessing weed response to simulated herbivory is one option to assist in the prioritization of available agents and prediction of their potential efficacy. Previously reported simulated herbivory studies suggested that a specialist herbivore in the leaf-feeding guild is desirable as an effective biological control agent for cat's claw creeper Macfadyena unguis-cati (Bignoniaceae), an environmental weed that is currently a target for biological control. In this study, we tested (i) whether the results from glasshouse-based simulated herbivory can be used to prioritise potential biological control agents by evaluating the impact of a leaf-sucking tingid bug Carvalhotingis visenda (Drake & Hambleton) (Hemiptera: Tingidae) in quarantine; and (ii) the likely effectiveness of low- and high-densities of the leaf-sucking tingid after its release in the field. The results suggest that a single generation of C. visenda has the potential to reduce leaf chlorophyll content significantly, resulting in reduced plant height and leaf biomass. However, the impact of one generation of tingid herbivory on below-ground plant components, including the roots and tuber size and biomass, were not significant. These findings are consistent with results obtained from a simulated herbivory trial, highlighting the potential role of simulated herbivory studies in agent prioritisation