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Zeolite-Catalyzed Isobutene Amination: Mechanism and Kinetics
Amination of isobutene with NH was investigated over Brønsted acidic zeolites at 1 atm and 453-483 K. To compare catalytic activities over different zeolites, the measured reaction rates are normalized by the number of active sites determined by tert-butylamine temperature-programmed desorption (TPD). Small- A nd medium-pore zeolites with one-dimensional channels exhibit low activity because of pore blockage by adsorbed tert-butylammonium ions. However, turnover frequencies and activation energies are not sensitive to framework identity, as long as the active site is accessible to isobutene and tert-butylamine. Kinetic measurements and FTIR spectroscopy reveal that the Brønsted acid sites in MFI are covered predominantly with tert-butylammonium ions under reaction conditions. The desorption of tert-butylamine is assisted by the concurrent adsorption of isobutene. DFT simulations show that at very low tert-butylamine partial pressures, for example, at the inlet to the reactor, tert-butylamine desorption is rate-limiting. However, at sufficiently high tert-butylamine partial pressures (>0.03 kPa), protonation of isobutene to the corresponding carbenium ion limits the rate of amination.
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High-Performance, Wearable Thermoelectric Generator Based on a Highly Aligned Carbon Nanotube Sheet
A high-performance, wearable thermoelectric generator (TEG) was fabricated with a highly aligned carbon nanotube (CNT) sheet. The aligned CNT sheet exhibits extraordinary electrical conductivity compared to disordered CNT sheets and also can be directly fabricated as a continuous TEG without metal electrode interconnects. This provides a significant reduction in contact resistance between TE legs and electrodes compared to traditional TEGs, resulting in higher power output. In addition, the continuity of the module without any disconnected parts provides high degrees of mechanical stability and durability. This robust and scalable approach to flexible TEG fabrication paves the way for CNT applications in lightweight, flexible, and wearable electronics
Effective health care for older people resident in care homes: the optimal study protocol for realist review
This is an Open Access article distributed under the terms of the Creative Commons Attribution License (http://creativecommons.org/licenses/by/4.0), which permits unrestricted use, distribution, and reproduction in any medium, provided the original work is properly credited. The Creative Commons Public Domain Dedication waiver (http://creativecommons.org/publicdomain/zero/1.0/) applies to the data made available in this article, unless otherwise stated.Background: Care homes in the UK rely on general practice for access to specialist medical and nursing care as well as referral to therapists and secondary care. Service delivery to care homes is highly variable in both quantity and quality. This variability is also evident in the commissioning and organisation of care home-specific services that range from the payment of incentives to general practitioners (GPs) to visit care homes, to the creation of care home specialist teams and outreach services run by geriatricians. No primary studies or systematic reviews have robustly evaluated the impact of these different approaches on organisation and resident-level outcomes. Our aim is to identify factors which may explain the perceived or demonstrated effectiveness of programmes to improve health-related outcomes in older people living in care homes. Methods/Design: A realist review approach will be used to develop a theoretical understanding of what works when, why and in what circumstances. Elements of service models of interest include those that focus on assessment and management of residents’ health, those that use strategies to encourage closer working between visiting health care providers and care home staff, and those that address system-wide issues about access to assessment and treatment. These will include studies on continence, dignity, and speech and language assessment as well as interventions to promote person centred dementia care, improve strength and mobility, and nutrition. The impact of these interventions and their different mechanisms will be considered in relation to five key outcomes: residents’ medication use, use of out of hours’ services, hospital admissions (including use of Accident and Emergency) and length of hospital stay, costs and user satisfaction. An iterative three-stage approach will be undertaken that is stakeholder-driven and optimises the knowledge and networks of the research team. Discussion: This realist review will explore why and for whom different approaches to providing health care to residents in care homes improves access to health care in the five areas of interest. It will inform commissioning decisions and be the basis for further research. This systematic review protocol is registered on the PROSPERO database reference number: CRD42014009112NIHR Health Services & Delivery Research Programme. Project number 11/1021/0
Characterization of Shewanella oneidensis MtrC: a cell-surface decaheme cytochrome involved in respiratory electron transport to extracellular electron acceptors
MtrC is a decaheme c-type cytochrome associated with the outer cell membrane of Fe(III)-respiring species of the Shewanella genus. It is proposed to play a role in anaerobic respiration by mediating electron transfer to extracellular mineral oxides that can serve as terminal electron acceptors. The present work presents the first spectropotentiometric and voltammetric characterization of MtrC, using protein purified from Shewanella oneidensis MR-1. Potentiometric titrations, monitored by UV–vis absorption and electron paramagnetic resonance (EPR) spectroscopy, reveal that the hemes within MtrC titrate over a broad potential range spanning between approximately +100 and approximately -500 mV (vs. the standard hydrogen electrode). Across this potential window the UV–vis absorption spectra are characteristic of low-spin c-type hemes and the EPR spectra reveal broad, complex features that suggest the presence of magnetically spin-coupled low-spin c-hemes. Non-catalytic protein film voltammetry of MtrC demonstrates reversible electrochemistry over a potential window similar to that disclosed spectroscopically. The voltammetry also allows definition of kinetic properties of MtrC in direct electron exchange with a solid electrode surface and during reduction of a model Fe(III) substrate. Taken together, the data provide quantitative information on the potential domain in which MtrC can operate
Fission yeast 26S proteasome mutants are multi-drug resistant due to stabilization of the pap1 transcription factor
Here we report the result of a genetic screen for mutants resistant to the microtubule poison methyl benzimidazol-2-yl carbamate (MBC) that were also temperature sensitive for growth. In total the isolated mutants were distributed in ten complementation groups. Cloning experiments revealed that most of the mutants were in essential genes encoding various 26S proteasome subunits. We found that the proteasome mutants are multi-drug resistant due to stabilization of the stress-activated transcription factor Pap1. We show that the ubiquitylation and ultimately the degradation of Pap1 depend on the Rhp6/Ubc2 E2 ubiquitin conjugating enzyme and the Ubr1 E3 ubiquitin-protein ligase. Accordingly, mutants lacking Rhp6 or Ubr1 display drug-resistant phenotypes
The role of Comprehension in Requirements and Implications for Use Case Descriptions
Within requirements engineering it is generally accepted that in writing specifications (or indeed any requirements phase document), one attempts to produce an artefact which will be simple to comprehend for the user. That is, whether the document is intended for customers to validate requirements, or engineers to understand what the design must deliver, comprehension is an important goal for the author. Indeed, advice on producing ‘readable’ or ‘understandable’ documents is often included in courses on requirements engineering. However, few researchers, particularly within the software engineering domain, have attempted either to define or to understand the nature of comprehension and it’s implications for guidance on the production of quality requirements.
Therefore, this paper examines thoroughly the nature of textual comprehension, drawing heavily from research in discourse process, and suggests some implications for requirements (and other) software documentation. In essence, we find that the guidance on writing requirements, often prevalent within software engineering, may be based upon assumptions which are an oversimplification of the nature of comprehension. Hence, the paper examines guidelines which have been proposed, in this case for use case descriptions, and the extent to which they agree with discourse process theory; before suggesting refinements to the guidelines which attempt to utilise lessons learned from our richer understanding of the underlying discourse process theory. For example, we suggest subtly different sets of writing guidelines for the different tasks of requirements, specification and design
Combined In Silico, In Vivo, and In Vitro Studies Shed Insights into the Acute Inflammatory Response in Middle-Aged Mice
We combined in silico, in vivo, and in vitro studies to gain insights into age-dependent changes in acute inflammation in response to bacterial endotoxin (LPS). Time-course cytokine, chemokine, and NO2-/NO3- data from "middle-aged" (6-8 months old) C57BL/6 mice were used to re-parameterize a mechanistic mathematical model of acute inflammation originally calibrated for "young" (2-3 months old) mice. These studies suggested that macrophages from middle-aged mice are more susceptible to cell death, as well as producing higher levels of pro-inflammatory cytokines, vs. macrophages from young mice. In support of the in silico-derived hypotheses, resident peritoneal cells from endotoxemic middle-aged mice exhibited reduced viability and produced elevated levels of TNF-α, IL-6, IL-10, and KC/CXCL1 as compared to cells from young mice. Our studies demonstrate the utility of a combined in silico, in vivo, and in vitro approach to the study of acute inflammation in shock states, and suggest hypotheses with regard to the changes in the cytokine milieu that accompany aging. © 2013 Namas et al
An advanced Bayesian model for the visual tracking of multiple interacting objects
Visual tracking of multiple objects is a key component of many visual-based systems. While there are reliable
algorithms for tracking a single object in constrained scenarios, the object tracking is still a challenge in
uncontrolled situations involving multiple interacting objects that have a complex dynamics. In this article, a novel
Bayesian model for tracking multiple interacting objects in unrestricted situations is proposed. This is accomplished
by means of an advanced object dynamic model that predicts possible interactive behaviors, which in turn depend
on the inference of potential events of object occlusion. The proposed tracking model can also handle false and
missing detections that are typical from visual object detectors operating in uncontrolled scenarios. On the other
hand, a Rao-Blackwellization technique has been used to improve the accuracy of the estimated object trajectories,
which is a fundamental aspect in the tracking of multiple objects due to its high dimensionality. Excellent results
have been obtained using a publicly available database, proving the efficiency of the proposed approach
Foot pain and foot health in an educated population of adults: results from the Glasgow Caledonian University Alumni Foot Health Survey
Abstract Background Foot pain is common amongst the general population and impacts negatively on physical function and quality of life. Associations between personal health characteristics, lifestyle/behaviour factors and foot pain have been studied; however, the role of wider determinants of health on foot pain have received relatively little attention. Objectives of this study are i) to describe foot pain and foot health characteristics in an educated population of adults; ii) to explore associations between moderate-to-severe foot pain and a variety of factors including gender, age, medical conditions/co-morbidity/multi-morbidity, key indicators of general health, foot pathologies, and social determinants of health; and iii) to evaluate associations between moderate-to-severe foot pain and foot function, foot health and health-related quality-of-life. Methods Between February and March 2018, Glasgow Caledonian University Alumni with a working email address were invited to participate in the cross-sectional electronic survey (anonymously) by email via the Glasgow Caledonian University Alumni Office. The survey was constructed using the REDCap secure web online survey application and sought information on presence/absence of moderate-to-severe foot pain, patient characteristics (age, body mass index, socioeconomic status, occupation class, comorbidities, and foot pathologies). Prevalence data were expressed as absolute frequencies and percentages. Multivariate logistic and linear regressions were undertaken to identify associations 1) between independent variables and moderate-to-severe foot pain, and 2) between moderate-to-severe foot pain and foot function, foot health and health-related quality of life. Results Of 50,228 invitations distributed, there were 7707 unique views and 593 valid completions (median age [inter-quartile range] 42 [31–52], 67.3% female) of the survey (7.7% response rate). The sample was comprised predominantly of white Scottish/British (89.4%) working age adults (95%), the majority of whom were overweight or obese (57.9%), and in either full-time or part-time employment (82.5%) as professionals (72.5%). Over two-thirds (68.5%) of the sample were classified in the highest 6 deciles (most affluent) of social deprivation. Moderate-to-severe foot pain affected 236/593 respondents (39.8%). High body mass index, presence of bunions, back pain, rheumatoid arthritis, hip pain and lower occupation class were included in the final multivariate model and all were significantly and independently associated with moderate-to-severe foot pain (p < 0.05), except for rheumatoid arthritis (p = 0.057). Moderate-to-severe foot pain was significantly and independently associated lower foot function, foot health and health-related quality of life scores following adjustment for age, gender and body mass index (p < 0.05). Conclusions Moderate-to-severe foot pain was highly prevalent in a university-educated population and was independently associated with female gender, high body mass index, bunions, back pain, hip pain and lower occupational class. Presence of moderate-to-severe foot pain was associated with worse scores for foot function, foot health and health-related quality-of-life. Education attainment does not appear to be protective against moderate-to-severe foot pain
Caspase-2 is upregulated after sciatic nerve transection and its inhibition protects dorsal root ganglion neurons from Apoptosis after serum withdrawal
Sciatic nerve (SN) transection-induced apoptosis of dorsal root ganglion neurons (DRGN) is one factor determining the efficacy of peripheral axonal regeneration and the return of sensation. Here, we tested the hypothesis that caspase-2(CASP2) orchestrates apoptosis of axotomised DRGN both in vivo and in vitro by disrupting the local neurotrophic supply to DRGN. We observed significantly elevated levels of cleaved CASP2 (C-CASP2), compared to cleaved caspase-3 (C-CASP3), within TUNEL+DRGN and DRG glia (satellite and Schwann cells) after SN transection. A serum withdrawal cell culture model, which induced 40% apoptotic death in DRGN and 60% in glia, was used to model DRGN loss after neurotrophic factor withdrawal. Elevated C-CASP2 and TUNEL were observed in both DRGN and DRG glia, with C-CASP2 localisation shifting from the cytosol to the nucleus, a required step for induction of direct CASP2-mediated apoptosis. Furthermore, siRNAmediated downregulation of CASP2 protected 50% of DRGN from apoptosis after serum withdrawal, while downregulation of CASP3 had no effect on DRGN or DRG glia survival. We conclude that CASP2 orchestrates the death of SN-axotomised DRGN directly and also indirectly through loss of DRG glia and their local neurotrophic factor support. Accordingly, inhibiting CASP2 expression is a potential therapy for improving both the SN regeneration response and peripheral sensory recovery
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