Glass transition in Ultrathin Polymer Films : A Thermal Expansion Study

Glass transition process gets affected in ultrathin films having thickness comparable to the size of the molecules. We observe systematic broadening of glass transition temperature (Tg) as the thickness of the polymer film reduces below the radius of gyration but the change in the average Tg was found to be very small. Existence of reversible negative and positive thermal expansion below and above Tg increased the sensitivity of our thickness measurements performed using energy dispersive x-ray reflectivity. A simple model of Tg variation as a function of depth expected from sliding motion could explain the results. We observe clear glass transition even for 4 nm polystyrene film that was predicted to be absent from ellipsometry measurements of thicker films.Comment: 11 pages, 5 figure

An expanded cavity hexaamine cage for copper(II)

The crystal structure of the bicyclic hexaamine complex [Cu(fac-Me-5-tricosane-N-6)](ClO4)(2) center dot H2O (fac-Me-5-tricosane-N-6 = facial-1,5,9,13,20-pentamethyl-3,7,11,15,18,22-hexaazabicyclo[7.7.7] tricosane) at 100 K defines an apparently tetragonally compressed octahedral geometry, which is attributed to a combination of dynamic interconversion and static disorder between two tetragonally elongated structures sharing a common short axis. This structure is fluxional at 60 K and above as shown by EPR spectroscopy. Aqueous cyclic voltammetry reveals that a remarkably stable Cu-I form of the complex is stabilised by the encapsulating nature of the expanded cage ligand

Lithium Transport through Ultrathin Silicon Layers

This contribution presents non-destructive measurements of lithium transport parameters (diffusivity, permeability) in nanometer sized silicon layers done by a novel neutron reflectometry (NR) based approach [4]

Towards transforming community eye care: an observational study and time-series analysis of optometrists' prescribing for eye disorders

Objectives: This study aimed to provide evidence on the therapeutic prescribing activity by community optometrists in Scotland and to determine its impact on workload in general practice and ophthalmology clinics. Study design: Scottish administrative healthcare data for a 53-month period (November 2013–April 2018) were used to analyse non-medical prescribing practice by optometrists. Methods: Using interrupted time-series regression (Autoregressive Integrated Moving Average), we assessed the impact of optometrist prescribing on ophthalmology outpatient attendances and general practice prescribing for eye disorders. Results: A total of 54,246 items were prescribed by 205 optometrists over the study period. Since the commencement of data recording, optometrist prescribing activity increased steadily from a baseline of zero to 1.2% of all ophthalmic items prescribed. Neither the monthly number of items prescribed nor the size of optometric workforce were associated with a reduction in ophthalmology outpatient appointments over time. Conclusions: Optometrists increasingly contribute to community ophthalmic prescribing in Scotland, releasing capacity and lessening general practice, but not secondary care workload. There appears to be an underutilisation of optometrists related to the management of dry eye, which represents an opportunity to release further capacity

Understanding Pathways into Care homes using Data (UnPiCD study) a retrospective cohort study using national linked health and social care data: a retrospective cohort study using national linked health and social care data

Background: Pathways into care are poorly understood but important life events for individuals and their families. UK policy is to avoid moving-in to care homes from acute hospital settings. This assumes that moves from secondary care represent a system failure. However, those moving to care homes from community and hospital settings may be fundamentally different groups, each requiring differing care approaches. Objective: To characterise individuals who move-in to a care home from hospital and compare with those moving-in from the community. Design and setting: A retrospective cohort study using cross-sectoral data linkage of care home data. Methods: We included adults moving-in to care homes between 1/4/13 and 31/3/16, recorded in the Scottish Care Home Census. Care home data were linked to general and psychiatric hospital admissions, community prescribing and mortality records to ascertain comorbidities, significant diagnoses, hospital resource use, polypharmacy and frailty. Multivariate logistic regression identified predictors of moving-in from hospital compared to from community. Results: We included 23,892 individuals moving-in to a care home, 13,564 (56.8%) from hospital and 10,328 (43.2%) from the community. High frailty risk adjusted Odds Ratio (aOR) 5.11 (95% Confidence Interval (CI): 4.60–5.68), hospital discharge with diagnosis of fracture aOR 3.91 (95%CI: 3.41–4.47) or stroke aOR 8.42 (95%CI: 6.90–10.29) were associated with moving-in from hospital. Discharge from in-patient psychiatry was also a highly significant predictor aOR 19.12 (95%CI: 16.26–22.48). Conclusions: Individuals moving-in to care homes directly from hospital are clinically distinct from those from the community. Linkage of cross-sectoral data can allow exploration of pathways into care at scale

Hexanuclear Ln6L6 Complex Formation by using an Unsymmetric Ligand

Multinuclear, self‐assembled lanthanide complexes present clear opportunities as sensors and imaging agents. Despite the widely acknowledged potential of this class of supramolecule, synthetic and characterization challenges continue to limit systematic studies into their self‐assembly restricting the number and variety of lanthanide architectures reported relative to their transition metal counterparts. Here we present the first study evaluating the effect of ligand backbone symmetry on multinuclear lanthanide complex self‐assembly. Replacement of a symmetric ethylene linker with an unsymmetric amide at the centre of a homoditopic ligand governs formation of an unusual Ln6L6 complex with coordinatively unsaturated metal centres. The choice of triflate as a counterion, and the effect of ionic radii are shown to be critical for formation of the Ln6L6 complex. The atypical Ln6L6 architecture is characterized using a combination of mass spectrometry, luminescence, DOSY NMR and EPR spectroscopy measurements. Luminescence experiments support clear differences between comparable Eu6L6 and Eu2L3 complexes, with relatively short luminescent lifetimes and low quantum yields observed for the Eu6L6 structure indicative of non‐radiative decay processes. Synthesis of the Gd6L6analogue allows three distinct Gd···Gd distance measurements to be extracted using homo‐RIDME EPR experiments

Lithium diffusion in congruent LiNbO3 single crystals at low temperatures probed by neutron reflectometry

The self-diffusion of lithium in congruent LiNbO3 single crystals was investigated at low temperatures between 379 and 523 K by neutron reflectometry. From measurements on 6LiNbO3 (amorphous film)/natLiNbO3 (single crystal) samples, Li self-diffusivities were determined in single crystals down to extremely low values of 1 × 10−25 m2 s−1 on small length scales of 1–10 nm. The measured diffusivities are in excellent agreement with (extrapolated) literature data obtained by experiments based on Secondary Ion Mass Spectrometry and Impedance Spectroscopy. The tracer diffusivities can be described by a single Arrhenius line over ten orders of magnitude with an activation enthalpy of 1.33 eV, which corresponds to the migration energy of a single Li vacancy. A deviation from the Arrhenius behaviour at low temperatures, e.g., due to defect cluster formation is not observed.EC/FP7/226507DFG/Schm 1569/18DFG/He 1574/13CP-CSA_INFRA-2008-1.1.1 Number 226507-NMI

Alternative splicing substantially diversifies the transcriptome during early photomorphogenesis and correlates with the energy availability in arabidopsis

Plants use light as source of energy and information to detect diurnal rhythms and seasonal changes. Sensing changing light conditions is critical to adjust plant metabolism and to initiate developmental transitions. Here we analyzed transcriptome-wide alterations in gene expression and alternative splicing (AS) of etiolated seedlings undergoing photomorphogenesis upon exposure to blue, red, or white light. Our analysis revealed massive transcriptome reprograming as reflected by differential expression of ~20% of all genes and changes in several hundred AS events. For more than 60% of all regulated AS events, light promoted the production of a presumably protein-coding variant at the expense of an mRNA with nonsense-mediated decay-triggering features. Accordingly, AS of the putative splicing factor REDUCED RED-LIGHT RESPONSES IN CRY1CRY2 BACKGROUND 1 (RRC1), previously identified as a red light signaling component, was shifted to the functional variant under light. Downstream analyses of candidate AS events pointed at a role of photoreceptor signaling only in monochromatic but not in white light. Furthermore, we demonstrated similar AS changes upon light exposure and exogenous sugar supply, with a critical involvement of kinase signaling. We propose that AS is an integration point of signaling pathways that sense and transmit information regarding the energy availability in plants

The SCottish Alcoholic Liver disease Evaluation: a population-level matched cohort study of hospital-based costs, 1991-2011

Studies assessing the costs of alcoholic liver disease are lacking. We aimed to calculate the costs of hospitalisations before and after diagnosis compared to population controls matched by age, sex and socio-economic deprivation. We aimed to use population level data to identify a cohort of individuals hospitalised for the first time with alcoholic liver disease in Scotland between 1991 and 2011.Incident cases were classified by disease severity, sex, age group, socio-economic deprivation and year of index admission. 5 matched controls for every incident case were identified from the Scottish population level primary care database. Hospital costs were calculated for both cases and controls using length of stay from morbidity records and hospital-specific daily rates by specialty. Remaining lifetime costs were estimated using parametric survival models and predicted annual costs. 35,208 incident alcoholic liver disease hospitalisations were identified. Mean annual hospital costs for cases were 2.3 times that of controls pre diagnosis (£804 higher) and 10.2 times (£12,774 higher) post diagnosis. Mean incident admission cost was £6,663. Remaining lifetime cost for a male, 50-59 years old, living in the most deprived area diagnosed with acoholic liver disease was estimated to be £65,999 higher than the matched controls (£12,474 for 7.43 years remaining life compared to £1,224 for 21.8 years). In Scotland, alcoholic liver disease diagnosis is associated with significant increases in admissions to hospital both before and after diagnosis. Our results provide robust population level estimates of costs of alcoholic liver disease for the purposes of health-care delivery, planning and future cost-effectiveness analyses