We conducted a program of research to derive and test the reliability of a clinical prediction rule to identify high-risk older adults using paramedics' observations.
We developed the Paramedics ...assessing Elders at Risk of Independence Loss (PERIL) checklist of 43 yes or no questions, including the Identifying Seniors at Risk (ISAR) tool items. We trained 1,185 paramedics from three Ontario services to use this checklist, and assessed inter-observer reliability in a convenience sample. The primary outcome, return to the ED, hospitalization, or death within one month was assessed using provincial databases. We derived a prediction rule using multivariable logistic regression.
We enrolled 1,065 subjects, of which 764 (71.7%) had complete data. Inter-observer reliability was good or excellent for 40/43 questions. We derived a four-item rule: 1) "Problems in the home contributing to adverse outcomes?" (OR 1.43); 2) "Called 911 in the last 30 days?" (OR 1.72); 3) male (OR 1.38) and 4) lacks social support (OR 1.4). The PERIL rule performed better than a proxy measure of clinical judgment (AUC 0.62 vs. 0.56, p=0.02) and adherence was better for PERIL than for ISAR.
The four-item PERIL rule has good inter-observer reliability and adherence, and had advantages compared to a proxy measure of clinical judgment. The ISAR is an acceptable alternative, but adherence may be lower. If future research validates the PERIL rule, it could be used by emergency physicians and paramedic services to target preventative interventions for seniors identified as high-risk.
The rutile TiO2(110) surface has been doped with sub-monolayer metallic Cr, which oxidises and donates charge to specific surface Ti ions. X-Ray and ultra violet photoemission spectroscopy and first ...principles density functional theory with Hubbard U are used to assign the oxidation states of Cr and surface Ti and we find that Cr2+ forms on bridging oxygen ions and a 5-fold coordinated surface Ti atom is reduced to Ti3+ and the Cr ions readily react with oxygen (to Cr3+), which leads to depletion of surface Ti3+ 3d electrons.
Atomic layer deposition (ALD) is widely used in microelectronics and semiconductor industry to deposit thin films as part of device fabrication in nano- or subnano-dimensions. The key advantages of ...ALD are the conformality and precise thickness control at the atomic scale, which are difficult for physical or traditional chemical vapor deposition methods. Cobalt (Co) and Ruthenium (Ru) are used as seed layers for metallization of interconnects. They are also potential materials for the electrode in dynamic random-access memory (DRAM) capacitors and metal-oxide-semiconductor field-effect transistors (MOSFETs). Plasma-enhanced ALD (PE-ALD) is used for low-temperature thin film growth by alternating exposures of metal precursors and plasma reactants. During the PE-ALD growth of metals, N-plasma, for example, NH
3
or a mixture of N
2
and H
2
, has been applied to avoid surface metal oxidation. The PE-ALD of Ru and Co has been experimentally investigated using metal precursors such as RuCp
2
, Ru(EtCp)
2
, CoCp
2
, and CoCp(CO)
2
. However, the reaction mechanism is not clear and theoretical studies on the reaction mechanism is entirely lacking.
In this presentation, we study the PE-ALD growth of Co and Ru by first principle calculations. The (001) surface of both metals, with a hexagonal structure, is the most stable and the (100) surface with a zigzag structure is less stable but has high reactivity. These two surfaces allow the study of the influence of the surface facet. The surface saturation coverage was studied by considering individual adsorption and co-adsorption of NH and NH
2
to terminate both surfaces. On the (001) surface, the zero K saturation coverage for NH is 1ML on Ru and 6/9ML on Co. For NH
2
, the saturation coverages are 6/9ML on Co and Ru surfaces. On the (100) surface, the saturation coverages are 2ML for NH on Ru and Co surfaces, 1.33 ML for NH
2
on Ru, and 1ML for NH
2
on Co surface. The higher saturation coverage on (100) surface is attributed to the unique trench structure, which provides more available surface sites than that of (001) surface. We also consider co-adsorption of NH and NH
2
on (001) and (100) surfaces. The results are then analyzed with ab initio thermodynamics by calculating the Gibbs free energy. Both the ultra-high vacuum (UHV) condition and standard ALD operating condition are used to elucidate the effect of pressure and temperature on the termination of metal surfaces.
The adsorption and reactions of metal precursors (CoCp
2
and RuCp
2
) on NH
x
terminated metal surfaces were investigated with the inclusion of van der Waals corrections. Two possible adsorption structures, namely the precursor lying parallel and perpendicular to the NH
x
-terminated surfaces, were considered at zero K and ALD operating conditions. Possible reactions include: precursor adsorption, first hydrogen transfer, first Cp ligand dissociation, first Cp ligand desorption, second hydrogen transfer, and second Cp ligand desorption. The barrier for proton transfer was calculated using climbing image nudged elastic band (CI-NEB) method. Our results show that (100) surface has higher activity than (001) surface. In addition, the Cp ligand elimination of CoCp
2
has lower barrier than RuCp
2
, regardless of surface facet. After the metal precursor pulse, the surface is terminated with MCp fragment or M atom depending on surface facet, where M is Ru or Co. The surface N atom and H atom can be eliminated during the following plasma step by forming NH
3
, N
2
or H
2
. After a full cycle, the surface is an NH
x
-terminated metal surface and ready for the next cycle. This work will be important to reveal the mechanism and feasibility of atomic layer deposition of metals using N-plasma.
The photocatalytic oxidation of water to molecular oxygen is a key step in the water splitting reaction. The development of robust catalysts with high efficiency in this half-reaction is crucial for ...achieving technological application of water splitting. Density Functional Theory simulations can provide key insights into potential catalysts for this reaction. In this contribution we describe our work on modelling of surface modified TiO
2
focusing on water activation and the oxygen evolution mechanism on these heterostructures. Rutile and anatase TiO
2
are modified with nanostructures of metal oxides, namely alkaline earth oxides, cerium oxide and manganese oxides; these are also being prepared and characterised at collaborators laboratories in the framework of an EU H2020 M-ERA.net 2 project RATOCAT.
We find that nanoclusters of these oxides with different compositions and adsorption modes are strongly adsorbed and can induce a red shift in light absorption towards the visible region of the electromagnetic spectrum. A simple model of the photoexcited state allows the localisation of electrons and holes produce by excitation to be determined and understood. Typically, DFT studies neglect key issues issues such as reducibility of the oxide or the role of adsorbed hydroxyls on the properties and the water activation processes in OER. We include a detailed analysis of reduction of the heterostructures, in which we find that loss of oxygen is generally favourable. In addition, the surface hydroxylation (through adsorption and dissociation of water) and the cluster hydroxylation are examined. We find that a single water molecule will dissociate at the supported oxide nanocluster, with large energy gain that indicates hydroxyl groups will be present and must be accounted for.
With a suitable model of a hydroxylated oxide heterostructure, including oxygen vacancies, we explore water activation and find for those structures with hydroxyls and single oxygen vacancies, the water adsorption is dissociative but with moderate energy gains. Too high an energy gain and the subsequent OER steps are not favourable. We determine the step with the highest free energy cost and use this to estimate an overpotential for these heterostructures as well as determining key aspects of these structures that drive favourable OER.
Support for this work from Science Foundation Ireland through the H2020 M-ERA.net 2 co-fund program, Grant Number 16/M-ERA/3418 is acknowledged. We also acknowledge access to computing resources through the SFI funded Irish Centre for High End Computing, ICHEC.
To investigate the effect of repeated regrouping and relocation (R&R) on behaviour of steers, 72 Holstein–Friesian (14-month-old; 441
±
3.2
kg) steers were assigned to either control (
n
=
30; C) or ...regrouped (
n
=
42; R) treatments and housed six per pen in 12 pens. The R steers were exposed to six R&R over 84 days. New pen cohorts were allowed to stabilise for 14 days and none of the R steers were allowed to share the same pen or pen mates, where or with whom, they were previously housed. Control steers were housed in the same pen with the same pen mates. Each steer was marked on its back with an individual identification code. Twelve cameras were used to observe and record behaviour for each pen allowing observation of all individual steers continuously for a week following each R&R. The following behaviours were recorded for each steer: lying, standing, eating, drinking, head-to-head contact with another animal while not eating, head contact with the body of another animal and bodily contact with none, one, two or three steers. Behaviour was observed by instantaneous scan sampling after each R&R, at 2
min intervals for 2
h on day 1; at further 20
min intervals on days 1 and 2; and at 120
min intervals from day 3 to 7. Where appropriate, the % of time spent in each behaviour was calculated from the data on total counts in each behavioural category. The total count data were analysed by
χ
2-statistics for all behavioural categories. Steers were weighed before each R&R. Average daily gain from day 0 to 84 was analysed by ANOVA. During the first 2
h observation period following mixing, R steers displayed a greater (
P
<
0.05) % of time standing (following the first to sixth R&R), eating (first to fourth and sixth R&R) and drinking (first, third and fourth R&R) than control steers. In the 20
min observational period, a greater % (
P
<
0.05) of time was spent standing, eating and drinking in R than in C steers following each R&R. In the 120
min observation period, R steers spent a greater (
P
<
0.05) % of time lying with less body contact behaviours than C steers, and these findings increased in the fourth, fifth and sixth R&R. These data suggest that there was partial adaptation to repeated R&R at the first two R&R followed by complete adaptation at the third and subsequent R&R, with no detrimental effect on animal performance.
Laponite films provide versatile inorganic scaffolds with materials architectures that direct the self-assembly of CdSe quantum dots (QDs or EviTags) and catalytic surfaces that promote the in situ ...polymerization of polyaniline (PANI) to yield novel nanocomposites for light emitting diodes (LEDs) and solar cell applications. Water-soluble CdSe EviTags with varying, overlapping emission wavelengths in the visible spectrum were incorporated using soft chemistry routes within Na-Laponite host film platforms to achieve broadband emission in the visible spectrum. QD concentrations, composition and synthesis approach were varied to optimize photophysical properties of the films and to mediate self-assembly, optical cascading and energy transfer. In addition, aniline tetramers coupled to CdSe (QD-AT) surfaces using a dithioate linker were embedded within Cu-Laponite nanoscaffolds and electronically coupled to PANI via vapor phase exposure. Nanotethering and specific host−guest and guest−guest interactions that mediate nanocomposite photophysical behavior were probed using electronic absorption and fluorescence spectroscopies, optical microscopy, AFM, SEM, powder XRD, NMR and ATR-FTIR. Morphology studies indicated that Lap/QD-AT films synthesized using mixed solvent, layer by layer (LbL) methods exhibited anisotropic supramolecular structures with unique mesoscopic ordering that affords bifunctional networks to optimize charge transport.
Layered materials, such as MoS
2
, are of great interest to the research community due to their wide range of potential applications. They are of particular interest as supports for low dimensional ...metal catalysts, as well as for use in the electronics industry as ultra-thin diffusion barriers in semi-conductor device interconnects.
Thus, understanding the interaction between a variety of metal structures and the MoS
2
monolayer is of great importance. In previous studies the focus has been largely on the strength of the interaction between a single atom or a nanoparticle of a wide variety of metals, which creates a significant knowledge gap in thin film nucleation on 2D materials. To begin addressing this deficit, we present a density functional theory (DFT) study of the adsorption of small metal structures, with up to four atoms, on a monolayer of MoS
2
. The metals of interest are Cu, Co and Ru, chosen for their relevance in electronics applications. We show how the metal-substrate interaction changes depending on the particular metal, as well as the mode of adsorption and overall nanocluster structure. Further, we show the effect that the presence of a sulphur vacancy in the monolayer has on the metal-substrate interaction, as this is a commonly observed defect.
The strength of interaction between the metals and MoS
2
is in the order Co > Ru > Cu. The effect of adsorption on MoS
2
is localised to the metal cluster, however depending on the particular structure, some distortions of the MoS2 lattice can be observed upon adsorption of Ru.
RADAR OBSERVATIONS OF COMET 103P/HARTLEY 2 HARMON, John K; NOLAN, Michael C; HOWELL, Ellen S ...
The Astrophysical journal,
2011, Letnik:
734, Številka:
1
Journal Article
The use of the term ‘family (informal) carer’, as it is currently conceptualized, is recent and is largely the product of increased attention in the academic and policy literature over the last two ...decades. Despite their fairly late arrival on the scene, family carers now occupy centre stage in UK government policy, having being described by the Prime Minister, Tony Blair, as the ‘unsung heroes’ of British life, who are essential to the fabric and character of Britain. Such recognition stems from the growing realization that family carers are the lynchpin of community care, providing 80% of all the care needed at an estimated saving to the UK government of some £40 billion annually.
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