Defect-dependent colossal negative thermal expansion in UiO-66(Hf) metal-organic framework

Thermally-densified hafnium terephthalate UiO-66(Hf) is shown to exhibit the strongest isotropic negative thermal expansion (NTE) effect yet reported for a metal-organic framework (MOF). Incorporation of correlated vacancy defects within the framework affects both the extent of thermal densification and the magnitude of NTE observed in the densified product. We thus demonstrate that defect inclusion can be used to tune systematically the physical behaviour of a MOF.Comment: 8 pages, 4 figures, revise

Conformational modulation of sequence recognition in synthetic macromolecules

The different triplet sequences in high molecular weight aromatic copolyimides comprising pyromellitimide units ("I") flanked by either ether-ketone ("K") or ether-sulfone residues ("S") show different binding strengths for pyrene-based tweezer-molecules. Such molecules bind primarily to the diimide unit through complementary π-π-stacking and hydrogen bonding. However, as shown by the magnitudes of 1H NMR complexation shifts and tweezer-polymer binding constants, the triplet "SIS" binds tweezer-molecules more strongly than "KIS" which in turn bind such molecules more strongly than "KIK". Computational models for tweezer-polymer binding, together with single-crystal X-ray analyses of tweezer-complexes with macrocyclic ether-imides, reveal that the variations in binding strength between the different triplet sequences arise from the different conformational preferences of aromatic rings at diarylketone and diarylsulfone linkages. These preferences determine whether or not chain-folding and secondary π−π-stacking occurs between the arms of the tweezermolecule and the 4,4'-biphenylene units which flank the central diimide residue

Intelligent and adaptive tutoring for active learning and training environments

Active learning facilitated through interactive and adaptive learning environments differs substantially from traditional instructor-oriented, classroom-based teaching. We present a Web-based e-learning environment that integrates knowledge learning and skills training. How these tools are used most effectively is still an open question. We propose knowledge-level interaction and adaptive feedback and guidance as central features. We discuss these features and evaluate the effectiveness of this Web-based environment, focusing on different aspects of learning behaviour and tool usage. Motivation, acceptance of the approach, learning organisation and actual tool usage are aspects of behaviour that require different evaluation techniques to be used

'They're battle scars, I wear them well': A phenomenological exploration of young women's experiences of building resilience following adversity in adolescence

This is an Author's Accepted Manuscript of an article published in Journal of Youth Studies, 13(3), 273 - 290, 2010 [copyright Taylor & Francis], available online at: http://www.tandfonline.com/10.1080/13676260903520886.This phenomenological study explored young women's accounts of building resilience following chains of adverse life experiences in adolescence. Six participants were interviewed, aged 20–25 years. Most had, or were receiving, a university education. They described their recovery from adversity as starting with certain pivotal moments, followed by both short-term and longer-term strategies. Short-term strategies tended to offer respite from distress and emotional comfort, increased clarity about their experiences and social affirmation. Recovery involved gaining new perspectives on their adverse situation and recovering a positive self-image through three longer-term strategies. These involved making visible progress in their education, rebuilding relationships with family and friends, and participating in the ‘normalizing’ activities and developmental projects of adolescence. Participants believed that they were stronger and more compassionate although positive achievements co-existed with some regrets. Most perceived the adversity as catalyzing personal growth. These accounts of resilience revealed the complex psychosocial processes and resources available to some adolescents

Randomized trial comparing proactive, high-dose versus reactive, low-dose intravenous iron supplementation in hemodialysis (PIVOTAL) : Study design and baseline data

Background: Intravenous (IV) iron supplementation is a standard maintenance treatment for hemodialysis (HD) patients, but the optimum dosing regimen is unknown. Methods: PIVOTAL (Proactive IV irOn Therapy in hemodiALysis patients) is a multicenter, open-label, blinded endpoint, randomized controlled (PROBE) trial. Incident HD adults with a serum ferritin 700 μg/L and/or TSAT ≥40%) or a reactive, low-dose IV iron arm (iron sucrose administered if ferritin <200 μg/L or TSAT < 20%). We hypothesized that proactive, high-dose IV iron would be noninferior to reactive, low-dose IV iron for the primary outcome of first occurrence of nonfatal myocardial infarction (MI), nonfatal stroke, hospitalization for heart failure or death from any cause. If noninferiority is confirmed with a noninferiority limit of 1.25 for the hazard ratio of the proactive strategy relative to the reactive strategy, a test for superiority will be carried out. Secondary outcomes include infection-related endpoints, ESA dose requirements, and quality-of-life measures. As an event-driven trial, the study will continue until at least 631 primary outcome events have accrued, but the expected duration of follow-up is 2-4 years. Results: Of the 2,589 patients screened across 50 UK sites, 2,141 (83%) were randomized. At baseline, 65.3% were male, the median age was 65 years, and 79% were white. According to eligibility criteria, all patients were on ESA at screening. Prior stroke and MI were present in 8 and 9% of the cohort, respectively, and 44% of patients had diabetes at baseline. Baseline data for the randomized cohort were generally concordant with recent data from the UK Renal Registry. Conclusions: PIVOTAL will provide important information about the optimum dosing of IV iron in HD patients representative of usual clinical practice. Trial Registration: EudraCT number: 2013-002267-25.Peer reviewedFinal Published versio

Dust-Gas Scaling Relations and OH Abundance in the Galactic ISM

Observations of interstellar dust are often used as a proxy for total gas column density $N_\mathrm{H}$. By comparing $\textit{Planck}$ thermal dust data (Release 1.2) and new dust reddening maps from Pan-STARRS 1 and 2MASS (Green et al. 2018), with accurate (opacity-corrected) HI column densities and newly-published OH data from the Arecibo Millennium survey and 21-SPONGE, we confirm linear correlations between dust optical depth $\tau_{353}$, reddening $E(B{-}V)$ and the total proton column density $N_\mathrm{H}$ in the range (1$-$30)$\times$10$^{20}$cm$^{-2}$, along sightlines with no molecular gas detections in emission. We derive an $N_\mathrm{H}$/$E(B{-}V)$ ratio of (9.4$\pm$1.6)$\times$10$^{21}$cm$^{-2}$mag$^{-1}$ for purely atomic sightlines at $|b|$$>$5$^{\circ}$, which is 60$\%$ higher than the canonical value of Bohlin et al. (1978). We report a $\sim$40$\%$ increase in opacity $\sigma_{353}$=$\tau_{353}$/$N_\mathrm{H}$, when moving from the low column density ($N_\mathrm{H}$$<$5$\times$10$^{20}$cm$^{-2}$) to moderate column density ($N_\mathrm{H}$$>$5$\times$10$^{20}$cm$^{-2}$) regime, and suggest that this rise is due to the evolution of dust grains in the atomic ISM. Failure to account for HI opacity can cause an additional apparent rise in $\sigma_{353}$, of the order of a further $\sim$20$\%$. We estimate molecular hydrogen column densities $N_{\mathrm{H}_{2}}$ from our derived linear relations, and hence derive the OH/H$_2$ abundance ratio of $X_\mathrm{OH}$$\sim$1$\times$10$^{-7}$ for all molecular sightlines. Our results show no evidence of systematic trends in OH abundance with $N_{\mathrm{H}_{2}}$ in the range $N_{\mathrm{H}_{2}}$$\sim$(0.1$-$10)$\times$10$^{21}$cm$^{-2}$. This suggests that OH may be used as a reliable proxy for H$_2$ in this range, which includes sightlines with both CO-dark and CO-bright gas.Comment: The revised manuscript is accepted for publication in The Astrophysical Journa

On the Origin of Reversible and Irreversible Reactions in LiNix_{x}Co(1−x)/2_{(1-x)/2}Mn(1−x)/2_{(1-x)/2}O2_{2}

Bond formation and breakage is crucial upon energy storage in lithium transition metal oxides (LiMeO$_{2}$, Me = Ni, Co, Mn), i.e., the conventional cathode materials in Li ion batteries. Near-edge X-ray absorption finestructure spectroscopy (NEXAFS) of the Me L and O K edge performed upon the first discharge of LiNi$_{x}$Co$_{(1-x)/2}$Mn$_{(1-x)/2}$O$_{2}$ (x = 0.33: NCM111, x = 0.6: NCM622, x = 0.8: NCM811) in combination with charge transfer multiplet (CTM) calculations provide unambiguous evidence that redox reactions in NCMs proceed via a reversible oxidation of Ni associated with the formation of covalent bonds to O neighbors, and not, as widely assumed, via pure cationic or more recently discussed, pure anionic redox processes. Correlating these electronic changes with crystallographic data using operando synchrotron X-ray powder diffraction (SXPD) shows that the amount of ionic Ni limits the reversible capacity— at states of charge where all ionic Ni is oxidized (above 155 mAh g$^{-1}$), the lattice parameters collapse, and irreversible reactions are observed. Yet the covalence of the Ni–O bonds also triggers the electronic structure and thus the operation potential of the cathodes

Ammonia decomposition catalysis using lithium–calcium imide

Lithium–calcium imide is explored as a catalyst for the decomposition of ammonia. It shows the highest ammonia decomposition activity yet reported for a pure light metal amide or imide, comparable to lithium imide–amide at high temperature, with superior conversion observed at lower temperatures. Importantly, the post-reaction mass recovery of lithium–calcium imide is almost complete, indicating that it may be easier to contain than the other amide–imide catalysts reported to date. The basis of this improved recovery is that the catalyst is, at least partially, solid across the temperature range studied under ammonia flow. However, lithium–calcium imide itself is only stable at low and high temperatures under ammonia, with in situ powder diffraction showing the decomposition of the catalyst to lithium amide–imide and calcium imide at intermediate temperatures of 200–460 °C.</p

Cation Ordering and Exsolution in Copper-Containing Forms of the Flexible Zeolite Rho (Cu,M-Rho; M=H, Na) and Their Consequences for CO₂ Adsorption

Funding: UK Engineering and Physical Sciences Research Council. Grant Numbers: EP/N024613/1, EP/N032942/1, EP/L017008/1.The flexibility of the zeolite Rho framework offers great potential for tunable molecular sieving. The fully copper-exchanged form of Rho and mixed Cu,H- and Cu,Na-forms have been prepared. EPR spectroscopy reveals that Cu2+ ions are present in the dehydrated forms and Rietveld refinement shows these prefer S6R sites, away from the d8r windows that control diffusion. Fully exchanged Cu-Rho remains in an open form upon dehydration, the d8r windows remain nearly circular and the occupancy of window sites is low, so that it adsorbs CO2 rapidly at room temperature. Breakthrough tests with 10 % CO2/40 % CH4 mixtures show that Cu4.9-Rho is able to produce pure methane, albeit with a relatively low capacity at this pCO2 due to the weak interaction of CO2 with Cu cations. This is in strong contrast to Na-Rho, where cations in narrow elliptical window sites enable CO2 to be adsorbed with high selectivity and uptake but too slowly to enable the production of pure methane in similar breakthrough experiments. A series of Cu,Na-Rho materials was prepared to improve uptake and selectivity compared to Cu-Rho, and kinetics compared to Na-Rho. Remarkably, Cu,Na-Rho with >2 Cu cations per unit cell exhibited exsolution, due to the preference of Na cations for narrow S8R sites in distorted Rho and of Cu cations for S6R sites in the centric, open form of Rho. The exsolved Cu,Na-Rho showed improved performance in CO2/CH4 breakthrough tests, producing pure CH4 with improved uptake and CO2/CH4 selectivity compared to that of Cu4.9-Rho.Publisher PDFPeer reviewe