Evolution of Microphase Separation with Variations of Segments of Sequence-Controlled Multiblock Copolymers

Multiblock copolymers (MBCPs) are an emerging class of materials that are becoming more accessible in recent years. However, to date there is still a lack of fundamental understanding of their physical properties. In particular, the glass transition temperature (Tg) which is known to be affected by the phase separation has not been well characterized experimentally. To this end, we report the first experimental study on the evolution of the Tgs and the corresponding phase separation of linear MBCPs with increasing number of blocks while keeping the overall degree of polymerization (DP) constant (DP = 200). Ethylene glycol methyl ether acrylate (EGMEA) and tert-butyl acrylate (tBA) were chosen as monomers for reversible addition-fragmentation chain transfer polymerization to synthesize MBCPs. We found the Tgs (as measured by differential scanning calorimetry) of EGMEA and tBA segments within the MCBPs to converge with increasing number of blocks and decreasing block length, correlating with the loss of the heterogeneity as observed from small-angle X-ray scattering (SAXS) analysis. The Tgs of the multiblock copolymers were also compared to the Tgs of the polymer blends of the corresponding homopolymers, and we found that Tgs of the polymer blends were similar to those of the respective homopolymers, as expected. SAXS experiments further demonstrated microphase separation of multiblock copolymers. This work demonstrates the enormous potential of multiblock architectures to tune the physical properties of synthetic polymers, by changing their glass transition temperature and their morphologies obtained from microphase separation, with domain sizes reaching under 10 nm

Deep face profiler (DeFaP): Towards explicit, non-restrained, non-invasive, facial and gaze comprehension

Eye tracking and head pose estimation (HPE) have previously lacked reliability, interpretability, and comprehensibility. For instance, many works rely on traditional computer vision methods, which may not perform well in dynamic and realistic environments. Recently, a widespread trend has emerged, leveraging deep learning for HPE specifically framed as a regression task; however, considering the real-time applications, the problem could be better formulated as classification (e.g., left, centre, right head pose and gaze) using a hybrid approach. For the first time, we present a complete facial profiling approach to extract micro and macro facial movement, gaze, and eye state features, which can be used for various applications related to comprehension analysis. The multi-model approach provides discrete human-understandable head pose estimations utilising deep transfer learning, a newly introduced method of head roll calculation, gaze estimation via iris detection, and eye state estimation (i.e., open or closed). Unlike existing works, this approach can automatically analyse the input image or video frame to produce human-understandable binary codes (e.g., eye open or close, looking left or right, etc.) for each facial component (aka face channels). The proposed approach is validated on multiple standard datasets, indicating outperformance compared to existing methods in several aspects, including reliability, generalisation, completeness, and interpretability. This work will significantly impact several diverse domains, including psychological and cognitive tasks with a broad scope of applications, such as in police interrogations and investigations, animal behaviour, and smart applications, including driver behaviour analysis, student attention measurement, and automated camera flashes

Identifying chemokines as therapeutic targets in renal disease: Lessons from antagonist studies and knockout mice

Chemokines, in concert with cytokines and adhesion molecules, play multiple roles in local and systemic immune responses. In the kidney, the temporal and spatial expression of chemokines correlates with local renal damage and accumulation of chemokine receptor-bearing leukocytes. Chemokines play important roles in leukocyte trafficking and blocking chemokines can effectively reduce renal leukocyte recruitment and subsequent renal damage. However, recent data indicate that blocking chemokine or chemokine receptor activity in renal disease may also exacerbate renal inflammation under certain conditions. An increasing amount of data indicates additional roles of chemokines in the regulation of innate and adaptive immune responses, which may adversively affect the outcome of interventional studies. This review summarizes available in vivo studies on the blockade of chemokines and chemokine receptors in kidney diseases, with a special focus on the therapeutic potential of anti-chemokine strategies, including potential side effects, in renal disease. Copyright (C) 2004 S. Karger AG, Basel

Seasonal Heat Acclimatisation in Healthy Adults:A Systematic Review

BACKGROUND: Physiological heat adaptations can be induced following various protocols that use either artificially controlled (i.e. acclimation) or naturally occurring (i.e. acclimatisation) environments. During the summer months in seasonal climates, adequate exposure to outdoor environmental heat stress should lead to transient seasonal heat acclimatisation. OBJECTIVES: The aim of the systematic review was to assess the available literature and characterise seasonal heat acclimatisation during the summer months and identify key factors that influence the magnitude of adaptation. ELIGIBILITY CRITERIA: English language, full-text articles that assessed seasonal heat acclimatisation on the same sample of healthy adults a minimum of 3 months apart were included. DATA SOURCES: Studies were identified using first- and second-order search terms in the databases MEDLINE, SPORTDiscus, CINAHL Plus with Full Text, Scopus and Cochrane, with the last search taking place on 15 July 2021. RISK OF BIAS: Studies were independently assessed by two authors for the risk of bias using a modified version of the McMaster critical review form. DATA EXTRACTION: Data for the following outcome variables were extracted: participant age, sex, body mass, height, body fat percentage, maximal oxygen uptake, time spent exercising outdoors (i.e. intensity, duration, environmental conditions), heat response test (i.e. protocol, time between tests), core temperature, skin temperature, heart rate, whole-body sweat loss, whole-body and local sweat rate, sweat sodium concentration, skin blood flow and plasma volume changes. RESULTS: Twenty-nine studies were included in this systematic review, including 561 participants across eight countries with a mean summer daytime wet-bulb globe temperature (WBGT) of 24.9 °C (range: 19.5–29.8 °C). Two studies reported a reduction in resting core temperature (0.16 °C; p < 0.05), 11 reported an increased sweat rate (range: 0.03–0.53 L·h(−1); p < 0.05), two observed a reduced heart rate during a heat response test (range: 3–8 beats·min(−1); p < 0.05), and six noted a reduced sweat sodium concentration (range: − 22 to − 59%; p < 0.05) following summer. The adaptations were associated with a mean summer WBGT of 25.2 °C (range: 19.6–28.7 °C). LIMITATIONS: The available studies primarily focussed on healthy male adults and demonstrated large differences in the reporting of factors that influence the development of seasonal heat acclimatisation, namely, exposure time and duration, exercise task and environmental conditions. CONCLUSIONS: Seasonal heat acclimatisation is induced across various climates in healthy adults. The magnitude of adaptation is dependent on a combination of environmental and physical activity characteristics. Providing environmental conditions are conducive to adaptation, the duration and intensity of outdoor physical activity, along with the timing of exposures, can influence seasonal heat acclimatisation. Future research should ensure the documentation of these factors to allow for a better characterisation of seasonal heat acclimatisation. PROSPERO REGISTRATION: CRD42020201883. SUPPLEMENTARY INFORMATION: The online version contains supplementary material available at 10.1007/s40279-022-01677-0

Pre-existing virus-specific CD8+ T-cells provide protection against pneumovirus-induced disease in mice

Pneumoviruses such as pneumonia virus of mice (PVM), bovine respiratory syncytial virus (bRSV) or human (h)RSV are closely related pneumoviruses that cause severe respiratory disease in their respective hosts. It is well-known that T-cell responses are essential in pneumovirus clearance, but pneumovirus-specific T-cell responses also are important mediators of severe immunopathology. In this study we determined whether memory- or pre-existing, transferred virus-specific CD8 + T-cells provide protection against PVM-induced disease. We show that during infection with a sublethal dose of PVM, both natural killer (NK) cells and CD8 + T-cells expand relatively late. Induction of CD8 + T-cell memory against a single CD8 + T-cell epitope, by dendritic cell (DC)-peptide immunization, leads to partial protection against PVM challenge and prevents Th2 differentiation of PVM-induced CD4 T-cells. In addition, adoptively transferred PVM-specific CD8 + T-cells, covering the entire PVM-specific CD8 + T-cell repertoire, provide partial protection from PVM-induced disease. From these data we infer that antigen-specific memory CD8 + T-cells offer significant protection to PVM-induced disease. Thus, CD8 + T-cells, despite being a major cause of PVM-associated pathology during primary infection, may offer promising targets of a protective pneumovirus vaccine

Insights into the influence of solvent polarity on the crystallization of poly(ethylene oxide) spin-coated thin films via in situ grazing incidence wide-angle X-ray scattering

Controlling polymer thin-film morphology and crystallinity is crucial for a wide range of applications, particularly in thin-film organic electronic devices. In this work, the crystallization behavior of a model polymer, poly(ethylene oxide) (PEO), during spin-coating is studied. PEO films were spun-cast from solvents possessing different polarities (chloroform, THF, and methanol) and probed via in situ grazing incidence wide-angle X-ray scattering. The crystallization behavior was found to follow the solvent polarity order (where chloroform chloroform > methanol). When spun-cast from nonpolar chloroform, crystallization largely followed Avrami kinetics, resulting in the formation of morphologies comprising large spherulites. PEO solutions cast from more polar solvents (THF and methanol) do not form well-defined highly crystalline morphologies and are largely amorphous with the presence of small crystalline regions. The difference in morphological development of PEO spun-cast from polar solvents is attributed to clustering phenomena that inhibit polymer crystallization. This work highlights the importance of considering individual components of polymer solubility, rather than simple total solubility, when designing processing routes for the generation of morphologies with optimum crystallinities or morphologies

Personal health technologies, micropolitics and resistance: A new materialist analysis

Personal health technologies (PHTs) are near-body devices or applications designed for use by a single individual, principally outside healthcare facilities. They enable users to monitor physiological processes or body activity, are frequently communication-enabled, and sometimes also intervene therapeutically. This paper explores a range of PHTs, from blood pressure or blood glucose monitors purchased in pharmacies, fitness monitors such as FitBit and Nike+ Fuelband, through to drug pumps and implantable medical devices. It applies a new materialist analysis, first reverse engineering a range of PHTs to explore their micropolitics, and then forward-engineering PHTs to meet, variously, public health, corporate, patient and resisting-citizen agendas. The paper concludes with a critical discussion of PHTs, and the possibilities of designing devices and apps that might foster a subversive micropolitics and encourage collective and resisting ‘citizen-health’

Facile synthesis and proposed mechanism of α,ω‐oxetanyl-telechelic poly(3-nitratomethyl-3-methyl oxetane) by an SN2(i) nitrato displacement method in basic media

The synthesis of a novel heterocyclic–telechelic polymer, α,ω-oxetanyl-telechelic poly(3-nitratomethyl-3-methyl oxetane), is described. Infrared spectroscopy (IR), gel permeation chromatography (GPC), and nuclear magnetic resonance (NMR) spectroscopy have been used to confirm the successful synthesis, demonstrating the presence of the telechelic-oxetanyl moieties. Synthesis of the terminal functionalities has been achieved via displacement of nitrato groups, in a manner similar to that employed with other leaving groups such as azido, bromo, and nitro, initiated by nucleophiles. In the present case, displacement occurs on the ends of a nitrato-functionalized polymer driven by the formation of sodium nitrate, which is supported by the polar aprotic solvent N,N-dimethyl formamide. The formation of an alkoxide at the polymer chain ends is favored and allows internal back-biting to the nearest carbon bearing the nitrato group, intrinsically in an SN2(i) reaction, leading to α,ω-oxetanyl functionalization. The telechelic-oxetanyl moieties have the potential to be cross-linked by chemical (e.g., acidic) or radiative (e.g., ultraviolet) curing methods without the use of high temperatures, usually below 100°C. This type of material was designed for future use as a contraband simulant, whereby it would form the predominant constituent of elastomeric composites comprising rubbery polymer with small quantities of solids, typically crystals of contraband substances, such as explosives or narcotics. This method also provides an alternative approach to ring closure and synthesis of heterocycles

High susceptibility to lipopolysaccharide-induced lethal shock in encephalomyocarditis virus-infected mice

Secondary bacterial infection in humans is one of the pathological conditions requiring clinical attention. In this study, we examined the effect of lipopolysaccharide (LPS) on encephalomyocarditis virus (EMCV) infected mice. All mice inoculated with EMCV at 5 days before LPS challenge died within 24 h. LPS-induced TNF-α mRNA expression was significantly increased in the brain and heart at 5 days after EMCV infection. CD11b+/TLR4+ cell population in the heart was remarkably elevated at 5 days after EMCV infection, and sorted CD11b+ cells at 5 days after EMCV infection produced a large amount of TNF-α on LPS stimulation in vivo and in vitro. In conclusion, we found that the infiltration of CD11b+ cells into infected organs is involved in the subsequent LPS-induced lethal shock in viral encephalomyocarditis. This new experimental model can help define the mechanism by which secondary bacterial infection causes a lethal shock in viral encephalomyocarditis