Cooperative motion and growing length scales in supercooled confined liquids

Using molecular dynamics simulations we investigate the relaxation dynamics of a supercooled liquid close to a rough as well as close to a smooth wall. For the former situation the relaxation times increase strongly with decreasing distance from the wall whereas in the second case they strongly decrease. We use this dependence to extract various dynamical length scales and show that they grow with decreasing temperature. By calculating the frequency dependent average susceptibility of such confined systems we show that the experimental interpretation of such data is very difficult.Comment: 7 pages of Latex, 3 figure

Slow dynamics near glass transitions in thin polymer films

The $\alpha$-process (segmental motion) of thin polystyrene films supported on glass substrate has been investigated in a wider frequency range from 10$^{-3}$ Hz to 10$^4$ Hz using dielectric relaxation spectroscopy and thermal expansion spectroscopy. The relaxation rate of the $\alpha$-process increases with decreasing film thickness at a given temperature above the glass transition. This increase in the relaxation rate with decreasing film thickness is much more enhanced near the glass transition temperature. The glass transition temperature determined as the temperature at which the relaxation time of the $\alpha$-process becomes a macroscopic time scale shows a distinct molecular weight dependence. It is also found that the Vogel temperature has the thickness dependence, i.e., the Vogel temperature decreases with decreasing film thickness. The expansion coefficient of the free volume $\alpha_f$ is extracted from the temperature dependence of the relaxation time within the free volume theory. The fragility index $m$ is also evaluated as a function of thickness. Both $\alpha_f$ and $m$ are found to decrease with decreasing film thickness.Comment: 9 pages, 7 figures, and 2 table

'You were quiet - I did all the marching': Research processes involved in hearing the voices of South Asian girls

This article is available open access through the publisher’s website at the link below. Copyright @ 2011 A B Academic Publishers.This article provides insights into the outcomes of reflection following two interview approaches used to explore narratives of the lived, individual experiences of South-Asian girls living in West London. In attempting to illuminate and re-present the cultural experiences as told by these girls, the choice of interview approach became critical in allowing the voices to be effectively heard (Rogers, 2005). This article therefore considers how a semi-structured interview approach offered valuable insights into the girls' experiences but became constraining for both researcher and participant in unveiling the complexity and depth of their lives. These constraints emerged through reflection by both participants and researcher. As a result of reflexivity during the research process, the researcher moved towards the use of research conversations during the second phase of the study. Ultimately the study revealed how the girls felt empowered by the opportunity to narrate their individual experiences and tell of their lives. In narrating their reflections on being part of the research, there was a clear recognition that the process facilitated the articulation of new voices and ‘multi-voicedness’ (Moen, 2006

Synthesis and characterization of polystyrene-blockpoly(vinylbenzoic acid): a promising compound for manipulating photoresponsive properties at the nanoscale

"Published online: 27 January 2015"Using reversible addition-fragmentation chain transfer (RAFT) polymerization, the effect of PSt macroRAFT and 4VBA ratio on the synthesis of a carboxylic acid functional block copolymer (PSt-b-P4VBA) was studied. PSt macroRAFT polymer was initially prepared followed by the insertion of 4-vinylbenzoic acid (4VBA) monomer. The chemical structure of the diblock copolymer was confirmed by NMR and FTIR. The effect of PSt macroRAFT and 4VBA ratio on copolymerization yield and on molecular weight distribution was assessed by gel permeation chromatography. The rate of polymerization did not change as the 4VBA/PSt macroRAFT ratio increased, indicating an ideal amount of 4VBA insertion. An optimal ratio of [PSt macroRAFT]:[AIBN]:[4VBA] was 1.2:1:180. DSC and XRD confirmed the amorphous structure of homo and copolymer. Thermal stability was higher for PSt-b-P4VBA forming activated porous carbon char by dehydration, carbonization and oxidation. SEM and STEM observations showed a morphological evolution between PSt macroRAFT and the correspondent copolymer.The authors acknowledge the n-STeP-Nanostructured systems for Tailored Performance, with reference NORTE-07-0124-FEDER-000039, supported by the Programa Operacional Regional do Norte (ON.2), PEst-C/CTM/LA0025/2013 (Strategic Project-LA 25-2013-2014)

Two-Photon Fluorescence Microscopy Imaging of Cellular Oxidative Stress Using Profluorescent Nitroxides

A range of varying chromophore nitroxide free radicals and their nonradical methoxyamine analogues were synthesized and their linear photophysical properties examined. The presence of the proximate free radical masks the chromophore’s usual fluorescence emission, and these species are described as profluorescent. Two nitroxides incorporating anthracene and fluorescein chromophores (compounds 7 and 19, respectively) exhibited two-photon absorption (2PA) cross sections of approximately 400 G.M. when excited at wavelengths greater than 800 nm. Both of these profluorescent nitroxides demonstrated low cytotoxicity toward Chinese hamster ovary (CHO) cells. Imaging colocalization experiments with the commercially available CellROX Deep Red oxidative stress monitor demonstrated good cellular uptake of the nitroxide probes. Sensitivity of the nitroxide probes to H2O2-induced damage was also demonstrated by both one- and two-photon fluorescence microscopy. These profluorescent nitroxide probes are potentially powerful tools for imaging oxidative stress in biological systems, and they essentially “light up” in the presence of certain species generated from oxidative stress. The high ratio of the fluorescence quantum yield between the profluorescent nitroxide species and their nonradical adducts provides the sensitivity required for measuring a range of cellular redox environments. Furthermore, their reasonable 2PA cross sections provide for the option of using two-photon fluorescence microscopy, which circumvents commonly encountered disadvantages associated with one-photon imaging such as photobleaching and poor tissue penetration

Spectrum, risk factors and outcomes of neurological and psychiatric complications of COVID-19: a UK-wide cross-sectional surveillance study

SARS-CoV-2 is associated with new-onset neurological and psychiatric conditions. Detailed clinical data, including factors associated with recovery, are lacking, hampering prediction modelling and targeted therapeutic interventions. In a UK-wide cross-sectional surveillance study of adult hospitalized patients during the first COVID-19 wave, with multi-professional input from general and sub-specialty neurologists, psychiatrists, stroke physicians, and intensivists, we captured detailed data on demographics, risk factors, pre-COVID-19 Rockwood frailty score, comorbidities, neurological presentation and outcome. A priori clinical case definitions were used, with cross-specialty independent adjudication for discrepant cases. Multivariable logistic regression was performed using demographic and clinical variables, to determine the factors associated with outcome. A total of 267 cases were included. Cerebrovascular events were most frequently reported (131, 49%), followed by other central disorders (95, 36%) including delirium (28, 11%), central inflammatory (25, 9%), psychiatric (25, 9%), and other encephalopathies (17, 7%), including a severe encephalopathy (n = 13) not meeting delirium criteria; and peripheral nerve disorders (41, 15%). Those with the severe encephalopathy, in comparison to delirium, were younger, had higher rates of admission to intensive care and a longer duration of ventilation. Compared to normative data during the equivalent time period prior to the pandemic, cases of stroke in association with COVID-19 were younger and had a greater number of conventional, modifiable cerebrovascular risk factors. Twenty-seven per cent of strokes occurred in patients 60 years old, the younger stroke patients presented with delayed onset from respiratory symptoms, higher rates of multi-vessel occlusion (31%) and systemic thrombotic events. Clinical outcomes varied between disease groups, with cerebrovascular disease conferring the worst prognosis, but this effect was less marked than the pre-morbid factors of older age and a higher pre-COVID-19 frailty score, and a high admission white cell count, which were independently associated with a poor outcome. In summary, this study describes the spectrum of neurological and psychiatric conditions associated with COVID-19. In addition, we identify a severe COVID-19 encephalopathy atypical for delirium, and a phenotype of COVID-19 associated stroke in younger adults with a tendency for multiple infarcts and systemic thromboses. These clinical data will be useful to inform mechanistic studies and stratification of patients in clinical trials

Temperature- and thickness-dependent elastic moduli of polymer thin films

The mechanical properties of polymer ultrathin films are usually different from those of their counterparts in bulk. Understanding the effect of thickness on the mechanical properties of these films is crucial for their applications. However, it is a great challenge to measure their elastic modulus experimentally with in situ heating. In this study, a thermodynamic model for temperature- (T) and thickness (h)-dependent elastic moduli of polymer thin films Ef(T,h) is developed with verification by the reported experimental data on polystyrene (PS) thin films. For the PS thin films on a passivated substrate, Ef(T,h) decreases with the decreasing film thickness, when h is less than 60 nm at ambient temperature. However, the onset thickness (h*), at which thickness Ef(T,h) deviates from the bulk value, can be modulated by T. h* becomes larger at higher T because of the depression of the quenching depth, which determines the thickness of the surface layer δ