Ultrafast two-dimensional infrared (2D IR) vibrational echo spectroscopy has proven broadly useful for studying molecular dynamics in solutions. Here, we extend the technique to probing the ...interfacial dynamics and structure of a silica surface-tethered transition metal carbonyl complex—tricarbonyl (1,10-phenanthroline)rhenium chloride—of interest as a photoreduction catalyst. We interpret the data using a theoretical framework devised to separate the roles of structural evolution and excitation transfer in inducing spectral diffusion. The structural dynamics, as reported on by a carbonyl stretch vibration of the surface-bound complex, have a characteristic time of ~150 picoseconds in the absence of solvent, decrease in duration by a factor of three upon addition of chloroform, and decrease another order of magnitude for the bulk solution. Conversely, solvent-complex interactions increase the lifetime of the probed vibration by 160% when solvent is applied to the monolayer.
The Irish institute of technology sector is undergoing a major restructuring that will culminate in mergers, to form technological universities (TU). It is essential that the perspective of key ...stakeholders is fully considered throughout this process, in order to facilitate a successful transition. This research investigates the factors influencing attitudes of academic staff toward their institute becoming a TU. A theoretical model was developed, based on the extant literature, and validated using partial least squares structural equation modelling. Academic staff attitudes to the proposed change were found to relate to their sense of organisational commitment and their contribution to teaching and research. Levels of happiness and job satisfaction were also found to influence their sense of organisational affiliation and belonging. Those with greater organisational commitment and a greater research focus were more likely to report a positive attitude to the change. Academic staff with a predominately teaching focus reported a relatively more negative attitude to the change. These findings facilitate the prescription of targeted initiatives to secure stakeholder support, throughout the transition. Staff wellbeing initiatives can improve job satisfaction and cement organisational commitment, positively influencing attitude to the change. Promoting research activity, while reaffirming the importance of teaching, can also serve to promote a positive attitude to the change in status. The unique model presented in this research has the potential to inform stakeholder management in the implementation of major organisational change in higher education both nationally and internationally.
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Dostopno za:
BFBNIB, DOBA, IZUM, KILJ, NUK, PILJ, PNG, SAZU, SIK, UILJ, UKNU, UL, UM, UPUK
The sixth update of the Canadian Stroke Best Practice Recommendations: Rehabilitation, Recovery, and Reintegration following Stroke. Part one: Rehabilitation and Recovery Following Stroke is a ...comprehensive set of evidence-based guidelines addressing issues surrounding impairments, activity limitations, and participation restrictions following stroke. Rehabilitation is a critical component of recovery, essential for helping patients to regain lost skills, relearn tasks, and regain independence. Following a stroke, many people typically require rehabilitation for persisting deficits related to hemiparesis, upper-limb dysfunction, pain, impaired balance, swallowing, and vision, neglect, and limitations with mobility, activities of daily living, and communication. This module addresses interventions related to these issues as well as the structure in which they are provided, since rehabilitation can be provided on an inpatient, outpatient, or community basis. These guidelines also recognize that rehabilitation needs of people with stroke may change over time and therefore intermittent reassessment is important. Recommendations are appropriate for use by all healthcare providers and system planners who organize and provide care to patients following stroke across a broad range of settings. Unlike the previous set of recommendations, in which pediatric stroke was included, this set of recommendations includes primarily adult rehabilitation, recognizing many of these therapies may be applicable in children. Recommendations related to community reintegration, which were previously included within this rehabilitation module, can now be found in the companion module, Rehabilitation, Recovery, and Community Participation following Stroke. Part Two: Transitions and Community Participation Following Stroke.
We propose a novel Timed Intervention S, P, E, I, Q, R, D model for projecting the possible futures of the COVID-19 pandemic in the USA. The proposed model introduces a series of timed interventions ...that can account for the influence of real time changes in government policy and social norms. We consider three separate types of interventions: (i) Protective interventions: Where population moves from susceptible to protected corresponding to mask mandates, stay-at-home orders and/or social distancing. (ii) Release interventions: Where population moves from protected to susceptible corresponding to social distancing mandates and practices being lifted by policy or pandemic fatigue. (iii) Vaccination interventions: Where population moves from susceptible, protected, and exposed to recovered (meaning immune) corresponding to the mass immunization of the U.S. Population. By treating the pandemic with timed interventions, we are able to model the pandemic extremely effectively, as well as directly predicting the course of the pandemic under differing sets of intervention schedules. We show that without prompt effective protective/vaccination interventions the pandemic will be extended significantly and result in many millions of deaths in the U.S.
Population leakage outside the qubit subspace presents a particularly harmful source of error that cannot be handled by standard error correction methods. Using a trapped ^{171}Yb^{+} ion, we ...demonstrate an optical pumping scheme to suppress leakage errors in atomic hyperfine qubits. The selection rules and narrow linewidth of a quadrupole transition are used to selectively pump population out of leakage states and back into the qubit subspace. Each pumping cycle reduces the leakage population by a factor of ∼3, allowing for an exponential suppression in the number of cycles. We use interleaved randomized benchmarking on the qubit subspace to show that this pumping procedure has negligible side effects on the qubit subspace, bounding the induced qubit memory error by ≤2.0(8)×10^{-5} per cycle, and qubit population decay to ≤1.4(3)×10^{-7} per cycle. These results clear a major obstacle for implementations of quantum error correction and error mitigation protocols.
Touch is an important means through which mothers and infants co-regulate during periods of stress or perturbation. The present study examined the synchrony of maternal and infant touching behaviours ...among 41 mother-infant dyads, some of whom were deemed at-risk due to maternal depressive symptomatology. Mothers and their 4-month-old infants participated in the Still-Face (maternal emotional unavailability; SF) and Separation (maternal physical unavailability; SP) procedures. Infant crying was examined across procedures and investigated as a brief period of perturbation. Results revealed that mothers and infants displayed a positive pattern of tactile synchrony (coordinated, analogous changes in touch) during infant crying episodes. However, dyads in the high depression group displayed significantly less affectionate touch during instances of infant crying. Furthermore, more depressive symptoms were associated with less maternal and infant touch and lower rates of infant crying. This group of dyads may be less expressive via touch, be less affected by disruptions in their interactions, have impaired regulatory abilities, or simply require minimal amounts of touch to mutually regulate following social stressors and during brief perturbation periods. These findings enrich our limited knowledge about the dynamic interplay of maternal and infant touch and inform preventative intervention programs for at-risk groups.
•Mothers and infants displayed a positive pattern of tactile synchrony during infant crying episodes.•Dyads in the high depression group displayed significantly less affectionate touching behaviours during instances of infant crying.•More depressive symptoms were associated with less maternal and infant touch and lower rates of infant crying.
The complex MnII(R,R-mcp)(CF3SO3)2 is an efficient and practical catalyst for the epoxidation of electron-deficient olefins. This catalyst is capable of epoxidizing olefins with as little as 0.1 mol ...% catalyst in under 5 min using 1.2 equiv of peracetic acid as the terminal oxidant. A wide scope of substrates are epoxidized including terminal, tertiary, cis and trans internal, enones, and methacrylates with >85% isolated yields.
Biomimetic functional models of the mononuclear copper enzyme galactose oxidase are presented that catalytically oxidize benzylic and allylic alcohols to aldehydes with O$_2$ under mild conditions. ...The mechanistic fidelity between the models and the natural system is pronounced. Modest structural mimicry proves sufficient to transfer an unusual ligand-based radical mechanism, previously unprecedented outside the protein matrix, to a simple chemical system.
We present a new and simplified two-qubit randomized benchmarking procedure that operates only in the symmetric subspace of a pair of qubits and is well suited for benchmarking trapped-ion systems. ...By performing benchmarking only in the symmetric subspace, we drastically reduce the experimental complexity, a number of gates required, and run time. The protocol is demonstrated on trapped ions using collective single-qubit rotations and the Mølmer-Sørenson (MS) interaction to estimate an entangling gate error of 2(1)×10^{−3}. We analyze the expected errors in the MS gate and find that the population remains mostly in the symmetric subspace. The errors that mix symmetric and antisymmetric subspaces appear as leakage and we characterize them by combining our protocol with recently proposed leakage benchmarking. Generalizations and limitations of the protocol are also discussed.
Coronavirus pneumonia is accompanied by rapid virus replication, where a large number of inflammatory cell infiltration and cytokine storm may lead to acute lung injury, acute respiratory distress ...syndrome (ARDS) and death. The uncontrolled release of pro-inflammatory cytokines, including interleukin (IL)-1β and IL-6, is associated with ARDS. This constituted the first study to report on the variability in physicochemical properties of β-glucans extracts from the same edible mushroom Lentinus edodes on the reduction of these pro-inflammatory cytokines and oxidative stress. Specifically, the impact on the immunomodulatory and cytoprotective properties of our novel in ‘house’ (IH-Lentinan, IHL) and a commercial (Carbosynth-Lentinan, CL) Lentinan extract were investigated using in vitro models of lung injury and macrophage phagocytosis. CL comprised higher amounts of α-glucans and correspondingly less β-glucans. The two lentinan extracts demonstrated varying immunomodulatory activities. Both Lentinan extracts reduced cytokine-induced NF-κB activation in human alveolar epithelial A549 cells, with the IHL extract proving more effective at lower doses. In contrast, in activated THP-1 derived macrophages, the CL extract more effectively attenuated pro-inflammatory cytokine production (TNF-α, IL-8, IL-2, IL-6, IL-22) as well as TGF-β and IL-10. The CL extract attenuated oxidative stress-induced early apoptosis, while the IHL extract attenuated late apoptosis. Our findings demonstrate significant physicochemical differences between Lentinan extracts, which produce differential in vitro immunomodulatory and pulmonary cytoprotective effects that may also have positive relevance to candidate COVID-19 therapeutics targeting cytokine storm.
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•β-Glucans from shiitake mushroom reduces IL-1β, IL-6 in in vitro lung injury model.•β-Glucans from same source can differ in immunomodulatory and pulmonary cytoprotective effects.•β-Glucans can reduce oxidative stress and activate macrophages.•β-Glucans may ameliorate cytokine storm that causes ARDS as seen with COVID-19.
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