Transition Barrier Research Articles

Structure and conformational analysis of 5,5-bis(bromomethyl)-2-trichloromethyl-1,3-dioxane by XRD, NMR and computer simulation

According to the NMR 1Н, 13С and X-ray analysis data molecules of 5,5-bis(bromomethyl)-2-trichloromethyl-1,3-dioxane in the crystalline phase and in solution have a chair conformation with an equatorial trichloromethyl group. The route of conformational transformations for isolated molecule and for a cluster with five chloroform molecules, as well as a transition states and barriers to the internal rotation of the axial and equatorial trichloromethyl group have been established using DFT approximation PBE/3ξ.

Gender differences in retirement transition goals and barriers: a case study in the university sector

ABSTRACT Australia’s retirement system is often heralded as world-class. Yet research investigating the superannuation system has reported highly gendered outcomes even in the university sector, which has generous superannuation provisions and established career management practices. This study investigates gender differences in retirement transition goals and barriers in the sector. Data from university employees who are 50 years or older show that gender differences exist. Women are more likely than men to be frustrated in their attempts to transition into retirement as desired and are more likely to desire a reduction in workdays per week. Men are more likely to prefer to continue working as currently or to reduce responsibility. Economic reasons are more likely to be the barrier for women, while organisational reasons are more likely to be the barrier for men.

Emergency department care transition barriers: A qualitative study of care partners of older adults with cognitive impairment.

INTRODUCTIONAfter emergency department (ED) discharge, persons living with cognitive impairment (PLWCI) and their care partners are particularly at risk for adverse outcomes. We sought to identify the barriers experienced by care partners of PLWCI during ED discharge care transitions.METHODSWe conducted a qualitative study of 25 care partners of PLWCI discharged from four EDs. We used the validated 4AT and care partner‐completed AD8 screening tools, respectively, to exclude care partners of older adults with concern for delirium and include care partners of older adults with cognitive impairment. We conducted recorded, semi‐structured interviews using a standardized guide, and two team members coded and analyzed all professional transcriptions to identify emerging themes and representative quotations.RESULTSCare partners’ mean age was 56.7 years, 80% were female, and 24% identified as African American. We identified four major barriers regarding ED discharge care transitions among care partners of PLWCI: (1) unique care considerations while in the ED setting impact the perceived success of the care transition, (2) poor communication and lack of care partner engagement was a commonplace during the ED discharge process, (3) care partners experienced challenges and additional responsibilities when aiding during acute illness and recovery phases, and (4) navigating the health care system after an ED encounter was perceived as difficult by care partners.DISCUSSIONOur findings demonstrate critical barriers faced during ED discharge care transitions among care partners of PLWCI. Findings from this work may inform the development of novel care partner‐reported outcome measures as well as ED discharge care transition interventions targeting care partners.

Mechanism of internal magnetic energy of Cu-rich phase precipitation in Fe<sub>84</sub>Cu<sub>15</sub>Mn<sub>1</sub> alloy by phase field method

Based on the continuous phase field model, the precipitation behavior of Cu rich phase in Fe-Cu-Mn alloy under the action of internal magnetic energy is studied. The effects of internal magnetic energy on the average particle radius, volume fraction and Gibbs free energy of Cu rich phase at different temperatures and different Mn content and Cu content are investigated. The simulation results show that the lower the Mn content and the higher the Curie temperature, the greater the contribution of internal magnetic energy to free energy is, and the contribution of internal magnetic energy decreases with temperature increasing. The internal magnetic energy reduces the phase structure transition barrier and promotes the phase structure transition. The volume fraction of precipitated phase increases with Cu content increasing. Compared with the effect of internal magnetic energy on the volume fraction of precipitated phase, the effect of internal magnetic energy leads to a large volume fraction of precipitated phase. Therefore, under the action of internal magnetic energy, the Cu rich phase has larger average particle size, volume fraction and smaller coercivity. Finally, the change trend of alloy hardness is predicted.

Implementation of an intelligent supply chain control tower: a socio-technical systems case study

Despite the proliferation of Industry 4.0 technologies, there is little guidance concerning how companies can integrate them in their supply chains. This study examines the implementation of a supply chain (SC) control tower (SCCT) by a large manufacturing company aiming to create an intelligent supply chain. This study applies Socio-Technical systems (STS) theory using the technology typology (long-linked, mediating, intensive) in the context of industry 4.0. The company followed a three-phase implementation plan (I: Initiation, II: Live, III: Continuous improvement) to transit from outsourcing supply chain control to developing the SCCT control structure and then creating intelligent SC assets and capabilities. The study shows that the SCCT needs to integrate all three technology types to reflect the intelligent supply chain. Further, it shows that the interactions of technologies with the SCCT team, internal and external supply chain stakeholders are critical in managing the development, implementation, and growth of intelligent supply chains. It identifies transition barriers including system misalignment, poor socio-technical integration, and an invert of trust between internal and external supply chain stakeholders. The intelligent supply chain emerges as a result of managing socio-technical interactions systematically.

Residue Folding Degree-Relationship to Secondary Structure Categories and Use as Collective Variable.

Recently, we have shown that the residue folding degree, a network-based measure of folded content in proteins, is able to capture backbone conformational transitions related to the formation of secondary structures in molecular dynamics (MD) simulations. In this work, we focus primarily on developing a collective variable (CV) for MD based on this residue-bound parameter to be able to trace the evolution of secondary structure in segments of the protein. We show that this CV can do just that and that the related energy profiles (potentials of mean force, PMF) and transition barriers are comparable to those found by others for particular events in the folding process of the model mini protein Trp-cage. Hence, we conclude that the relative segment folding degree (the newly proposed CV) is a computationally viable option to gain insight into the formation of secondary structures in protein dynamics. We also show that this CV can be directly used as a measure of the amount of -helical content in a selected segment.

An integrated electrode strengthened by dense layer for aqueous zinc ion batteries with long lifespan

Rechargeable aqueous zinc ion batteries have attracted increasing attention for large-scale energy storage system. Restricted by the zinc deposition and dendrite growth, the practical application was hindered seriously by the poor rechargeability and instability. The strategy of utilizing Zn-Al-layered double hydroxides hexagonal nanoplates modifying zinc metal anode was employed by a scalable method of spinning coating. This integrated electrode can not only realize ions well-distributed reaction on the electrode surface due to the dense protection layer weak adsorption behavior and low surface area, but also can efficiently avoid excessive zinc deposition and growth of zinc dendrites. The nucleation and dissolution energy barriers in the phase transition between zinc ions and the integrated electrode are decreased as well. The integrated electrode harvests a long-term stability of 1000 h at 1.0 mA h cm-2 and effectively suppresses side reactions in the Zn//Zn symmetric cells. In addition, coupled with MnO2 as full cell, the capacity remains 195 mA h g-1 with the retention of 81.2% after 200 cycles. It is promising that the employed scalable strategy will provide new pathway into Zn metal anode protection and accelerate the practical application of aqueous zinc ion batteries.

Barriers of School Transition for Children with Disability: Lived Experience of Parents in Kathmandu Valley

This study aimed to explore the barrier of school transition for the children with disability from the parent's prospective. This study adopted qualitative method along with hermeneutics phenomenology. On the behalf of philosophical orientation, multiple realities were ontological basis and lived experiences of participants were epistemological assumption. The construct of critical disability theory was applied in this study. Purposefully 5 parents were selected from Kathmandu Valley. Data sources included field's notes, indepth interviews and artifacts. Interviewed data were transcribed and categorized to develop theme. Result revealed that several challenges such as awareness, attitude, accessibility, misconception, infrastructure, lack of policy implementation and ill motivation about disability are the major barrier towards transition. The perception of parents toward special school and rehabilitation centre are inadequately supporting to smooth transition. This study might be valuable support for policy maker in ensuring the no child left behind for the welfare state.

Potential optical molecular switch: Lithium@cyclo[18]carbon complex transforming between two stable configurations

Doping alkali metal atoms, especially lithium (Li), in nanocarbon materials has always been considered to be one of the most effective methods to improve the optical properties of the system. In this theoretical work, we doped a Li atom to the recently observed all-carboatomic molecule, cyclo[18]carbon (C18), and finally obtained two stable configurations with Li inside and outside the ring. The calculation results show that the energy barrier of transition between the two Li@C18 configurations is low, so the conversion is easy to occur at ambient temperature. Further study reveals that the state of Li@C18 complex, namely its dominant configuration, can be switched by applying a proper external electric field (EEF). The electronic structure, absorption spectrum, and optical nonlinearity of the two configurations are found to be significantly different, which indicates that the optical properties of the Li@C18 complex can be effectively regulated by switching the location of doped Li atom between inside and outside the carbon ring. With the help of various wavefunction analysis methods, the nature of the discrepancies in the properties of Li@C18 complex with different configurations was deeply revealed. The relevant results are expected to provide theoretical guidance for development of cyclocarbon-based optical molecular switches.

Biopsychosocial factors related to transition among adolescents and young adults with sickle cell disease: A systematic review.

It is critical to support adolescents and young adults (AYAs) with sickle cell disease (SCD) during transition to adult healthcare. We provide a systematic review of literature related to biopsychosocial influences on transition among AYAs with SCD. Data sources included studies published between January 2010 and May 2020. Forty-four studies were included. Biopsychosocial factors related to improved transition outcomes included older AYA age, greater disease severity, intact neurocognitive functioning, and greater pain coping skills. Financial and insurance barriers were noted. The importance of cultural considerations and provider communication were noted across two qualitative studies. Ten studies assessed efficacy of transition interventions, with 80 % resulting in improvements; however, retention in programs was low and gaps in knowledge and skills remained. Incorporation of early, ongoing assessments of transition readiness and barriers into culturally-tailored interventions aimed at improving transition outcomes is recommended. Examination of longitudinal relationships and interactions across biopsychosocial influences is needed.

Boosting the Redox Kinetics of High‐Voltage P2‐Type Cathode by Radially Oriented {010} Exposed Nanoplates for High‐Power Sodium‐Ion Batteries

High‐voltage P2‐type cathode with large capacity, high air stability, and low cost has attracted extensive attention. However, large ionic radius of Na+ and Na+/vacancy ordering result in low reaction kinetics and poor high‐rate capability. Herein, cobalt‐doped hierarchical structure assembled by radially oriented {010} exposed nanoplates is developed. With radially oriented grains infiltrating from surface to interior, all the {010} exposed surfaces are electrochemically active planes, and Na+ ions diffuse directly into electrolyte without passing through grain boundaries, building up 3D transfer channels. The trivalent cobalt substitution suppresses unwanted Na+/vacancy ordering and increases energy barrier of the phase transition from P2‐ to O2‐type oxide. These synergetic effects remarkably boost the redox kinetics of high‐voltage P2‐type cathode. Consequently, a large reversible capacity of 112 mAh g−1 is achieved even at 20 C, indicating excellent high‐rate capability. The absence of P2–O2 phase transition also gives rise to superior cycling stability, maintaining a capacity retention of 85% after 200 cycles. In addition, full cells composed of this hierarchical P2‐type cathode and hard carbon anode deliver high energy‐ and power‐densities. These achievements offer a new insight into boosting redox kinetics of P2‐ and O3‐type layered cathodes for high‐power sodium‐ion batteries.

Molecular Dynamics Simulations of the Breathing Phase Transition of MOF Nanocrystallites II: Explicitly Modeling the Pressure Medium.

One of the most investigated properties of porous crystalline metal-organic frameworks (MOFs) is their potential flexibility to undergo large changes in unit cell size upon guest adsorption or other stimuli, referred to as “breathing”. Computationally, such phase transitions are usually investigated using periodic boundary conditions, where the system’s volume can be controlled directly. However, we have recently shown that important aspects like the formation of a moving interface between the open and the closed pore form or the free energy barrier of the first-order phase transition and its size effects can best be investigated using non-periodic nanocrystallite (NC) models [Keupp et al. (Adv. Theory Simul., 2019, 2, 1900117)]. In this case, the application of pressure is not straightforward, and a distance constraint was used to mimic a mechanical strain enforcing the reaction coordinate. In contrast to this prior work, a mediating particle bath is used here to exert an isotropic hydrostatic pressure on the MOF nanocrystallites. The approach is inspired by the mercury nanoporosimetry used to compress flexible MOF powders. For such a mediating medium, parameters are presented that require a reasonable additional numerical effort and avoid unwanted diffusion of bath particles into the MOF pores. As a proof-of-concept, NCs of pillared-layer MOFs with different linkers and sizes are studied concerning their response to external pressure exerted by the bath. By this approach, an isotropic pressure on the NC can be applied in analogy to corresponding periodic simulations, without any bias for a specific mechanism. This allows a more realistic investigation of the breathing phase transformation of a MOF NC and further bridges the gap between experiment and simulation.

Exploring fields of ambiguity in the sustainability transition of universities

PurposeThe purpose of this paper is to develop a framework that systematically captures the ambiguity of different understandings about science, the university and its relation to society, while conceptualising sustainability. Following Corley and Gioia (2004, p. 174) on identity ambiguity and change, it seems pivotal to better understanding the ambiguity of sustainability in relation to academic cultures and university models to manage the transition more effectively.Design/methodology/approachThe nature of this paper’s objectives as well as the wide thematic scope leads to the need of exploring a broad knowledge base. This was best addressed by an exploratory literature review with data collection from primary and secondary sources. The data was interpreted through a hermeneutic analysis and resulted in the inductive development of first categories and goals (further referred to as category development). In addition, a multi-method approach further adjusted the categories and raised their empirical validity and social robustness.FindingsImplementing sustainability involves dealing with a double bound ambiguity due to organisational and individual identity reasons. Five fields of ambiguity were developed to systemise the conceptualisation of a sustainable university along contradictory understandings of science, the university and sustainability. These fields offer a framework to qualitatively assess the degree of sustainability in higher education institutions. Arguments for and against sustainability in universities have been categorised around five criteria and associated to the fields of ambiguity. The finding indicates that meaning in organisational change management for sustainability can be considered both, a potential driver and barrier for a sustainability transition in universities.Research limitations/implicationsThis paper exclusively focussed on the internal perspective and left aside any external factors that influence the sustainability transition, such as political measures to stimulate sustainability in higher education. In addition, the operational dimension of a sustainable university has been neglected, which is by all means a necessary and important aspect. The interrelation of the identified goals has not been discussed.Originality/valueThis paper focusses on the conceptualisation and understanding of sustainability within the institution, an often-forgotten but fundamental aspect of implementation. The fields of ambiguity are designed to be applied for assessing the “degree of maturity” of a sustainable university. The fields reveal the different understandings about the role, the mission and the governance of universities, stemming from competing preferences about goals and their assumed relations by various stakeholders of a higher education institutions. The five fields are not an attempt to resolve the hidden contradictions and tensions in a sustainability transition, but to state them clearly to anticipate resistances and conflicts that hinder the development of a shared understanding.

Material Science for catalysis: Quo vadis?

Material Science for catalysis: Quo vadis?

Roles of alkali metal dopants and surface defects on polymeric carbon nitride in photocatalytic peroxymonosulfate activation towards water decontamination

Polymeric carbon nitride (PCN) has been extensively employed in peroxymonosulfate (PMS) activation for water decontamination. However, limited photocatalytic efficiency can be achieved by pristine PCN due to its intrinsic deficiencies like high electron-hole recombination rate and resistance to charge transfer. Herein, in a two-stage thermal treatment process, the nontoxic and stable Na and K were successfully anchored among the PCN skeleton with surface defects created, leading to an elevated photocatalytic activity for PMS activation. The SO4·- and 1O2 were identified as the dominant reactive oxygen species, which were generated from electron transfer processes between PMS and catalyst. Experimental and theoretical analyses suggested that the defective structures and metal dopants improved the optical properties of catalyst, endowing it a wider light absorption range and a lower energy barrier for electron transitions. The modified structures were also beneficial to electron transfer processes due to the weaker electron confinement effect, accelerating the production of SO4·- on the defective sites and 1O2 on the metal sites. The synergy of radical and non-radical species weakened the influence of side reactions between radicals from PMS and coexisting inorganic anions in practical water, hence to promote the resistance of modified catalysts in complex water matrices.

Parent Perspectives on Supports and Barriers for Autistic Youth Transitioning to Adulthood.

Knowledge is needed about specific supports and barriers for successful transitions to adulthood for autistic youth, especially from the perspective of parents, who are highly involved in transition preparation. We conducted a qualitative thematic analysis of previously conducted semi-structured interviews with 39 parents of 41 autistic adolescents to identify themes related to supports and barriers; we then used Bronfenbrenner's Ecological System's Theory to aid in interpreting the themes. We identified three main supports and four main barriers to the transition to adulthood from the parent interviews. The supports and barriers represent factors to consider at each theorized ecological level. Results point to opportunities to promote person-environment fit and support the transition to adulthood for autistic youth at multiple system levels.

What happens after high school? A review of independent living practices to support youth with disabilities transitioning to adult life

BACKGROUND: Centers for Independent Living (CILs) can help out-of-school youth with disabilities. CIL services may be particularly important for minority youth with disabilities that face additional transition barriers. OBJECTIVE: This literature review documents existing practices that might aid CILs as they seek to help youth, including minority youth, with disabilities transition to adult life. METHODS: First, we conducted a literature search to identify practices that might help CILs assist youth with disabilities transition to independent living (IL) in early adult life. Then we examined various literature syntheses of postsecondary transition interventions with evidence of promise or efficacy for any IL-related outcome—regardless of whether the intervention targeted youth with disabilities. RESULTS: We discovered a variety of practices CILs might learn from or consider adopting to help youth with disabilities transition to adult life. However, the practices rarely focused on minority youth and usually had limited or no evidence about whether they improved IL outcomes. CONCLUSIONS: The limitations of the evidence we found suggest the need to develop and test interventions that help transition age youth with disabilities—especially minority youth with disabilities—achieve their IL goals.

Chances and barriers for Germany's low carbon transition - Quantifying uncertainties in key influential factors

With the energy sector being one of the largest sources of global greenhouse-gas emissions, a swift change in the ways of energy generation and consumption is needed for a fulfilment of climate goals. But while the existence of global warming and the resulting need for action are widely agreed upon, there is a lot of discussion around the concrete measures and their timeline. A major cause of this discussion is that of uncertainty, both with regard to possible outcomes, as well as to a multitude of factors such as future technology innovation (concerning both availability and costs), and final energy demands, but also socio-economic factors such as employment or sufficiency. This paper aims to give valuable insights into this uncertainty by applying the method of exploratory sensitivity analysis to an application of the Global Energy System Model (GENeSYS-MOD) for the German energy system. By computing over 1500 sensitivities across 11 core parameters, the key influential factors for the German Energiewende can be quantified, and possible chances, such as so-called no-regret options, as well as potentials barriers (if assumptions are not met) can be distilled. Results show that final energy demand developments, renewable potentials and costs, as well as carbon pricing are among the main drivers of the analyzed energy pathways. It would thus be highly beneficial for policy makers to focus on these key issues to ensure a timely transformation of the energy system and reach set climate targets.

Reduction of hysteresis in (La1-xCex) y(MnzFe11.4-z)Si1.6 magnetocaloric compounds for cryogenic magnetic refrigeration

(La,Ce)(Mn,Fe,Si)13-based compounds which show a giant magnetocaloric effect are potential materials for the cryogenic magnetic refrigeration. However, large hysteresis originating from the first order magneto-elastic phase transition deteriorates cyclic performance of these materials, hindering their practical applications. In this work, Curie temperature of (La1-xCex)y(MnzFe11.4-z)Si1.6 compounds was tuned to the cryogenic temperatures below 77 K and hysteresis was successfully reduced to 1.5 K by tuning first order magneto-elastic transition to the critical point of second order magnetic phase transition. Based on detail microstructure characterizations, the reason for the reduction of hysteresis is ascribed to the change of a secondary phase from a paramagnetic LaFeSi phase to ferromagnetic Ce2Fe17 and α-Fe phases. Cryogenic Lorentz microscopy observations and micromagnetic simulations showed the α-Fe ferromagnetic phase produces a large stray field of ∼0.7 T at their interface. This causes the magnetic field assisted paramagnetic/ferromagnetic phase transition in the NaZn13-type phase. Cryogenic X-ray diffraction analysis indicated the energy barrier of magneto-elastic transition was reduced, resulting in an enhancement of their mechanical stability during the cyclic performance. This work has shown that the hysteresis in the magnetocaloric materials with first order magneto-elastic transition can be tuned by engineering the size, distribution, and magnetism of the secondary phases.

A qualitative exploration of postpartum care uptake among vulnerable women

Introduction Postpartum care can help provide a good start in life for newborns and their families. In the Netherlands, every woman qualifies for eight consecutive days of postpartum care at home. Maternity care assistants (MCAs), supervised by midwives, provide supportive care focused on coping with the new situation and increasing parents’ confidence. As vulnerable women generally use less postpartum care, we aimed to gain insight into their postpartum care uptake process including perceived barriers and facilitators.MethodsWe conducted a qualitative semi-structured interview study among vulnerable women. Vulnerable women, as determined by their healthcare professional, were asked to participate from third trimester until 12 weeks postpartum. Purposive sampling was applied to include 23 participants (sixteen postpartum and seven pregnant women). All interviews were audio-taped and transcribed verbatim. The data was analyzed using a Grounded Theory approach.ResultsPostpartum care uptake among vulnerable women was experienced as a process of chronological phases during the perinatal period, which included four stages: expectations, decisions, experiences, and evaluations regarding (the uptake of) postpartum care. Within these stages three main themes were identified that may act as facilitators or barriers in transition between stages: information provision, a woman’s self-efficacy, and her social network.Information provision on content of care was perceived as essential but was often insufficient, thus acting as a barrier to postpartum care uptake. All women stated that postpartum care enhanced their self-efficacy. Low self-efficacy prior to postpartum care led to high expectations and evaluations, while negatively influencing their ability to make decisions regarding care uptake.Vulnerable women differed with respect to their social network. Absence of a social network facilitated positive expectations, experiences and evaluations of postpartum care but negatively influenced informed decisions. An extensive social network facilitated negative and positive expectations prior to postpartum care, while it also acted as a barrier to care uptake. Discussion and conclusionsThe generated conceptual framework shows the uptake of postpartum care among vulnerable women is a complex process influenced by potential barriers and facilitators in different stadia of the care process. To improve the benefits of postpartum care, it is essential to consider the particular stage and relevant themes applying to individual women and adapt care accordingly. As the experienced insufficient information provision may be grounded in health illiteracy, providing adequate and comprehensible information combined with enhancing self-efficacy is advocated.Lessons learned• Healthcare professionals including MCAs should provide adequate and comprehensible information on postpartum care to reduce the influence of vulnerable women’s unfamiliarity regarding content of care. • Optimization of information provision, enhancing self-efficacy, and insight in vulnerable women’s social networks may be beneficial in order to tailor care to the specific situation and needs of individual women.Limitations Our qualitative study identified barriers and facilitators to postpartum care uptake perceived by vulnerable women. As these depend on their perception, they may not accurately reflect the whole spectrum of barriers and facilitators.Suggestions for future research The proposed framework should be tested in an intervention study among a broader population of vulnerable women.