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The present study examined what older people regret, and the relationships between regret, health and life satisfaction. The study also explored the role of secondary interpretive control beliefs in relation to regret. Participants (N = 228; 79-98 years old) were asked to report on the content and frequency of their regret, secondary interpretive control beliefs (e.g., beliefs in finding the 'silver lining' in a dark cloud), health, and life satisfaction. A content analysis revealed that participants most commonly reported feeling regret due to things they had not done, the death of a loved one, and their own or others' health problems. Regression analyses indicated that experiencing regret more frequently was associated with poorer health and life satisfaction. Moreover, evidence for an emotion-modifying role of secondary interpretive control beliefs was shown through its negative association with regret. Results suggest that older adults may be experiencing age-related regrets that differ in content from those experienced at younger ages and that certain control beliefs may serve to lessen regret. [ABSTRACT FROM AUTHOR]

Control beliefs are adaptive for athletes coping with significant obstacles to sport. Our study tested whether the effects of setback-related primary (PC) and secondary control (SC) on adaptive sport-related outcomes were mediated via setback rumination in collegiate athletes. We recruited 200 collegiate athletes using Prolific, from both Canada and the United States of America (Mage = 22.3 years; 125 women, 69 men, five nonbinary individuals, and one nonresponse). We used structural equation modelling to test direct paths from Time 1 PC and SC and rumination to Time 2 competition anxiety and sport commitment and test indirect paths of PC and SC to the outcomes through rumination. Findings revealed PC directly increased sport commitment, and through higher rumination, PC predicted higher competition anxiety. Athletes' SC predicted lower competition anxiety via lower rumination. We discuss the implications of these findings for athletes managing significant sport setbacks and for sport personnel supporting athletes.

Six rhenium hydride complexes, [(6,6'-R 2 -bpy)Re(CO) 3 H] (bpy = 2,2'-bipyridine, R = OEt, OMe, NHMe, Me, F, Br), were synthesized. These complexes insert CO 2 to form rhenium formate complexes of the type [(6,6'-R 2 -bpy)Re(CO) 3 {OC(O)H}]. All the rhenium formate species were characterized using X-ray crystallography, which revealed that the bpy ligand is not coplanar with the metal coordination plane containing the two nitrogen donors of the bpy ligand but tilted. A solid-state structure of [(6,6'-Me 2 -bpy)Re(CO) 3 H] determined using MicroED also featured a tilted bpy ligand. The kinetics of CO 2 insertion into complexes of the type [(6,6'-R 2 -bpy)Re(CO) 3 H] were measured experimentally and the thermodynamic hydricities of [(6,6'-R 2 -bpy)Re(CO) 3 H] species were determined using theoretical calculations. A Brønsted plot constructed using the experimentally determined rate constants for CO 2 insertion and the calculated thermodynamic hydricities for [(6,6'-R 2 -bpy)Re(CO) 3 H] revealed a linear free energy relationship (LFER) between thermodynamic and kinetic hydricity. This LFER is different to the previously determined relationship for CO 2 insertion into complexes of the type [(4,4'-R 2 -bpy)Re(CO) 3 H]. At a given thermodynamic hydricity, CO 2 insertion is faster for complexes containing a 6,6'-substituted bpy ligand. This is likely in part due to the tilting observed for systems with 6,6'-substituted bpy ligands. Notably, the 6,6'-(NHMe) 2 -bpy ligand could in principle stabilize the transition state for CO 2 insertion via hydrogen bonding. This work shows that if only the rate of CO 2 insertion into [(6,6'-(NHMe) 2 -bpy)Re(CO) 3 H] is compared to [(4,4'-R 2 -bpy)Re(CO) 3 H] systems, the increase in rate could be easily attributed to hydrogen bonding, but in fact all 6,6'-substituted systems lead to faster than expected rates.

Two compounds were discovered in the well-studied BaO-Y 2 O 3 -SiO 2 phase field. Two different experimental routines were used for the exploration of this system due to the differences of synthetic conditions and competition with a glass field. The first phase Ba 5 Y 13 [SiO 4 ] 8 O 8.5 was isolated through a combination of energy dispersive X-ray spectroscopy analysis and diffraction techniques which guided the exploration. The second phase Ba 3 Y 2 [Si 2 O 7 ] 2 was located using iterative algorithmic identification of target compositions. The structure solution of the new compounds was aided by continuous rotation electron diffraction, and the structures were refined against combined synchrotron and neutron time-of-flight powder diffraction. Ba 5 Y 13 [SiO 4 ] 8 O 8.5 crystallizes in I 4̄2 m , a = 18.92732(1), c = 5.357307(6) Å and represents its own structure type which combines elements of structures of known silicates embedded in columns of interconnected yttrium-centred polyhedra characteristic of high-pressure phases. Ba 3 Y 2 [Si 2 O 7 ] 2 has P 2 1 symmetry with a pseudo-tetragonal cell ( a = 16.47640(4), b = 9.04150(5), c = 9.04114(7) Å, β = 90.0122(9)°) and is a direct superstructure of the Ca 3 BaBi[P 2 O 7 ] 2 structure. Despite the lower symmetry, the structure of Ba 3 Y 2 [Si 2 O 7 ] 2 retains disorder in both Ba/Y sites and disilicate network, thus presenting a superposition of possible locally-ordered fragments. Ba 5 Y 13 [SiO 4 ] 8 O 8.5 has low thermal conductivity of 1.04(5) W m -1 K -1 at room temperature. The two discovered phases provide a rich structural platform for further functional material design. The interplay of automated unknown phase composition identification with multiple diffraction methods offers acceleration of the time-consuming exploration of high-dimensional chemical spaces for new structures., Competing Interests: The authors declare no competing interests., (This journal is © The Royal Society of Chemistry.)

Ge 4+ substitution into the recently discovered superionic conductor Li 7 Si 2 S 7 I is demonstrated by synthesis of Li 7 Si 2-x Ge x S 7 I, where x≤1.2. The anion packing and tetrahedral silicon location of Li 7 Si 2 S 7 I are retained upon substitution. Single crystal X-ray diffraction shows that substitution of larger Ge 4+ for Si 4+ expands the unit cell volume and further increases Li + site disorder, such that Li 7 Si 0.88 Ge 1.12 S 7 I has one Li + site more (sixteen in total) than Li 7 Si 2 S 7 I. The ionic conductivity of Li 7 Si 0.8 Ge 1.2 S 7 I (x=1.2) at 303 K is 1.02(3)×10 -2  S cm -1 with low activation energies for Li + transport demonstrated over a wide temperature range by AC impedance and 7 Li NMR spectroscopy. All sixteen Li + sites remain occupied to temperatures as low as 30 K in Li 7 Si 0.88 Ge 1.12 S 7 I as a result of the structural expansion. This differs from Li 7 Si 2 S 7 I, where the partial Li + site ordering observed below room temperature reduces the ionic conductivity. The suppression of Li + site depopulation by Ge 4+ substitution retains the high mobility to temperatures as low as 200 K, yielding low temperature performance comparable with state-of-the-art Li + ion conducting materials., (© 2024 The Authors. Angewandte Chemie International Edition published by Wiley-VCH GmbH.)

Setbacks are common occurrences in sport. Recently, setbacks such as injuries and deselection have been accompanied, and confounded, by setbacks related to COVID-19. How students manage a setback may depend on the interaction of two control beliefs: primary control (PC) to directly influence the setback and secondary control (SC) to adjust to it. Purpose: This study investigates the relationships between athletes' PC and SC and two important sport setback-related outcomes-anxiety and rumination. Method: We employed a cross-sectional design examining collegiate athletes in the USA and Canada ( N  = 200; M age  = 20.9 years, 143 women, 52 men, 3 non-binary, 2 did not disclose). Using regression tests controlling for setback severity, we examined the interaction effects of athletes' PC and SC beliefs relative to setbacks, on the anxiety and rumination variables. Results: We found SC beliefs were beneficial to setback-related anxiety and rumination. A significant interaction indicated that particularly when PC was low, SC had negative associations with setback-related anxieties about letting others down (β = -.45, p  < .001) and experiencing pain (β = -.37, p  < .001). Conclusion: The findings suggest SC beliefs are important for managing setbacks-specifically for attenuating harmful rumination, and specific setback anxieties. We discuss the possibility of enhancing SC beliefs for combatting sport setbacks through control-enhancing interventions as a direction for future research.

The development of fast Li ion-conducting materials for use as solid electrolytes that provide sufficient electrochemical stability against electrode materials is paramount for the future of all-solid-state batteries. Advances on these fast ionic materials are dependent on building structure-ionic mobility-function relationships. Here, we exploit a series of multinuclear and multidimensional nuclear magnetic resonance (NMR) approaches, including 6 Li and 31 P magic angle spinning (MAS), in conjunction with density functional theory (DFT) to provide a detailed understanding of the local structure of the ultraphosphate Li 3 P 5 O 14 , a promising candidate for an oxide-based Li ion conductor that has been shown to be a highly conductive, energetically favorable, and electrochemically stable potential solid electrolyte. We have reported a comprehensive assignment of the ultraphosphate layer and layered Li 6 O 16 26- chains through 31 P and 6 Li MAS NMR, respectively, in conjunction with DFT. The chemical shift anisotropy of the eight resonances with the lowest 31 P chemical shift is significantly lower than that of the 12 remaining resonances, suggesting the phosphate bonding nature of these P sites being one that bridges to three other phosphate groups. We employed a number of complementary 6,7 Li NMR techniques, including MAS variable-temperature line narrowing spectra, spin-alignment echo (SAE) NMR, and relaxometry, to quantify the lithium ion dynamics in Li 3 P 5 O 14 . Detailed analysis of the diffusion-induced spin-lattice relaxation data allowed for experimental verification of the three-dimensional Li diffusion previously proposed computationally. The 6 Li NMR relaxation rates suggest sites Li1 and Li5 (the only five-coordinate Li site) are the most mobile and are adjacent to one another, both in the a-b plane (intralayer) and on the c -axis (interlayer). As shown in the 6 Li- 6 Li exchange spectroscopy NMR spectra, sites Li1 and Li5 likely exchange with one another both between adjacent layered Li 6 O 16 26- chains and through the center of the P 12 O 36 12- rings forming the three-dimensional pathway. The understanding of the Li ion mobility pathways in high-performing solid electrolytes outlines a route for further development of such materials to improve their performance., Competing Interests: The authors declare no competing financial interest., (© 2024 The Authors. Published by American Chemical Society.)

A 2×2×1 superstructure of the P6 3 /mmc NiAs structure is reported in which kagome nets are stabilized in the octahedral transition metal layers of the compounds Ni 0.7 Pd 0.2 Bi, Ni 0.6 Pt 0.4 Bi, and Mn 0.99 Pd 0.01 Bi. The ordered vacancies that yield the true hexagonal kagome motif lead to filling of trigonal bipyramidal interstitial sites with the transition metal in this family of "kagome-NiAs" type materials. Further ordering of vacancies within these interstitial layers can be compositionally driven to simultaneously yield kagome-connected layers and a net polarization along the c axes in Ni 0.9 Bi and Ni 0.79 Pd 0.08 Bi, which adopt Fmm2 symmetry. The polar and non-polar materials exhibit different electronic transport behaviour, reflecting the tuneability of both structure and properties within the NiAs-type bismuthide materials family., (© 2024 The Authors. Angewandte Chemie International Edition published by Wiley-VCH GmbH.)

Magnesium batteries attract interest as alternative energy-storage devices because of elemental abundance and potential for high energy density. Development is limited by the absence of suitable cathodes, associated with poor diffusion kinetics resulting from strong interactions between Mg 2+ and the host structure. V 2 PS 10 is reported as a positive electrode material for rechargeable magnesium batteries. Cyclable capacity of 100 mAh g -1 is achieved with fast Mg 2+ diffusion of 7.2 × ${\times }$ 10 -11 -4 × ${\times }$ 10 -14  cm 2  s -1 . The fast insertion mechanism results from combined cationic redox on the V site and anionic redox on the (S 2 ) 2- site; enabled by reversible cleavage of S-S bonds, identified by X-ray photoelectron and X-ray absorption spectroscopy. Detailed structural characterisation with maximum entropy method analysis, supported by density functional theory and projected density of states analysis, reveals that the sulphur species involved in anion redox are not connected to the transition metal centres, spatially separating the two redox processes. This facilitates fast and reversible Mg insertion in which the nature of the redox process depends on the cation insertion site, creating a synergy between the occupancy of specific Mg sites and the location of the electrons transferred., (© 2024 The Authors. Angewandte Chemie International Edition published by Wiley-VCH GmbH.)

Mixed anion halide-chalcogenide materials have recently attracted attention for a variety of applications, owing to their desirable optoelectronic properties. We report the synthesis of a previously unreported mixed-metal chalcohalide material, CuBiSeCl 2 ( Pnma ), accessed through a simple, low-temperature solid-state route. The physical structure is characterized through single-crystal X-ray diffraction and reveals significant Cu displacement within the CuSe 2 Cl 4 octahedra. The electronic structure of CuBiSeCl 2 is investigated computationally, which indicates highly anisotropic charge carrier effective masses, and by experimental verification using X-ray photoelectron spectroscopy, which reveals a valence band dominated by Cu orbitals. The band gap is measured to be 1.33(2) eV, a suitable value for solar absorption applications. The electronic and thermal properties, including resistivity, Seebeck coefficient, thermal conductivity, and heat capacity, are also measured, and it is found that CuBiSeCl 2 exhibits a low room temperature thermal conductivity of 0.27(4) W K -1 m -1 , realized through modifications to the phonon landscape through increased bonding anisotropy., Competing Interests: The authors declare no competing financial interest., (© 2024 The Authors. Published by American Chemical Society.)

Fast cation transport in solids underpins energy storage. Materials design has focused on structures that can define transport pathways with minimal cation coordination change, restricting attention to a small part of chemical space. Motivated by the greater structural diversity of binary intermetallics than that of the metallic elements, we used two anions to build a pathway for three-dimensional superionic lithium ion conductivity that exploits multiple cation coordination environments. Li 7 Si 2 S 7 I is a pure lithium ion conductor created by an ordering of sulphide and iodide that combines elements of hexagonal and cubic close-packing analogously to the structure of NiZr. The resulting diverse network of lithium positions with distinct geometries and anion coordination chemistries affords low barriers to transport, opening a large structural space for high cation conductivity.

High-throughput synthetic methods are well-established for chemistries involving liquid- or vapour-phase reagents and have been harnessed to prepare arrays of inorganic materials. The versatile but labour-intensive sub-solidus reaction pathway that is the backbone of the functional and electroceramics materials industries has proved more challenging to automate because of the use of solid-state reagents. We present a high-throughput sub-solidus synthesis workflow that permits rapid screening of oxide chemical space that will accelerate materials discovery by enabling simultaneous expansion of explored compositions and synthetic conditions. This increases throughput by using manual steps where actions are undertaken on multiple, rather than individual, samples which are then further combined with researcher-hands-free automated processes. We exemplify this by extending the BaY x Sn 1- x O 3- x /2 solid solution beyond the reported limit to a previously unreported composition and by exploring the Nb-Al-P-O composition space showing the applicability of the workflow to polyanion-based compositions beyond oxides., Competing Interests: There are no conflicts to declare., (This journal is © The Royal Society of Chemistry.)

Most of what researchers know about the challenges students with learning disabilities (LDs) experience during postsecondary education is based on experiences during face-to-face learning on campus. Less is known about challenges students with LD face during learning online-the mode of instruction students had to navigate during the COVID-19 pandemic. Therefore, the purpose of our research was to examine the lived experience of undergraduate students with LD during their first full semester of online instruction as a result of the pandemic. We interviewed six students in Western Canada and used a phenomenological approach to analyze their experiences. Overall, we extracted six main themes from their interviews. Two of these themes, (a) the broad impact of having LD and (b) accommodations during COVID-19, were specific to being a student with LD. The remaining four themes were more generally related to their overall student experience: (c) online learning is different, (d) the role of others, (e) emotional impact, and (f) resilience and perseverance. We discuss these results in terms of recommendations for future research and teaching in online learning environments., Competing Interests: The author(s) declared no potential conflicts of interest with respect to the research, authorship, and/or publication of this article., (© Hammill Institute on Disabilities 2022.)

Although many studies have examined reasons for sexting among young people, few have taken into account the underlying motivations associated with different reasons and how that may be associated with divergent positive or negative outcomes. This study addressed this gap by employing Self-determination Theory to assess how autonomous and controlled motivations for sexting were related to subjective well-being and relationship quality among emerging adults. Online survey data from 267 emerging adults (72 men, 195 women) ages 18-25 who had sent sexually explicit images or videos of themselves through electronic means to a committed partner were analyzed using Structural Equation Modeling. Autonomous and controlled motivations for sexting were significantly related to pleasant affect, with autonomous motivation predicting more pleasant affect and controlled motivation predicting less pleasant affect. Autonomous motivations for sexting were related to enhanced relationship quality, whereas controlled motivations for sexting were related to decreased relationship quality. Neither form of motivation had a statistically significant relationship with unpleasant affect or life satisfaction. These results demonstrate that the quality of motivations for sexting among emerging adults in committed relationships may contribute to different outcomes, particularly in terms of relationship quality. Implications for counselors, educators, and practitioners working with emerging adults who sext are discussed., (© 2022. The Author(s), under exclusive licence to Springer Science+Business Media, LLC, part of Springer Nature.)

Li-containing materials providing fast ion transport pathways are fundamental in Li solid electrolytes and the future of all-solid-state batteries. Understanding these pathways, which usually benefit from structural disorder and cation/anion substitution, is paramount for further developments in next-generation Li solid electrolytes. Here, we exploit a range of variable temperature 6 Li and 7 Li nuclear magnetic resonance approaches to determine Li-ion mobility pathways, quantify Li-ion jump rates, and subsequently identify the limiting factors for Li-ion diffusion in Li 3 AlS 3 and chlorine-doped analogue Li 4.3 AlS 3.3 Cl 0.7 . Static 7 Li NMR line narrowing spectra of Li 3 AlS 3 show the existence of both mobile and immobile Li ions, with the latter limiting long-range translational ion diffusion, while in Li 4.3 AlS 3.3 Cl 0.7 , a single type of fast-moving ion is present and responsible for the higher conductivity of this phase. 6 Li- 6 Li exchange spectroscopy spectra of Li 3 AlS 3 reveal that the slower moving ions hop between non-equivalent Li positions in different structural layers. The absence of the immobile ions in Li 4.3 AlS 3.3 Cl 0.7 , as revealed from 7 Li line narrowing experiments, suggests an increased rate of ion exchange between the layers in this phase compared with Li 3 AlS 3 . Detailed analysis of spin-lattice relaxation data allows extraction of Li-ion jump rates that are significantly increased for the doped material and identify Li mobility pathways in both materials to be three-dimensional. The identification of factors limiting long-range translational Li diffusion and understanding the effects of structural modification (such as anion substitution) on Li-ion mobility provide a framework for the further development of more highly conductive Li solid electrolytes., Competing Interests: The authors declare no competing financial interest., (© 2022 The Authors. Published by American Chemical Society.)

Argyrodite is a key structure type for ion-transporting materials. Oxide argyrodites are largely unexplored despite sulfide argyrodites being a leading family of solid-state lithium-ion conductors, in which the control of lithium distribution over a wide range of available sites strongly influences the conductivity. We present a new cubic Li-rich (>6 Li + per formula unit) oxide argyrodite Li 7 SiO 5 Cl that crystallizes with an ordered cubic ( P 2 1 3) structure at room temperature, undergoing a transition at 473 K to a Li + site disordered F 4̅3 m structure, consistent with the symmetry adopted by superionic sulfide argyrodites. Four different Li + sites are occupied in Li 7 SiO 5 Cl (T5, T5a, T3, and T4), the combination of which is previously unreported for Li-containing argyrodites. The disordered F 4̅3 m structure is stabilized to room temperature via substitution of Si 4+ with P 5+ in Li 6+ x P 1- x Si x O 5 Cl (0.3 < x < 0.85) solid solution. The resulting delocalization of Li + sites leads to a maximum ionic conductivity of 1.82(1) × 10 -6 S cm -1 at x = 0.75, which is 3 orders of magnitude higher than the conductivities reported previously for oxide argyrodites. The variation of ionic conductivity with composition in Li 6+ x P 1- x Si x O 5 Cl is directly connected to structural changes occurring within the Li + sublattice. These materials present superior atmospheric stability over analogous sulfide argyrodites and are stable against Li metal. The ability to control the ionic conductivity through structure and composition emphasizes the advances that can be made with further research in the open field of oxide argyrodites.

The mixed anion material Bi 4 O 4 SeCl 2 has an ultralow thermal conductivity of 0.1 W m -1 K -1 along its stacking axis ( c axis) at room temperature, which makes it an ideal candidate for electronic band structure optimization via doping to improve its thermoelectric performance. Here, we design and realize an optimal doping strategy for Bi 4 O 4 SeCl 2 from first principles and predict an enhancement in the density of states at the Fermi level of the material upon Sn and Ge doping. Experimental work realizes the as-predicted behavior in Bi 4- x Sn x O 4 SeCl 2 ( x = 0.01) through the precise control of composition. Careful consideration of multiple accessible dopant sites and charge states allows for the effective computational screening of dopants for thermoelectric properties in Bi 4 O 4 SeCl 2 and may be a suitable route for assessing other candidate materials., Competing Interests: The authors declare no competing financial interest., (© 2022 The Authors. Published by American Chemical Society.)

A tetragonal argyrodite with >7 mobile cations, Li 7 Zn 0.5 SiS 6 , is experimentally realized for the first time through solid state synthesis and exploration of the Li-Zn-Si-S phase diagram. The crystal structure of Li 7 Zn 0.5 SiS 6 was solved ab initio from high-resolution X-ray and neutron powder diffraction data and supported by solid-state NMR. Li 7 Zn 0.5 SiS 6 adopts a tetragonal I 4 structure at room temperature with ordered Li and Zn positions and undergoes a transition above 411.1 K to a higher symmetry disordered F 43 m structure more typical of Li-containing argyrodites. Simultaneous occupation of four types of Li site (T5, T5a, T2, T4) at high temperature and five types of Li site (T5, T2, T4, T1, and a new trigonal planar T2a position) at room temperature is observed. This combination of sites forms interconnected Li pathways driven by the incorporation of Zn 2+ into the Li sublattice and enables a range of possible jump processes. Zn 2+ occupies the 48 h T5 site in the high-temperature F 43 m structure, and a unique ordering pattern emerges in which only a subset of these T5 sites are occupied at room temperature in I 4 Li 7 Zn 0.5 SiS 6 . The ionic conductivity, examined via AC impedance spectroscopy and VT-NMR, is 1.0(2) × 10 -7 S cm -1 at room temperature and 4.3(4) × 10 -4 S cm -1 at 503 K. The transition between the ordered I 4 and disordered F 43 m structures is associated with a dramatic decrease in activation energy to 0.34(1) eV above 411 K. The incorporation of a small amount of Zn 2+ exercises dramatic control of Li order in Li 7 Zn 0.5 SiS 6 yielding a previously unseen distribution of Li sites, expanding our understanding of structure-property relationships in argyrodite materials., Competing Interests: The authors declare no competing financial interest., (© 2022 The Authors. Published by American Chemical Society.)

Objectives: During COVID-19 athletes have had games canceled, seasons postponed, and social supports lost. These changes negatively impact their motivation, and potentially identity, as athletes. We draw on self-determination theory to examine motivation in sport and its relationship with athlete identity during COVID-19., Design: A cross-sectional study design was employed consisting of online quantitative surveys., Method: We gathered background engagement and motivation data from 115 athletes involved in organized sport. They responded to questions on basic psychological needs satisfaction (competence, relatedness, autonomy) and athlete identity., Results: When reflecting on their basic psychological needs during the pandemic, most athletes considered them important. Athletes' competence and relatedness in sport were associated with social-related athlete identity, but not autonomy. Only relatedness in sport was associated with exclusivity-related social identity., Conclusions: Using a self-determination theoretical lens, our findings contribute to understanding athlete motivation and identities when sport is interrupted., Competing Interests: The authors declare that the research was conducted in the absence of any commercial or financial relationships that could be construed as a potential conflict of interest., (Copyright © 2022 Parker, Beeby and Daniels.)

Research suggests that when dealing with personal setbacks, secondary control (SC) adjustment and acceptance beliefs can foster psychological wellbeing. However, little research has examined these beliefs, in combination, and how they impact students in their academic development. We conducted secondary analysis using an eight-month longitudinal study design over a two-semester introductory course on a sample of university students ( n  = 237; 64% female; M age = 19 years old). Multiple regression analyses assessed whether the students' Semester 1 adjustment and acceptance SC beliefs influenced Semester 2 learning-related emotions, perceived stress, and perceived course success, and whether Adjustment x Acceptance interactions emerged involving these outcomes. Adjustment beliefs promoted learning-related positive emotions (hope, pride), perceived course success, and reduced perceived stress; acceptance predicted higher shame and perceived stress. Students' adjustment predicted lower helplessness for students with high acceptance beliefs. These findings are discussed in light of the role that SC beliefs might play in curbing psychological distress reported by students on postsecondary campuses., Competing Interests: Competing interestsThe authors have no relevant financial or non-financial interests to disclose., (© The Author(s), under exclusive licence to Springer Nature B.V. 2022.)

We report a metal-organic framework where an ordered array of two linkers with differing length and geometry connect [Zr 6 (OH) 4 O 4 ] 12+ clusters into a twelve-connected fcu net that is rhombohedrally distorted from cubic symmetry. The ordered binding of equal numbers of terephthalate and fumarate ditopic carboxylate linkers at the trigonal antiprismatic Zr 6 core creates close-packed layers of fumarate-connected clusters that are connected along the single remaining threefold axis by terephthalates. This well-defined linker arrangement retains the three-dimensional porosity of the Zr cluster-based UiO family while creating two distinct windows within the channels that define two distinct guest diffusion paths. The ordered material is accessed by a restricted combination of composition and process parameters that were identified by high-throughput synthesis., (© 2021 The Authors. Angewandte Chemie International Edition published by Wiley-VCH GmbH.)

Li-rich rocksalt oxides are promising candidates as high-energy density cathode materials for next-generation Li-ion batteries because they present extremely diverse structures and compositions. Most reported materials in this family contain as many cations as anions, a characteristic of the ideal cubic closed-packed rocksalt composition. In this work, a new rocksalt-derived structure type is stabilized by selecting divalent Cu and pentavalent Sb cations to favor the formation of oxygen vacancies during synthesis. The structure and composition of the oxygen-deficient Li 4 CuSbO 5.5 □ 0.5 phase is characterized by combining X-ray and neutron diffraction, ICP-OES, XAS, and magnetometry measurements. The ordering of cations and oxygen vacancies is discussed in comparison with the related Li 2 CuO 2 □ 1 and Li 5 SbO 5 □ 1 phases. The electrochemical properties of this material are presented, with only 0.55 Li + extracted upon oxidation, corresponding to a limited utilization of cationic and/or anionic redox, whereas more than 2 Li + ions can be reversibly inserted upon reduction to 1 V vs Li + /Li, a large capacity attributed to a conversion reaction and the reduction of Cu 2+ to Cu 0 . Control of the formation of oxygen vacancies in Li-rich rocksalt oxides by selecting appropriate cations and synthesis conditions affords a new route for tuning the electrochemical properties of cathode materials for Li-ion batteries. Furthermore, the development of material models of the required level of detail to predict phase diagrams and electrochemical properties, including oxygen release in Li-rich rocksalt oxides, still relies on the accurate prediction of crystal structures. Experimental identification of new accessible structure types stabilized by oxygen vacancies represents a valuable step forward in the development of predictive models.

Ultrasound (US)-guided central venous catheter (CVC) insertion is a procedure that carries the risk of significant complications. Simulation provides a safe learning atmosphere, but most CVC simulators are not available outside of simulation centers. To explore longitudinal trends in US-guided CVC insertion competency in internal medicine (IM) interns, we studied the use of a low-fidelity, gelatin-based, US-guided CVC insertion simulation model combined with a simulation curriculum. This prospective observational study of IM interns was performed over the course of one academic year. Interns (n = 56) underwent model-based, US-guided procedure simulation training program and a repeated training course prior to their intensive care unit (ICU) rotation. CVC insertion competency at different timepoints was recorded. Survey data about intern experience and attitudes were also collected. Out of the 56 interns initially trained, 40 were included in the final analysis. Across all outcomes, interns experienced skill atrophy between initial training and the beginning of their ICU month. However, by the end of the month, there was a significant improvement in competency as compared to initial procedural training, which then waned by the end of the intern year. Attitudes toward the model were generally positive and self-reported confidence improved throughout the course of the year and correlated with objective measures of competency. Over the course of their intern year, which included simulation training using a gelatin-based model, interns demonstrated consistent competency trends. The use of a gelatin-based CVC insertion simulation model warrants further study as an adjunctive aid to existing simulation training.

Mixed anion materials and anion doping are very promising strategies to improve solid-state electrolyte properties by enabling an optimized balance between good electrochemical stability and high ionic conductivity. In this work, we present the discovery of a novel lithium aluminum sulfide-chloride phase, obtained by substitution of chloride for sulfur in Li 3 AlS 3 and Li 5 AlS 4 materials. The structure is strongly affected by the presence of chloride anions on the sulfur site, as the substitution was shown to be directly responsible for the stabilization of a higher symmetry phase presenting a large degree of cationic site disorder, as well as disordered octahedral lithium vacancies. The effect of disorder on the lithium conductivity properties was assessed by a combined experimental-theoretical approach. In particular, the conductivity is increased by a factor 10 3 compared to the pure sulfide phase. Although it remains moderate (10 -6 S·cm -1 ), ab initio molecular dynamics and maximum entropy (applied to neutron diffraction data) methods show that disorder leads to a 3D diffusion pathway, where Li atoms move thanks to a concerted mechanism. An understanding of the structure-property relationships is developed to determine the limiting factor governing lithium ion conductivity. This analysis, added to the strong step forward obtained in the determination of the dimensionality of diffusion, paves the way for accessing even higher conductivity in materials comprising an hcp anion arrangement., Competing Interests: The authors declare no competing financial interest., (© 2021 The Authors. Published by American Chemical Society.)

Boredom is a salient emotion experienced in postsecondary settings, and evidence reveals that it can negatively impact academic achievement and motivation. Drawing from the control-value theory (CVT) of achievement emotions (Pekrun, 2006) and the component process model of emotions (CPM; Scherer, 1984), our study examines the first phase of a multi-sequenced online boredom intervention training (BIT) program. The goal of Phase I of BIT was to increase university students' ( N = 85) knowledge about boredom as a scholarly construct. Students completed four components of the Phase I BIT session, including: (a) a baseline survey and knowledge quiz, (b) a psychoeducational video, (c) a consolidation exercise, and (d) a follow-up knowledge quiz. We employed a repeated measures analysis to measure changes in knowledge after students watched the psychoeducational boredom video. Our findings reveal that students became more knowledgeable about boredom, learned something novel, and were interested in the intervention. The results are discussed in terms of the implications for research, theory, and practice.

Extended anionic frameworks based on condensation of polyhedral main group non-metal anions offer a wide range of structure types. Despite the widespread chemistry and earth abundance of phosphates and silicates, there are no reports of extended ultraphosphate anions with lithium. We describe the lithium ultraphosphates Li 3 P 5 O 14 and Li 4 P 6 O 17 based on extended layers and chains of phosphate, respectively. Li 3 P 5 O 14 presents a complex structure containing infinite ultraphosphate layers with 12-membered rings that are stacked alternately with lithium polyhedral layers. Two distinct vacant tetrahedral sites were identified at the end of two distinct finite Li 6 O 16 26- chains. Li 4 P 6 O 17 features a new type of loop-branched chain defined by six PO 4 3- tetrahedra. The ionic conductivities and electrochemical properties of Li 3 P 5 O 14 were examined by impedance spectroscopy combined with DC polarization, NMR spectroscopy, and galvanostatic plating/stripping measurements. The structure of Li 3 P 5 O 14 enables three-dimensional lithium migration that affords the highest ionic conductivity (8.5(5) × 10 -7 S cm -1 at room temperature for bulk), comparable to that of commercialized LiPON glass thin film electrolytes, and lowest activation energy (0.43(7) eV) among all reported ternary Li-P-O phases. Both new lithium ultraphosphates are predicted to have high thermodynamic stability against oxidation, especially Li 3 P 5 O 14 , which is predicted to be stable to 4.8 V, significantly higher than that of LiPON and other solid electrolytes. The condensed phosphate units defining these ultraphosphate structures offer a new route to optimize the interplay of conductivity and electrochemical stability required, for example, in cathode coatings for lithium ion batteries.

The selection of the elements to combine delimits the possible outcomes of synthetic chemistry because it determines the range of compositions and structures, and thus properties, that can arise. For example, in the solid state, the elemental components of a phase field will determine the likelihood of finding a new crystalline material. Researchers make these choices based on their understanding of chemical structure and bonding. Extensive data are available on those element combinations that produce synthetically isolable materials, but it is difficult to assimilate the scale of this information to guide selection from the diversity of potential new chemistries. Here, we show that unsupervised machine learning captures the complex patterns of similarity between element combinations that afford reported crystalline inorganic materials. This model guides prioritisation of quaternary phase fields containing two anions for synthetic exploration to identify lithium solid electrolytes in a collaborative workflow that leads to the discovery of Li 3.3 SnS 3.3 Cl 0.7. The interstitial site occupancy combination in this defect stuffed wurtzite enables a low-barrier ion transport pathway in hexagonal close-packing., (© 2021. The Author(s).)

We report a new polymorph of lithium aluminum pyrophosphate, LiAlP 2 O 7 , discovered through a computationally guided synthetic exploration of the Li-Mg-Al-P-O phase field. The new polymorph formed at 973 K, and the crystal structure, solved by single-crystal X-ray diffraction, adopts the orthorhombic space group Cmcm with a = 5.1140(9) Å, b = 8.2042(13) Å, c = 11.565(3) Å, and V = 485.22(17) Å 3 . It has a three-dimensional framework structure that is different from that found in other LiM III P 2 O 7 materials. It transforms to the known monoclinic form (space group P 2 1 ) above ∼1023 K. Density functional theory (DFT) calculations show that the new polymorph is the most stable low-temperature structure for this composition among the seven known structure types in the A I M III P 2 O 7 (A = alkali metal) families. Although the bulk Li-ion conductivity is low, as determined from alternating-current impedance spectroscopy and variable-temperature static 7 Li NMR spectra, a detailed analysis of the topologies of all seven structure types through bond-valence-sum mapping suggests a potential avenue for enhancing the conductivity. The new polymorph exhibits long (>4 Å) Li-Li distances, no Li vacancies, and an absence of Li pathways in the c direction, features that could contribute to the observed low Li-ion conductivity. In contrast, we found favorable Li-site topologies that could support long-range Li migration for two structure types with modest DFT total energies relative to the new polymorph. These promising structure types could possibly be accessed from innovative doping of the new polymorph.

Growth and fixed mindset messaging is gaining popularity. In our pilot study, we examine the mindsets of students with learning disabilities (LD) to determine how their self-beliefs relate to this messaging. Our results demonstrate that students with LD endorse growth mindsets more than fixed mindsets which is consistent with their peers without LD. Moreover, in their comments about being a student with LD, participants highlight important components of growth mindset messaging. However, some comments may reflect a false-growth mindset wherein students are only focused on effort and not the additional resources required for growth. We provide directions for future research., Competing Interests: Declaration of Conflicting Interests: The author(s) declared no potential conflicts of interest with respect to the research, authorship, and/or publication of this article., (© The Authors 2021.)

The thermal conductivity of crystalline materials cannot be arbitrarily low, as the intrinsic limit depends on the phonon dispersion. We used complementary strategies to suppress the contribution of the longitudinal and transverse phonons to heat transport in layered materials that contain different types of intrinsic chemical interfaces. BiOCl and Bi 2 O 2 Se encapsulate these design principles for longitudinal and transverse modes, respectively, and the bulk superlattice material Bi 4 O 4 SeCl 2 combines these effects by ordering both interface types within its unit cell to reach an extremely low thermal conductivity of 0.1 watts per kelvin per meter at room temperature along its stacking direction. This value comes within a factor of four of the thermal conductivity of air. We demonstrated that chemical control of the spatial arrangement of distinct interfaces can synergically modify vibrational modes to minimize thermal conductivity., (Copyright © 2021 The Authors, some rights reserved; exclusive licensee American Association for the Advancement of Science. No claim to original U.S. Government Works.)

We report the aperiodic titanate Ba 10 Y 6 Ti 4 O 27 with a room-temperature thermal conductivity that equals the lowest reported for an oxide. The structure is characterised by discontinuous occupancy modulation of each of the sites and can be considered as a quasicrystal. The resulting localisation of lattice vibrations suppresses phonon transport of heat. This new lead material for low-thermal-conductivity oxides is metastable and located within a quaternary phase field that has been previously explored. Its isolation thus requires a precisely defined synthetic protocol. The necessary narrowing of the search space for experimental investigation was achieved by evaluation of titanate crystal chemistry, prediction of unexplored structural motifs that would favour synthetically accessible new compositions, and assessment of their properties with machine-learning models., (© 2021 The Authors. Angewandte Chemie International Edition published by Wiley-VCH GmbH.)

Background: Previous research has shown that pre-service teachers have low responsibility for student motivation and feel underprepared to deal with motivational issues. As an extension, researchers have designed interventions to shift teachers' beliefs about motivation or equip them with approaches to instruction, but never both., Aims: Following best practices for motivation interventions, we created a one-session online intervention and tested its efficacy to shift pre-service teachers' self-reported beliefs and approaches to instruction to be more supportive of student motivation. The intervention included priming, materials designed for mindsets and/or for approaches to instruction, a consolidation activity, and take-home materials., Sample: A convenience sample of 384 pre-service teachers from one Canadian university participated., Methods: We embedded an experimental design into multiple sections of a required assessment course. After completing a pre-test, participants were randomly assigned to one of four conditions: beliefs-only, approaches-only, combined beliefs and approaches, or control. After completing the online module, students received a lecture on assessment practices and motivation., Results: The results from our MANCOVA showed that pre-service teachers who participated in the beliefs-only condition reported increased levels of responsibility for student motivation, more growth mindset beliefs, and less fixed mindset beliefs than participants in the other conditions. The approaches-only condition did not influence self-reported mastery or performance approaches to instruction and the combined condition had no effect on beliefs or approaches., Conclusions: We discuss the implications for educating pre-service teachers about student motivation and suggest that beliefs and approaches to instruction need to be addressed separately., (© 2020 The British Psychological Society.)

A hexagonal analogue, Li 6 SiO 4 Cl 2 , of the cubic lithium argyrodite family of solid electrolytes is isolated by a computation-experiment approach. We show that the argyrodite structure is equivalent to the cubic antiperovskite solid electrolyte structure through anion site and vacancy ordering within a cubic stacking of two close-packed layers. Construction of models that assemble these layers with the combination of hexagonal and cubic stacking motifs, both well known in the large family of perovskite structural variants, followed by energy minimization identifies Li 6 SiO 4 Cl 2 as a stable candidate composition. Synthesis and structure determination demonstrate that the material adopts the predicted lithium site-ordered structure with a low lithium conductivity of ∼10 -10 S cm -1 at room temperature and the predicted hexagonal argyrodite structure above an order-disorder transition at 469.3(1) K. This transition establishes dynamic Li site disorder analogous to that of cubic argyrodite solid electrolytes in hexagonal argyrodite Li 6 SiO 4 Cl 2 and increases Li-ion mobility observed via NMR and AC impedance spectroscopy. The compositional flexibility of both argyrodite and perovskite alongside this newly established structural connection, which enables the use of hexagonal and cubic stacking motifs, identifies a wealth of unexplored chemistry significant to the field of solid electrolytes., Competing Interests: The authors declare no competing financial interest., (© 2021 The Authors. Published by American Chemical Society.)

The piezoelectric devices widespread in society use noncentrosymmetric Pb-based oxides because of their outstanding functional properties. The highest figures of merit reported are for perovskites based on the parent Pb(Mg 1/3 Nb 2/3 )O 3 (PMN), which is a relaxor: a centrosymmetric material with local symmetry breaking that enables functional properties, which resemble those of a noncentrosymmetric material. We present the Pb-free relaxor (K 1/2 Bi 1/2 )(Mg 1/3 Nb 2/3 )O 3 (KBMN), where the thermal and (di)electric behavior emerges from the discrete structural roles of the s 0 K + and s 2 Bi 3+ cations occupying the same A site in the perovskite structure, as revealed by diffraction methods. This opens a distinctive route to Pb-free piezoelectrics based on relaxor parents, which we demonstrate in a solid solution of KBMN with the Pb-free ferroelectric (K 1/2 Bi 1/2 )TiO 3 , where the structure and function evolve together, revealing a morphotropic phase boundary, as seen in PMN-derived systems. The detailed multiple-length-scale understanding of the functional behavior of KBMN suggests that precise chemical manipulation of the more diverse local displacements in the Pb-free relaxor will enhance performance.

A large proportion of antibiotic use associated with hospitalization occurs immediately after discharge, representing an important focus for antimicrobial stewardship programs. This review identified few studies evaluating the effect of interventions aimed at improving discharge antibiotic prescribing. Antimicrobial stewardship to improve postdischarge antibiotic prescribing is an unmet need warranting further study.

During the northern hemisphere Winter 2020 academic term, university students had to adjust to remote learning in response to the COVID-19 pandemic. This abrupt change provided a unique opportunity to examine students' motivation, engagement and perceptions of success and cheating under two learning conditions, namely traditional and remote. We used a single survey to collect retrospective self-report data from a convenience sample of Canadian undergraduate students ( n  = 98) about their motivation, engagement and perceptions of success and cheating before COVID-19 and then in remote learning. Students' achievement goals, engagement and perceptions of success all significantly decreased, while their perceptions of cheating increased. Moreover, we used regression analyses to examine associations amongst achievement goals and engagement, perceptions of success and cheating concerns. Mastery-approach goals were positively associated with more engagement and higher perceptions of success. Achievement goals were unrelated to cheating. Students in large classes and who were originally concerned about cheating became more concerned about cheating in remote learning conditions. Our study provides information to researchers and instructors about how achievement goals relate to student outcomes across learning conditions. By extension, we provide timely recommendations for instructors as they continue to wrestle with how to deliver their courses during the COVID-19 pandemic., Competing Interests: Conflicts of interestNot applicable., (© The Author(s), under exclusive licence to Springer Nature B.V. part of Springer Nature 2021.)

Objectives: Pneumonia is a frequent cause of hospitalization among nursing home (NH) residents, but little information is available as to how clinical presentation and other characteristics relate to hospitalization, and the differential use of antimicrobials based on hospitalization status. This study examined how hospitalized and nonhospitalized NH residents with pneumonia differ., Design: Data from a 2-year prospective study of residents who participated in a randomized controlled trial., Setting and Participants: All residents from 14 NHs in North Carolina followed for pneumonia over a 2-year period., Methods: Clinical features, antimicrobial treatment, hospitalization, and demographic data on residents with a pneumonia diagnosis were abstracted from charts; NH information was obtained from NH administrators., Results: A total of 509 pneumonia episodes were reported for 395 unique residents; the incidence was not higher in the winter months, and 28% were hospitalized. The likelihood of hospitalization did not differ by clinical characteristics except that residents with a respiratory rate >25 breaths per minute were more likely to be hospitalized. Being on hospice [odds ratio (OR) 3.3, 95% confidence interval (CI) 1.5-7.4] and not having dementia (OR 1.9, 95% CI 1.1-3.2) also related to increased likelihood of hospitalization. Fluoroquinolone (usually levofloxacin) monotherapy was the most common treatment (54%) in both settings, and ceftriaxone monotherapy varied by hospitalization status (7% of hospitalized vs 16% treated on-site). Approximately 36% of nonhospitalized residents received antimicrobials for more than 7 days., Conclusions/implications: Respiratory rate is associated with hospitalization but was not documented for more than a quarter of residents, suggesting the clinical benefit of more consistently conducting this assessment. Differential hospitalization rates for persons with dementia and on hospice suggest that care is being tailored to individuals' wishes, but this assumption merits study, as does use of fluoroquinolones (due to side effects) and treatment duration (due to potential contribution to antibiotic resistance)., (Copyright © 2020 AMDA – The Society for Post-Acute and Long-Term Care Medicine. Published by Elsevier Inc. All rights reserved.)

Purpose: Successful use of alteplase and argatroban to treat a patient with coronavirus disease 2019 (COVID-19)-associated massive pulmonary embolism with cardiac arrest is reported., Summary: This case report describes a 42-year-old male with COVID-19 who developed a massive pulmonary embolism resulting in cardiac arrest after suspected failure of low-molecular-weight heparin therapy for a deep venous thrombosis. Administration of two 50-mg doses of intravenous alteplase resulted in return of spontaneous circulation, and low-dose argatroban was used as follow-up anticoagulation therapy without complications. This is the first case report of use of argatroban in a patient with COVID-19 with cardiac arrest-associated massive pulmonary embolism after failure of previous anticoagulation efforts., Conclusion: Argatroban may be used as an alternate anticoagulation strategy in COVID-19 patients who fail low-molecular weight therapy. A risk versus benefit discussion should be had regarding appropriateness of therapy as well as dosing. More data is needed to understand the unique hypercoagulable condition in COVID-19 patients as well as research that further highlights the role of argatroban and bivalirudin therapy in this patient population., (© American Society of Health-System Pharmacists 2020. All rights reserved. For permissions, please e-mail: journals.permissions@oup.com.)

Objective: Patients with epithelial ovarian cancers experience the highest fatality rates among all gynecological malignancies which require development of novel treatment strategies. Tumor cell necrosis was previously reported in a number of cancer cell lines following treatment with a p53-derived anti-cancer peptide called PNC-27. This peptide induces necrosis by transmembrane pore formation with HDM-2 protein that is expressed in the cancer cell membrane. We aimed to extend these studies further by investigating expression of membrane HDM-2 protein in ovarian cancer as it relates to susceptibility to PNC-27., Procedures: Herein, we measured HDM-2 membrane expression in two ovarian cancer cell lines (SKOV-3 and OVCAR-3) and a non-transformed control cell line (HUVEC) by flow cytometric and western blot analysis. Immunofluorescence was used to visualize colocalization of PNC-27 with membrane HDM-2. Treatment effects with PNC-27 and control peptide were assessed using a MTT cell proliferation assay while direct cytotoxicity was measured by lactate dehydrogenase (LDH) release and induction of apoptotic markers; annexin V and caspase-3., Results: HDM-2 protein was highly expressed and frequently detected in the membranes of SKOV-3 and OVCAR-3 cells; a prominent 47.6 kDa HDM-2 plasma membrane isoform was present in both cell lines whereas 25, 29, and 30 kDa isoforms were preferentially expressed in OVCAR-3. Notably, PNC-27 colocalized with HDM-2 in the membranes of both cancer cell lines that resulted in rapid cellular necrosis. In contrast, no PNC-27 colocalization and cytotoxicity was observed with non-transformed HUVEC demonstrating minimal expression of membrane HDM-2., Conclusions: Our results suggest that HDM-2 is highly expressed in the membranes of these ovarian cancer cell lines and colocalizes with PNC-27. We therefore conclude that the association of PNC-27 with preferentially expressed membrane HDM-2 isoforms results in the proposed model for the formation of transmembrane pores and epithelial ovarian cancer tumor cell necrosis, as previously described in a number of solid tissue and hematologic malignancies., (© 2020 by the Association of Clinical Scientists, Inc.)

Objective: Placental disease is a leading cause of stillbirth. Our purpose was to characterize stillbirths associated with placental disease., Study Design: The Stillbirth Collaborative Research Network conducted a prospective, case-control study of stillbirths and live births from 2006 to 2008. This analysis includes 512 stillbirths with cause of death assignment and a comparison group of live births. We compared exposures between women with stillbirth due to placental disease and those due to other causes as well as between women with term (≥ 37 weeks) stillbirth due to placental disease and term live births., Results: A total of 121 (23.6%) out of 512 stillbirths had a probable or possible cause of death due to placental disease by Initial Causes of Fetal Death. Characteristics were similar between stillbirths due to placental disease and other stillbirths. When comparing term live births to stillbirths due to placental disease, women with non-Hispanic black race, Hispanic ethnicity, lack of insurance, or who were born outside of the United States had higher odds of stillbirth due to placental disease. Nulliparity and antenatal bleeding also increased risk of stillbirth due to placental disease., Conclusion: Multiple discrete exposures were associated with stillbirth caused by placental disease. The relationship between these factors and utility of surveillance warrants further study., Competing Interests: None declared., (Thieme Medical Publishers 333 Seventh Avenue, New York, NY 10001, USA.)

A paucity of data currently exists regarding drug-drug interaction (DDI) with tacrolimus and isavuconazole coadministration. Current literature provides conflicting recommendations on whether an empiric tacrolimus dose reduction is necessary when coadministered with isavuconazole. A 47-year-old African American female with acute lymphoblastic leukemia underwent an allogenic stem cell transplant (alloSCT) and was subsequently placed on routine posttransplant therapy including tacrolimus for immunosuppression and posaconazole for antifungal prophylaxis. Tacrolimus was empirically dose reduced due to the expected DDI with posaconazole based on current recommendations. Due to a persistently prolonged QTc interval and need for mold coverage, antifungal prophylaxis was ultimately changed to isavuconazole at standard recommended dosing. Tacrolimus was empirically dose reduced by 40% based on limited available literature at the time; however, tacrolimus trough concentrations subsequently declined, requiring an increase in tacrolimus dose to maintain therapeutic trough concentrations. Adequate isavuconazole absorption was documented through pharmacokinetic and pharmacodynamic data by measuring an isavuconazole trough concentration and directly observing isavuconazole's shortening effect on the QTc interval, respectively. Our experience in an alloSCT patient suggests that an empiric tacrolimus dose reduction is not required when isavuconazole is initiated, but close tacrolimus therapeutic drug monitoring should rather be performed to guide tacrolimus dosing.

Mixed ionic-electronic conductors (MIECs) that display high oxide ion conductivity (σ o ) and electronic conductivity (σ e ) constitute an important family of electrocatalysts for a variety of applications including fuel cells and oxygen separation membranes. Often MIECs exhibit sufficient σ e but inadequate σ o . It has been a long-standing challenge to develop MIECs with both high σ o and stability under device operation conditions. For example, the well-known perovskite oxide Ba 0.5 Sr 0.5 Co 0.8 Fe 0.2 O 3- δ (BSCF) exhibits exceptional σ o and electrocatalytic activity. The reactivity of BSCF with CO 2 , however, limits its use in practical applications. Here, the perovskite oxide Bi 0.15 Sr 0.85 Co 0.8 Fe 0.2 O 3- δ (BiSCF) is shown to exhibit not only exceptional bulk transport properties, with a σ o among the highest for known MIECs, but also high CO 2 tolerance. When used as an oxygen separation membrane, BiSCF displays high oxygen permeability comparable to that of BSCF and much higher stability under CO 2 . The combination of high oxide transport properties and CO 2 tolerance in a single-phase MIEC gives BiSCF a significant advantage over existing MIECs for practical applications., (© 2019 The Authors. Published by WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.)

With the goal of finding new lithium solid electrolytes by a combined computational-experimental method, the exploration of the Li-Al-O-S phase field resulted in the discovery of a new sulfide Li 3 AlS 3 . The structure of the new phase was determined through an approach combining synchrotron X-ray and neutron diffraction with 6 Li and 27 Al magic-angle spinning nuclear magnetic resonance spectroscopy and revealed to be a highly ordered cationic polyhedral network within a sulfide anion hcp -type sublattice. The originality of the structure relies on the presence of Al 2 S 6 repeating dimer units consisting of two edge-shared Al tetrahedra. We find that, in this structure type consisting of alternating tetrahedral layers with Li-only polyhedra layers, the formation of these dimers is constrained by the Al/S ratio of 1/3. Moreover, by comparing this structure to similar phases such as Li 5 AlS 4 and Li 4.4 Al 0.2 Ge 0.3 S 4 ((Al + Ge)/S = 1/4), we discovered that the AlS 4 dimers not only influence atomic displacements and Li polyhedral distortions but also determine the overall Li polyhedral arrangement within the hcp lattice, leading to the presence of highly ordered vacancies in both the tetrahedral and Li-only layer. AC impedance measurements revealed a low lithium mobility, which is strongly impacted by the presence of ordered vacancies. Finally, a composition-structure-property relationship understanding was developed to explain the extent of lithium mobility in this structure type., Competing Interests: The authors declare no competing financial interest., (Copyright © 2019 American Chemical Society.)

Background: Zollinger-Ellison syndrome (ZES) is a rare condition characterized by hypersecretion of gastrin by gastrinoma tumors leading to severe peptic ulcer disease with potential development of gastric carcinoid tumors. Herein, we report the clinical course of a 68-year-old patient with multiple endocrine neoplasia type 1 (MEN-1) who underwent several surgeries to ultimately undergo optimal tumor cytoreduction of locally advanced gastrinomas and symptomatic gastric carcinoids. The patient was subsequently maintained on octreotide long-acting release (LAR). This case report supports consideration for aggressive tumor cytoreduction and octreotide in similar patients with MEN-1-associated ZES for durable disease control and symptom management., Case Presentation: The patient is a 68-year-old male with multiple endocrine neoplasia type 1 (MEN-1), diagnosed in 1993 after presenting with recurrent renal calculi and hypercalcemia. Soon thereafter, he presented with symptoms and elevated gastrin levels suggestive of ZES prompting abdominal exploration with partial resection of the duodenum to remove gastrinoma tumor nodules. Within 4 years of the operation, he represented with intractable hypergastrinemia despite optimal medical management with peak gastrin levels exceeding 29,000 pg/mL, in 2006. In January 2007, the patient returned to the operating room for resection of regional peripancreatic and perigastric lymph nodes and enucleation of pancreatic body and tail gastrinoma tumors. Although his gastrin level decreased to 5000 pg/mL with resultant improvement of symptoms, in less than 2 years, he developed disease progression with obstructive symptomatology from enlarging gastric carcinoids and rising gastrin levels. In May of 2008, he underwent pancreaticoduodenectomy and near-total gastrectomy. Since June of 2008, the patient shows no demonstrable progression of disease and remains asymptomatic on LAR octreotide (30 mgs). Gastrin levels have been well controlled (range, 100-624 pg/mL; current 114 pg/mL)., Conclusion: Success of this procedure in our case report highlights the potential role for optimal tumor cytoreduction and LAR octreotide to control disease progression in a patient with MEN-I and Zollinger-Ellison syndrome with locally advanced gastrinoma and secondary large gastric carcinoids.